WO2000010705A1 - Procede fischer-tropsch a base de catalyseurs en xerogel et aerogel - Google Patents

Procede fischer-tropsch a base de catalyseurs en xerogel et aerogel Download PDF

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WO2000010705A1
WO2000010705A1 PCT/US1999/018962 US9918962W WO0010705A1 WO 2000010705 A1 WO2000010705 A1 WO 2000010705A1 US 9918962 W US9918962 W US 9918962W WO 0010705 A1 WO0010705 A1 WO 0010705A1
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catalyst
metal
cobalt
group
mole percent
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Leo E. Manzer
Konstantinos Kourtakis
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ConocoPhillips Co
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Conoco Inc
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Priority claimed from US09/377,008 external-priority patent/US6235677B1/en
Priority claimed from US09/376,873 external-priority patent/US6319872B1/en
Application filed by Conoco Inc filed Critical Conoco Inc
Priority to AU55751/99A priority Critical patent/AU5575199A/en
Publication of WO2000010705A1 publication Critical patent/WO2000010705A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/8913—Cobalt and 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts

Definitions

  • the present invention relates to a process for the preparation of hydrocarbons from synthesis gas, (i.e., a mixture of carbon monoxide and hydrogen), typically labeled the Fischer-Tropsch process.
  • this invention relates to catalysts containing a xerogel or aerogel matrix, containing titanium oxide, zirconium oxide or tantalum oxide, for the Fischer-Tropsch process.
  • methane the main component of natural gas, are available in many areas of the world.
  • Methane can be used as a starting material for the production of hydrocarbons.
  • the conversion of methane to hydrocarbons is typically carried out in two steps. In the first step methane is reformed with water or partially oxidized with oxygen to produce carbon monoxide and hydrogen
  • syngas (i.e., synthesis gas or syngas).
  • syngas is converted to hydrocarbons.
  • hydrocarbons from synthesis gas is well known in the art and is usually referred to as Fischer-Tropsch synthesis, the Fischer-Tropsch process, or Fischer-Tropsch reaction(s).
  • Catalysts for use in such synthesis usually contain a catalytically active Group VHI (CAS) metal.
  • CAS catalytically active Group VHI
  • iron, cobalt, nickel, and ruthenium have been abundantly used as the catalytically active metals.
  • Cobalt and ruthenium have been found to be most suitable for catalyzing a process in which synthesis gas is converted to primarily hydrocarbons having five or more carbon atoms (i.e., where the C5 + selectivity of the catalyst is high).
  • the catalysts often contain one or more promoters and a support or carrier material. Rhenium is a widely used promoter.
  • the Fischer-Tropsch reaction involves the catalytic hydrogenation of carbon monoxide to produce a variety of products ranging from methane to higher aliphatic alcohols. The methanation reaction was first described in the early 1900's, and the later work by Fischer and Tropsch dealing with higher hydrocarbon synthesis was described in the 1920's.
  • the Fischer-Tropsch synthesis reactions are highly exothermic and reaction vessels must be designed for adequate heat exchange capacity. Because the feed streams to Fischer-Tropsch reaction vessels are gases while the product streams include liquids, the reaction vessels must have the ability to continuously produce and remove the desired range of liquid hydrocarbon products.
  • the process has been considered for the conversion of carbonaceous feedstock, e.g., coal or natural gas, to higher value liquid fuel or petrochemicals.
  • the first major commercial use of the Fischer-Tropsch process was in Germany during the 1930's. More than 10,000 B/D (barrels per day) of products were manufactured with a cobalt based catalyst in a fixed-bed reactor. This work has been described by Fischer and Pichler in Ger. Pat. No. 731,295 issued Aug. 2, 1936.
  • Catalyst supports for catalysts used in Fischer-Tropsch synthesis of hydrocarbons have typically been oxides (e.g., silica, alumina, titania, zirconia or mixtures thereof, such as silica- alumina). It has been claimed that the Fischer-Tropsch synthesis reaction is only weakly dependent on the chemical identity of the metal oxide support (see E. Iglesia et al. 1993, In: "Computer-Aided Design of Catalysts," ed. E. R. Becker et al., p. 215, New York, Marcel Dekker, Inc.). The products prepared by using these catalysts usually have a very wide range of molecular weights.
  • oxides e.g., silica, alumina, titania, zirconia or mixtures thereof, such as silica- alumina.
  • U.S. Pat. No. 4,477,595 discloses ruthenium on titania as a hydrocarbon synthesis catalyst for the production of C 5 to C 40 hydrocarbons, with a majority of paraffins in the C 5 to C 20 range.
  • Pat. No. 4,542,122 discloses a cobalt or cobalt-thoria on titania having a preferred ratio of rutile to anatase, as a hydrocarbon synthesis catalyst.
  • U.S. Pat. No. 4,088,671 discloses a cobalt-ruthenium catalyst where the support can be titania but preferably is alumina for economic reasons.
  • U.S. Pat. No. 4,413,064 discloses an alumina supported catalyst having cobalt, ruthenium and a Group IIIA or Group IVB metal oxide, e.g., thoria.
  • European Patent No. 142,887 discloses a silica supported cobalt catalyst together with zirconium, titanium, ruthenium and/or chromium.
  • U.S. Pat. No. 4,801,573 discloses a promoted cobalt and rhenium catalyst, preferably supported on alumina that is characterized by low acidity, high surface area, and high purity, which properties are said to be necessary for high activity, low deactivation, and high molecular weight products.
  • the amount of cobalt is most preferably about 10 to 40 wt % of the catalyst.
  • the content of rhenium is most preferably about 2 to 20 wt % of the cobalt content.
  • Related U.S. Pat. No. 4,857,559 discloses a catalyst most preferably having 10 to 45 wt % cobalt and a rhenium content of about 2 to 20 wt % of the cobalt content.
  • U.S. Pat. No. 5,545,674 discloses a cobalt-based catalyst wherein the active metal is dispersed as a very thin film on the surface of a particulate support, preferably silica or titania or a titania-containing support.
  • the catalyst may be prepared by spray techniques.
  • U.S. Pat. No. 5,028,634 discloses supported cobalt-based catalysts, preferably supported on high surface area aluminas.
  • High surface area supports are said to be preferred because greater cobalt dispersion can be achieved as cobalt is added, with less tendency for one crystal of cobalt to fall on another crystal of cobalt.
  • the cobalt loading on a titania support is preferably 10 to 25 wt %, while the preferred cobalt loading on an alumina support is 5 to 45 wt %.
  • U.S. Pat. No. 5,302,622 discloses a supported cobalt and ruthenium based catalyst including other components and preferably prepared by a gelling procedure to incorporate the catalyst components in an alcogel formed from a hydrolyzable compound of silicon, and/or aluminum, and optional compounds.
  • the cobalt content after calcination is preferably between 14 and 40 wt % of the catalyst.
  • UK Patent Application GB 2,258,414A discloses a supported catalyst containing cobalt, molybdenum and/or tungsten, and an additional element.
  • the support is preferably one or more oxides of the elements Si, Al, Ti, Zr, Sn, Zn, Mg, and elements with atomic numbers from 57 to 71.
  • the preferred cobalt content is from 5 to 40 wt % of the catalyst.
  • a preferred method of preparation of the catalyst includes the preparation of a gel containing the cobalt and other elements.
  • This invention provides a process and catalyst for producing hydrocarbons, and a method for preparing the catalyst.
  • the process comprises contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising hydrocarbons.
  • the catalyst used in the process comprises an aerogel or xerogel matrix comprising a matrix metal selected from the group consisting of titanium, tantalum, zirconium, aluminum, and combinations thereof, and one or more catalytically active metals selected from the group consisting of iron, cobalt, nickel, and ruthenium dispersed in the matrix.
  • This invention also provides a catalyst comprising the dried reaction product of a first reagent comprising an alkoxide of a metal selected from the group consisting of titanium, tantalum, zirconium, and combinations thereof in a non-aqueous solvent, and a second reagent comprising a solution comprising one or more catalytically active metals selected from the group consisting of iron, cobalt, nickel, and ruthenium, wherein the product is an aerogel or xerogel.
  • a first reagent comprising an alkoxide of a metal selected from the group consisting of titanium, tantalum, zirconium, and combinations thereof in a non-aqueous solvent
  • a second reagent comprising a solution comprising one or more catalytically active metals selected from the group consisting of iron, cobalt, nickel, and ruthenium, wherein the product is an aerogel or xerogel.
  • This invention also provides a Fischer-Tropsch catalyst comprising an aerogel or xerogel formed from the hydrolysis and condensation reaction of a solution of a catalytically active metal selected from the group consisting of iron, cobalt, nickel, ruthenium, and combinations thereof and a matrix reagent comprising a non-aqueous solution of a metal selected from the group consisting of titanium, tantalum, zirconium, and combinations thereof.
  • a Fischer-Tropsch catalyst comprising an aerogel or xerogel formed from the hydrolysis and condensation reaction of a solution of a catalytically active metal selected from the group consisting of iron, cobalt, nickel, ruthenium, and combinations thereof and a matrix reagent comprising a non-aqueous solution of a metal selected from the group consisting of titanium, tantalum, zirconium, and combinations thereof.
  • This invention also includes a method for the preparation of a Fischer-Tropsch catalyst comprising mixing a non-aqueous solution of an alkoxide of a metal selected from the group consisting of titanium, tantalum, zirconium, and combinations thereof with one or more catalytically active metals selected from the group consisting of iron, cobalt, nickel, and ruthenium in a solvent, forming a gel, and drying the aged gel.
  • This invention provides a process for producing hydrocarbons, comprising contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising hydrocarbons, wherein the catalyst comprises a catalytically active metal selected from the group consisting of iron, cobalt, nickel, ruthenium, and combinations thereof dispersed in an aerogel or xerogel comprising a derivative of the hydrolysis and condensation of one or more alkoxides of a matrix metal selected from the group consisting of titanium, tantalum, zirconium, and combinations thereof and, optionally, aluminum.
  • a catalytically active metal selected from the group consisting of iron, cobalt, nickel, ruthenium, and combinations thereof dispersed in an aerogel or xerogel comprising a derivative of the hydrolysis and condensation of one or more alkoxides of a matrix metal selected from the group consisting of titanium, tantalum, zirconium, and combinations thereof and,
  • This invention also provides a process characterized by using a catalyst prepared by a method comprising (1) forming a catalyst gel by mixing (a) at least one dissolved compound of a catalytic metal for Fischer-Tropsch reactions (e.g., at least one compound of a metal selected from the group consisting of iron, cobalt, nickel and ruthenium dissolved in water and/or ethanol); (b) (i) at least one dissolved alkoxide of a metal selected from the group consisting of titanium, zirconium and tantalum and optionally (ii) at least one dissolved aluminum compound, said alkoxide component (i) and said optional aluminum compound component (ii) being dissolved in a non-aqueous solvent (e.g., ethanol); and at least when necessary to hydrolyze the alkoxide component (i) and aluminum compound component (ii), (c) an aqueous supplement (e.g., water, aqueous acid or aqueous base); and (2) drying the gel.
  • the feed gases charged to the process of the invention comprise hydrogen, or a hydrogen source, and carbon monoxide.
  • H ,/CO mixtures suitable as a feedstock for conversion to hydrocarbons according to the process of this invention can be obtained from light hydrocarbons such as methane by means of steam reforming, partial oxidation, or other processes known in the art.
  • the hydrogen is preferably provided by free hydrogen, although some Fischer-Tropsch catalysts have sufficient water gas shift activity to convert some water to hydrogen for use in the Fischer-Tropsch process. It is preferred that the molar ratio of hydrogen to carbon monoxide in the feed be greater than 0.5:1 (e.g., from about 0.67 to 2.5).
  • the feed gas stream preferably contains hydrogen and carbon monoxide in a molar ratio of about 2:1.
  • the feed gas stream preferably contains hydrogen and carbon monoxide in a molar ratio of about 0.67:1.
  • the feed gas may also contain carbon dioxide.
  • the feed gas stream should contain a low concentration of compounds or elements that have a deleterious effect on the catalyst, such as poisons.
  • the feed gas may need to be pre-treated to ensure that it contains low concentrations of sulfur or nitrogen compounds, such as hydrogen sulfide, ammonia and carbonyi sulfides.
  • the feed gas is contacted with the catalyst in a reaction zone.
  • Mechanical arrangements of conventional design may be employed as the reaction zone including, for example, fixed bed, fluidized bed, slurry phase, slurry bubble column or ebullating bed reactors, among others, may be used. Accordingly, the size and physical form of the catalyst particles may vary depending on the reactor in which they are to be used.
  • a component of the catalysts used in this invention is the matrix material, which is essentially derived from solution (b) and which incorporates the active catalyst component, which is derived from dissolved component (a).
  • a matrix is a skeletal framework of oxides and oxyhydroxides derived from the hydrolysis and condensation of alkoxides and other reagents. The framework typically comprises 30% or more, by weight, of the total catalyst composition.
  • the matrix material comprises tantalum, titanium, or zirconium, and optionally aluminum oxide/hydroxide, xerogels or aerogels or mixtures thereof totaling from 99.9 to 30 mole %, preferably from 65 to 85 mole % of the catalyst composition.
  • Various compounds can be used as precursors to the aluminum oxides/hydroxides, including by way of illustration and not limitation, aluminum: nitrates, acetates, alkoxides, acetylacetonates, and chlorides.
  • Combinations where the matrix metal is Ti, combinations where the matrix metal is a combination of Ti and Al, and combinations where the matrix metal is Zr are typical.
  • Preferred combinations include combinations where the matrix metal is a combination of Ti and Al, where the atomic ratio Ti:Al is between about 1:9 and about 9:1.
  • Also preferred are combinations including Al where the atomic ratio of Al to the total of Ta, Ti and Zr is about 1.01:1.
  • a gel may be described as a coherent, rigid three-dimensional polymeric network.
  • the present gels are formed in a liquid medium, usually water, alcohol, or a mixture thereof.
  • the term "alcogel” describes gels in which the pores are filled with predominantly alcohol. Gels whose pores are filled primarily with water may be referred to as aquagels or hydrogels.
  • a "xerogel” is a gel from which the liquid medium has been removed and replaced by a gas.
  • the structure is compressed and the porosity reduced significantly by the surface tension forces that occur as the liquid is removed.
  • surface tension creates concave menisci in the gel's pores.
  • the menisci retreat into the gel body, compressive forces build up around its perimeter, and the perimeter contracts, drawing the gel body inward.
  • surface tension causes significant collapse of the gel body and a reduction of volume, often as much as two- thirds or more of the original volume. This shrinkage causes a significant reduction in the porosity, often as much as 90 to 95 percent depending on the system and pore sizes.
  • an "aerogel” is a gel from which the liquid has been removed in such a way as to prevent significant collapse or change in the structure as liquid is removed. This is typically accomplished by heating the liquid-filled gel in an autoclave while maintaining the prevailing pressure above the vapor pressure of the liquid until the critical temperature of the liquid has been exceeded, and then gradually releasing the vapor, usually by gradually reducing the pressure either incrementally or continuously, while maintaining the temperature above the critical temperature.
  • the critical temperature is the temperature above which it is impossible to liquefy a gas, regardless of how much pressure is applied. At temperatures above the critical temperature, the distinction between liquid and gas phases disappears and so do the physical manifestations of the gas/liquid interface.
  • Aerogels produced by supercritical drying typically have high porosities, on the order of from 50 to 99 percent by volume.
  • one or more metal alkoxides may be used as starting material for preparing the gels.
  • the inorganic metal alkoxides used in this invention may include any alkoxide that contains from 1 to 20 carbon atoms and preferably contains 1 to 5 carbon atoms in the alkoxide group, and is preferably are soluble in the liquid reaction medium.
  • C1-C4 alkoxides such as tantalum n-butoxide, titanium isopropoxide and zirconium isopropoxide are preferred.
  • Commercially available alkoxides can be used. However, inorganic alkoxides can be prepared by other routes.
  • Examples include alkoxides prepared by the direct reaction of zero valent metals with alcohols in the presence of a catalyst. Many alkoxides can be formed by reaction of metal halides with alcohols. Alkoxy derivatives can be synthesized by the reaction of the alkoxide with alcohol in a ligand interchange reaction. Direct reactions of metal dialkylamides with alcohol also form alkoxide derivatives. Additional examples are disclosed in "Metal Alkoxides" by D.C. Bradley et al., Academic Press, (1978), which is incorporated herein by reference in its entirety.
  • the first step in the synthesis of the gels containing alcohol, or alcogels consists of preparing non-aqueous solutions of the alkoxides and other reagents, and separate solutions containing protic solvents such as water. When the alkoxide solutions are mixed with the solutions containing the protic solvents, the alkoxides will react and polymerize to form a gel.
  • the medium utilized in the process generally is preferably a solvent for both the inorganic alkoxide or alkoxides that are used and the additional metal reagents and promoters that are added in the single step synthesis. Solubility of all of the components in their respective media (aqueous and non-aqueous) is preferred to produce highly dispersed materials.
  • soluble reagents By employing soluble reagents in this manner, mixing and dispersion of the active metals and promoter reagents can be near atomic, mirroring their dispersion in their respective solutions.
  • the gel thus produced by this process will therefore contain highly dispersed active metals and promoters. High dispersion results in catalyst metal particles in the nanometer size range, and highly efficient use of the catalytically active components.
  • Preferred embodiments include those wherein the catalytic metal of (a) is dissolved in a separate protic solvent (e.g., water) and this solution of catalytic metal compound(s) is mixed with the non-aqueous solution of (b).
  • the catalytic metal is dissolved in the same non-aqueous solution as components (i) and (ii), and aqueous supplement (c) is used.
  • concentration of the solvent used is linked to the alkoxide content.
  • a molar ratio of 26.5:1 ethanol:total alkoxide can be used, although the molar ratio of ethanoktotal alkoxide can be from about 5:1 to 53:1, or even greater. If a large excess of alcohol is used, gelation will not generally occur immediately; some solvent evaporation will be needed. At lower solvent concentrations, it is thought that a heavier gel will be formed, having less pore volume and surface area.
  • water and any aqueous solutions are added in a dropwise fashion to the alcohol soluble alkoxide and other reagents to induce hydrolysis and condensation reaction.
  • a discernible gel point can be reached in minutes or hours.
  • the molar ratio of the total water added to the total Ti, Zr, Ta, and Al added varies according to the specific inorganic alkoxide being reacted.
  • a molar ratio of wate ⁇ alkoxide from about of 0.1 :1 to 10:1 is used.
  • ratios close to 5:1 for tantalum(alkoxide)5 and 4:1 for zirconium(alkoxide)4 and titanium(alkoxides)4 can be used.
  • the amount of water utilized in the reaction is that calculated to hydro lyze the inorganic alkoxide in the reaction mixture.
  • a ratio lower than that needed to hydrolyze the alkoxide species will result in a partially hydrolyzed material, which in most cases will reach a gel point at a much slower rate, depending on the aging procedure and the presence of atmospheric moisture.
  • the addition of acidic or basic reagents to the inorganic alkoxide medium can have an effect on the kinetics of the hydrolysis and condensation reactions, and the microstructure of the oxide/hydroxide matrices derived from the alkoxide precursor which entraps or incorporates the soluble metal and promoter reagents.
  • a pH within the range of from 1 to 12 can be used, with a pH range of from 1 to 6 being preferred.
  • Removal of solvent from the alcogels can be accomplished by several methods. Removal by vacuum drying or heating in air results in the formation of a xerogel.
  • An aerogel of the material can typically be formed by charging in a pressurized system such as an autoclave.
  • the solvent-containing gel that is formed in the practice of this invention is placed in an autoclave, where it can be contacted with a fluid above its critical temperature and pressure by allowing the supercritical fluid to flow through the gel material until the solvent is no longer being extracted by the supercritical fluid.
  • various supercritical fluids can be utilized at their critical temperature and pressure.
  • fluorochlorocarbons typified by Freon® fluorochloromethanes (e.g., Freon® 11 (CC1 3 F), 12 (CC1 2 F 2 ) or 114 (CC1F 2 CC1F 2 ), ammonia and carbon dioxide are all suitable for this process.
  • the extraction fluids are gases at atmospheric conditions, so that pore collapse due to the capillary forces at the liquid/solid interface is avoided during drying.
  • the resulting material will, in most cases, possess a higher surface area than the non-supercritically dried materials.
  • the xerogels and aerogels thus produced can be described as precursor salts dispersed in an oxide or oxyhydroxide matrix.
  • the hydroxyl content is at this point undefined; a theoretical maximum corresponds to the valence of central metal atom.
  • Ta 2 (0 2 . x (OH) x )5 possesses a theoretical hydroxyl maximum when x is 2.
  • the molar H 2 0:alkoxide ratio can also impact the final xerogel stoichiometry; in this case, if H 2 0:Ta is less than 5, there will be residual -OR groups in the unaged gel.
  • reaction with atmospheric moisture will convert these to the corresponding -OH, and -O groups upon continued polymerization and dehydration. Aging, even under inert conditions, can also effect the condensation of the -OH, eliminating H 2 0, through continuation of cross-linking and polymerization, i.e., gel formation.
  • the catalytic metal is preferably selected from iron, cobalt, nickel and/or ruthenium. Normally, the catalytic metal component of the matrix is reduced to provide elemental metal (e.g., elemental iron, cobalt, nickel and/or ruthenium) before use.
  • the catalyst must contain a catalytically effective amount of the metal component(s). The amount of catalytic metal present in the catalyst may vary widely. Typically, the catalyst comprises from about 0.1 to 50 mole % (as the metal) of total supported iron, cobalt, nickel and/or ruthenium per total moles of catalytic metal and matrix metal, and preferably from about 10 to 30 mole %.
  • each of the catalytic metals can be used individually. Combinations, especially combinations of cobalt and ruthenium, can also be used. Preferred are catalysts comprising from about 2.5 to about 50 mole percent of a combination of cobalt and ruthenium where the ruthenium content is from about 0.001 to about 5 mole percent. Preferred matrix materials for these combinations include titanium and a combination of titanium and aluminum (e.g., a combination of titanium and aluminum having a Ti:Al atomic ratio between about 1 :9 and about 9: 1). Optionally, the catalyst of the present invention may also comprise one or more additional promoters or modifiers known to those skilled in the art.
  • suitable promoters include at least one metal selected from the group consisting of Group IA (CAS) metals (i.e., Na, K, Rb, Cs), Group HA metals (i.e., Mg, Ca, Sr, Ba), Group IB metals (i.e., Cu, Ag, and Au) Group HIB metals (i.e., Sc, Y and La), Group IVB metals (i.e., Ti, Zr and Hf), Group VB metals (i.e., V, Nb and Ta), and Rh, Pd, Os, Ir, PtMn, B, P, and Re.
  • CAS Group IA
  • CAS Group IA
  • Group HA metals i.e., Mg, Ca, Sr, Ba
  • Group IB metals i.e., Cu, Ag, and Au
  • Group HIB metals i.e., Sc, Y and La
  • Group IVB metals i.e., Ti, Zr and Hf
  • any additional promoters for the cobalt and/or ruthenium are selected from Sc, Y, La, Ti, Zr, Hf, Rh, Pd, Os, Ir, Pt, Re, Nb, Cu, Ag, Mn, B, P, and Ta.
  • any additional promoters for the iron catalysts are selected from Na, K, Rb, Cs, Mg, Ca, Sr, and Ba.
  • the amount of additional promoter, if present, is typically between 0.001 and 20 mole %, preferably from 2 to 5 mole %.
  • catalysts comprising from about 10 to 25 mole percent of a combination of cobalt and rhenium where the rhenium content is from about 0.001 to 10 mole percent; and catalysts comprising from about 10 to 25 mole percent of cobalt and both rhenium and ruthenium where the rhenium and ruthenium together total about 0.001 to about 10 mole percent.
  • Preferred matrix materials for these combinations include titanium and a combination of titanium and aluminum, for example, a combination of titanium and aluminum having a Ti:Al atomic ratio between about 1 :9 and about 9: 1.
  • the most preferred method of preparation may vary among those skilled in the art, depending for example on the desired catalyst particle size. Those skilled in the art are able to select the most suitable method for a given set of requirements.
  • the metal(s) of the catalytic metal component (a) of the catalysts of the present invention is present in a reduced state (i.e., in the metallic state). Therefore, it is normally advantageous to activate the catalyst prior to use by a reduction treatment, in the presence of hydrogen at an elevated temperature.
  • the catalyst is treated with hydrogen at a temperature in the range of from about 75°C to about 500°C, for about 0.5 to about 24 hours at a pressure of about 1 to about 75 atm. Pure hydrogen may be used in the reduction treatment, as well as a mixture of hydrogen and an inert gas such as nitrogen.
  • the amount of hydrogen may range from about 1% to about 100% by volume.
  • the Fischer-Tropsch process is typically run in a continuous mode.
  • the gas hourly space velocity through the reaction zone typically may range from about 100 volumes/hour/volume catalyst (v/hr/v) to about 10,000 v/hr/v, preferably from about 300 v/hr/v to about 2,000 v/hr/v.
  • the reaction zone temperature is typically in the range from about 160°C to about 300°C.
  • the reaction zone is operated at conversion promoting conditions at temperatures from about 190°C to about 260°C.
  • the reaction zone pressure is typically in the range of about 80 psig (653 kPa) to about 1000 psig (6994 kPa), preferably, from 80 psig (653 kPa) to about 600 psig (4237 kPa), and still more preferably, from about 140 psig (1066 kPa) to about 400 psig (2858 kPa).
  • the products resulting from the process will have a great range of molecular weights.
  • the carbon number range of the product hydrocarbons will start at methane and continue to the limits observable by modern analysis, about 50 to 100 carbons per molecule.
  • the process is particularly useful for making hydrocarbons having five or more carbon atoms, especially when the above-referenced preferred space velocity, temperature and pressure ranges are employed.
  • the wide range of hydrocarbons produced in the reaction zone will typically afford liquid phase products at the reaction zone operating conditions. Therefore the effluent stream of the reaction zone will often be a mixed phase stream including liquid and vapor phase products.
  • the effluent stream of the reaction zone may be cooled to effect the condensation of additional amounts of hydrocarbons and passed into a vapor-liquid separation zone separating the liquid and vapor phase products.
  • the vapor phase material may be passed into a second stage of cooling for recovery of additional hydrocarbons.
  • the liquid phase material from the initial vapor-liquid separation zone, together with any liquid from a subsequent separation zone, may be fed into a fractionation column.
  • a stripping column is employed first to remove light hydrocarbons such as propane and butane.
  • the remaining hydrocarbons may be passed into a fractionation column where they are separated by boiling point range into products such as naphtha, kerosene and fuel oils.
  • Hydrocarbons recovered from the reaction zone and having a boiling point above that of the desired products may be passed into conventional processing equipment such as a hydrocracking zone in order to reduce their molecular weight.
  • the gas phase recovered from the reactor zone effluent stream after hydrocarbon recovery may be partially recycled if it contains a sufficient quantity of hydrogen and/or carbon monoxide.
  • a 2 mL pressure vessel was heated at either 200°C or 225°C under 1000 psig (6994 kPa) of H 2 :CO (2:1) and maintained at that temperature and pressure for 1 hour when heated at 225°C or for
  • a C ⁇ j + Productivity (g C ⁇ ⁇ + /hour/kg catalyst) was calculated based on the integrated production of the Cj 1-C40 hydrocarbons per kg of catalyst per hour.
  • the logarithm of the weight fraction for each carbon number ln(W n /n) was plotted as the ordinate vs. number of carbon atoms in (W n /n) as the abscissa. From the slope, a value of alpha was obtained.
  • Some runs displayed a double alpha as shown in the tables.
  • the results of runs over a variety of catalysts at 225°C are shown in Table 1 and at 200°C are shown in Table 2.
  • Example 2 The same procedure and solutions were used as described in Example 1, adjusting the volumetric addition for the desired stoichiometries: ruthenium (III) chloride, 8.134 mL; titanium n-butoxide solution, 18.148 mL; ethanol, 41.42 mL; and nickel (II) chloride solution, 4.681 mL A dark alcogel formed within minutes of addition of the aqueous solution.
  • the final xerogel had a nominal composition of Ru (0.025)/Ni (0.125)/Ti (0.85).
  • Example 2 The same procedure and solutions were used as described in Example 1, adjusting the volumetric addition for the desired stoichiometries: ruthenium (III) chloride, 14.575 mL; titanium n-butoxide solution, 16.259 mL; ethanol, 37.108 mL; and nickel (II) chloride solution, 3.355 mL. A dark alcogel formed within minutes of addition of the aqueous solution. The final xerogel had a nominal composition of Ru (0.05)/Ni (0.1)/Ti (0.85).
  • EXAMPLE 5 The same procedure and solutions were used as described in Example 1, adjusting the volumetric addition for the desired stoichiometries: ruthenium (III) chloride, 1.794 mL; 1.0 M cobalt(II)chloride hexahydrate in ethanol, 2.993 mL; titanium n-butoxide solution, 20.008 mL; ethanol, 42.671 mL; and nickel (II) chloride solution, 2.993 mL. A dark-brown, glassy alcogel formed within minutes of addition of the aqueous solution. The final xerogel had a nominal composition of Ru (0.005)/Co (0.0725)/Ni (0.0725)/Ti (0.85).
  • EXAMPLE 6 The same procedure and solutions were used as described in Example 1, adjusting the volumetric addition for the desired stoichiometries: ruthenium (III) chloride, 1.794 mL; 1.0 M cobalt(II)chloride hexa
  • Example 2 The same procedure and solutions were used as described in Example 1, adjusting the volumetric addition for the desired stoichiometries: ruthenium (III) chloride, 3.497 mL; 1.0 M cobalt(II)chloride hexahydrate in ethanol, 2.818 mL; titanium n-butoxide solution, 19.508 mL; ethanol, 41.706 mL; and nickel (II) chloride solution, 2.818 mL. A dark- brown glassy alcogel formed within minutes of addition of the aqueous solution. The final xerogel had a nominal composition of Ru (0.01)/Co (0.07)/Ni (0.07)/Ti (0.85).
  • EXAMPLE 9 The same procedure and solutions were used as described in Example 8, adjusting the volumetric addition for the desired stoichiometries: ruthenium (III) chloride, 5.637 mL; 0.2871 M HAUCI4 in ethanol, 3.249 mL; titanium n-butoxide solution, 19.674 mL; and ethanol, 39.265 mL. A brown alcogel formed. The final xerogel had a nominal composition of Ru (0.05)/Au (0.025)/Ti (0.925).
  • EXAMPLE 10 The same procedure and solutions were used as described in Example 7, adjusting the volumetric addition for the desired stoichiometries: ruthenium (III) chloride, 7.737 mL; cobalt(II) chloride, 1.0 M in ethanol, 10.241 mL; titanium n-butoxide solution, 21.894 mL; and ethanol, 31.993 mL. A clear, red alcogel formed within minutes of the addition of aqueous solution. The same procedures were followed in subsequent processing steps, as described in Example 1. The final xerogel had a nominal composition of Ru (0.05)/Co (0.02)/Ti (0.75). EXAMPLE 11
  • EXAMPLE 13 The same procedure and solutions were used as described in Example 11 , adjusting the volumetric addition for the desired stoichiometries: ruthenium (III) chloride, 17.325 mL; titanium n-butoxide solution, 15.452 mL; 1.0 M cobalt (II) chloride hexahydrate in water, 5.082 mL; water, 1.957 mL; and ethanol, 30.184 mL.
  • the alcogel formed within minutes; it was clear, and red-blue in color.
  • the final xerogel had a nominal composition of Ru (0.05)/Co (0.15)/Ti (0.8).
  • the final xerogel had a nominal composition of Ru (0.05)/Co (0.3)/Ti (0.65).
  • EXAMPLE 15 The same procedure and solutions were used as described in Example 13, adjusting the volumetric addition for the desired stoichiometries: ruthenium (III) chloride, 24.136 mL; titanium n-butoxide solution, 13.454 mL; 1.0 M cobalt (II) chloride hexahydrate in water, 21.238 mL; water, 1.704 mL; and ethanol, 9.468 mL. The alcogel formed within minutes; it was clear, and blue in color. The final xerogel had a nominal composition of Ru (0.05)/Co (0.45)/Ti (0.50). EXAMPLE 16
  • the gel was aged at room temperature for twelve days prior to removal of solvent by supercritical C0 2 .
  • the material was placed in a stirred autoclave and extracted in C0 2 under supercritical conditions. CO 2 gas was purged over the catalyst for 7 hours at 40°C and
  • the material isolated was a free flowing powder.
  • the final aerogel had a nominal composition of 5.7 wt. % Ru/23 wt. % Re/71.3 wt. % TiO 2 .
  • Titanium n-butoxide (194.01 g) was added to ethanol (435.84 mL) in an inert atmosphere drybox.
  • ruthenium (III) chloride (6.223 g) was combined with water (41.08 mL) along with 70% nitric acid (3.82 mL) and glacial acetic acid (4.892 mL).
  • Ethanol (435.84 mL) was added to this water-based solution.
  • the water-based solution was loaded into a dropping funnel.
  • the titanium n-butoxide solution was added to a 1.5 L resin kettle inside of the drybox. Under an inert nitrogen blanket, with gentle stirring, the water-based solution was added to the alkoxide/alcohol solution.
  • Zirconium (IV) isopropoxide (186.709 g) was added to ethanol (435.84 mL) in an inert atmosphere drybox.
  • ruthenium (III) chloride (6.223 g) was combined with water (41.08 mL) along with 70% nitric acid (3.82 mL) and glacial acetic acid (4.892 mL).
  • Ethanol (435.84 mL) was added to this aqueous-based solution.
  • the aqueous-based solution was loaded into a dropping funnel.
  • the alkoxide solution was added to a 1.5 L resin kettle inside of the drybox.
  • the aqueous solution was added to the alkoxide/alcohol solution. A gel point was reached within minutes. The material was dark brown in color. The material was aged for approximately 24 hours, and subsequently dried under vacuum at 110°C for 5 hours. The resultant xerogel was dark brown in color.
  • the final catalyst had a nominal composition of 4.1 wt % Ru/ Zr0 2 .
  • Zirconium isopropoxide in propanol (6.527 mL, 2.231 M), titanium n-butoxide, 60 volume % in ethanol, (8.215 mL), and ethanol (36.386 mL) were added simultaneously to a 150 mL petri dish with gentle agitation.
  • 0.3309 M aqueous ruthenium (HI) chloride (4.632 mL) solution was added while gently agitating. A gel point was rapidly developed. The alcogel thus produced was grayish-blue in color. It was aged approximately 24 hours, dried under vacuum for 5 hours at 110°C.
  • the final xerogel had a nominal composition of Ru (0.05)/Ti (0.475)/Zr (0.475).
  • the catalyst used was the same as that of Example 7.
  • EXAMPLE 22 Isobutyl alcohol (61.32 mL) was combined with tantalum ethoxide (40.491 g) in an inert atmosphere N drybox. In a separate container, ruthenium trichloride (RuCl3»0.2H O, 0.156 g) and rhenium trioxide (0.3884 g) were combined with water (8.978 g) and additional ethanol (61.32 mL). Glacial acetic acid (0.8978 mL) and 70 wt. % nitric acid (0.835 L) were added to the water mixture.
  • RuCl3 ruthenium trichloride
  • rhenium trioxide (0.3884 g) were combined with water (8.978 g) and additional ethanol (61.32 mL).
  • Glacial acetic acid (0.8978 mL) and 70 wt. % nitric acid (0.835 L) were added to the water mixture.
  • the aqueous solution containing the ruthenium chloride and rhenium trioxide was added, in a dropwise fashion, to the tantalum alkoxide solution.
  • the apparatus was blanketed in nitrogen.
  • a clear solution was obtained.
  • the gel point was reached within 15 minutes.
  • the gel was aged at room temperature for twelve days prior to removal of solvent by supercritical CO 2 .
  • the material was placed in a stirred autoclave and extracted in C0 2 under supercritical conditions. C0 gas was purged over the catalyst for 7 hours at 40°C and 3500 psig
  • the material isolated was a free flowing powder.
  • the final aerogel had a nominal composition of 0.33 wt.% Ru/1.33 wt.% Re/Ta 2 O5.
  • Cobalt (II) chloride (5.273 mL, 1.0 M in ethanol), titanium n-butoxide (10.898 mL, 60 volume % in ethanol), and ethanol (19.6 mL) were combined in a 150 mL petri dish with gentle swirling, under a nitrogen atmosphere.
  • a solution containing ruthenium (HI) chloride (1.992 mL, 0.3309 M aqueous solution) and platinum (IV) chloride (7.236 mL, 0.1822 M aqueous solution) was added to the alkoxide solution.
  • a gel point was realized within minutes.
  • the material was dried in a vacuum oven for five hours to produce the final xerogel.
  • the final xerogel had a nominal composition of Ru (0.025)/Co (0.2)/Pt (0.05)Ti (0.725).
  • a solution containing ruthenium (III) chloride (4.753 mL, 0.3309 M aqueous solution), platinum (IV) chloride (8.633 mL, 0.1822 M aqueous solution) and aluminum nitrate (Al(N ⁇ 3)3*9H 2 O, 11.01 mL, 1 M aqueous solution) was added to the alkoxide solution to induce gel formation.
  • the material was dried in a vacuum oven for five hours to produce the final xerogel catalyst.
  • the final xerogel had a nominal composition of Ru (0.05)/Co (0.2)/Pt (0.05)Ti (0.35)/ Al (0.35).
  • Example 23 A procedure similar to that described for Example 23 was used. Titanium n-butoxide (8.009 mL, 60 volume % in ethanol) and ethanol (18.273 mL) were combined in a 150 mL petri dish with gentle swirling, under a nitrogen atmosphere. In a second step a solution containing ruthenium (III) chloride (4.516 mL, 0.3309 M aqueous solution) and aluminum nitrate nine hydrate (14.197 mL, 1 M aqueous solution) was added to the alkoxide solution to induce gel formation. After aging for about 24 hours at room temperature, the material was dried in a vacuum oven for five hours to produce the final xerogel catalyst. The final xerogel had a nominal composition of Ru (0.05)/ Ti (0.47)/ Al (0.475).
  • Example 23 A procedure similar to that described for Example 23 was used. Titanium n-butoxide (11.752 mL, 60 volume % in ethanol), and ethanol (26.823 mL) were combined in a 150 mL petri dish with gentle swirling, under a nitrogen atmosphere. In a second step a solution containing ruthenium (III) chloride (3.367 mL, 0.3309 M aqueous solution), platinum (IV) chloride (3.058 mL,
  • the final xerogel had a nominal composition of Ru (0.05)/Pt (0.025)/Ti
  • the final xerogel had a nominal composition of Ru (0.05)/Pt (0.05)/Ti (0.90).
  • the final xerogel had a nominal composition of Ru (0.05)/Pt (0.025)/Ti (0.925).
  • EXAMPLE 31 A procedure similar to that described for Example 23 was used. Ruthenium trichloride (15.503 mL, 0.09777 M in ethanol), titanium n-butoxide (15.986 mL, 60 volume % in ethanol), and ethanol (36.486 mL) were combined in a 150 mL petri dish with gentle swirling, under a nitrogen atmosphere. In a second step, palladium dichloride (4.031 mL, 0.188 M in water) was added to the alkoxide solution to induce formation of a red gel. After aging for about 24 hours at room temperature, the material was dried in a vacuum oven for five hours to produce the final xerogel. The final xerogel had a nominal composition of Ru (0.05)/Pd (0.025)/Ti (0.925). EXAMPLE 32
  • the final xerogel had a nominal composition of Ru (0.05)/Co (0.15) Pd (0.025)/Ti (0.775).
  • the final xerogel had a nominal composition of Ru (0.05)/Co (0.3)/Pd (0.05)/Ti (0.90).
  • the catalyst testing unit was composed of a syngas feed system, a tubular reactor, which had a set of wax and cold traps, back pressure regulators, and three gas chromatographs (one on-line and two off-line).
  • the carbon monoxide was purified before being fed to the reactor over a 22% lead oxide on alumina catalyst placed in a trap to remove any iron carbonyls present.
  • the individual gases or mixtures of the gases were mixed in a 300 mL vessel filled with glass beads before entering the supply manifold feeding the reactor.
  • the reactor was made of 3/8 in. (0.95 cm) O.D. by 1/4 in. (0.63 cm) I.D. stainless steel tubing.
  • the length of the reactor tubing was 14 in. (35.6 cm).
  • the actual length of the catalyst bed was 10 in. (25.4 cm) with 2 in. (5.1 cm) of 25/30 mesh (0.71/0.59 mm) glass beads and glass wool at the inlet and outlet of the reactor.
  • the wax and cold traps were made of 75 mL pressure cylinders.
  • the wax traps were set at 140°C while the cold traps were set at 0°C.
  • the reactor had two wax traps in parallel followed by two cold traps in parallel. At any given time products from the reactor flowed through one wax and one cold trap in series. Following a material balance period, the hot and cold traps used were switched to the other set in parallel, if needed.
  • the wax traps collected a heavy hydrocarbon product distribution (usually between Cg and above) while the cold traps collected a lighter hydrocarbon product distribution (usually between C3 and C 2 Q). Water, a major product of the Fischer-Tropsch process was collected in both the traps.
  • the uncondensed gaseous products from the reactors were analyzed using a common on-line HP Refinery Gas Analyzer.
  • the Refinery Gas Analyzer was equipped with two thermal conductivity detectors and measured the concentrations of CO, H 2 , N 2 , C0 2 , CH4, C 2 to C5 alkenes/alkanes/isomers and water in the uncondensed reactor products.
  • the products from each of the hot and cold traps were separated into an aqueous and an organic phase.
  • the organic phase from the hot trap was usually solid at room temperature. A portion of this solid product was dissolved in carbon disulfide before analysis.
  • the organic phase from the cold trap was usually liquid at room temperature and was analyzed as obtained.
  • the aqueous phase from the two traps was combined and analyzed for alcohols and other oxygenates.
  • Catalyst Testing Procedure Catalyst (3 g) to be tested was mixed with 4 grams of 25/30 mesh (0.71/0.59 mm) and 4 grams of 2 mm glass beads. The 14 in. (35.6 cm) tubular reactor was first loaded with 25/30 mesh (0.71/0.59 mm) glass beads so as to occupy 2 in. (5.1 cm) length of the reactor. The catalyst/glass bead mixture was then loaded and occupied 10 in. (25.4 cm) of the reactor length. The remaining 2 in. (5.1 cm) of reactor length was once again filled with 25/30 mesh (0.71/0.59 mm) glass beads. Both ends of the reactor were plugged with glass wool. Catalyst activation was subsequently carried out using the following procedure.
  • the reactor was heated to 120°C under nitrogen flow (100 cc/min and 40 psig (377 kPa)) at a rate of 1.5°C/min. The reactor was maintained at 120°C under these conditions for two hours for drying of the catalyst. At the end of the drying period, the flow was switched from nitrogen to hydrogen. The reactor was heated under hydrogen flow (100 cc/min and 40 psig (377 kPa)) at a rate of 1.4°C/min. to 350°C. The reactor was maintained at 350°C under these conditions for sixteen hours for catalyst reduction. At the end of the reduction period, the flow was switched back to nitrogen and the reactor cooled to reaction temperature (usually 220°C).
  • the reactor was pressurized to the desired reaction pressure and cooled to the desired reaction temperature. Syngas, with a 2: 1 H 2 /CO ratio was then fed to the reactor when reaction conditions were reached.
  • the first material balance period started at about four hours after the start of the reaction. A material balance period lasted for between 16 to 24 hours.
  • data were collected for feed syngas and exit uncondensed gas flow rates and compositions, weights and compositions of aqueous and organic phases collected in the wax and cold traps, and reaction conditions such as temperature and pressure.
  • the information collected was then analyzed to get a total as well as individual carbon, hydrogen and oxygen material balances. From this information, CO Conversion (%), Selectivity/Alpha plot for all (C ⁇ to C40) of the hydrocarbon products, C5+
  • Table 3 lists the catalyst composition, CO Conversion (%), Alpha value from the Anderson- Shultz-Flory plot of the hydrocarbon product distribution, C5+ Productivity (g C5+/hour/kg catalyst) and weight percent methane in the total hydrocarbon product (%).
  • the temperature was 220°C
  • the pressure was from 340 psig (2445 kPa) to 362 (2597 kPa) and the space velocity was 2 NL/hour/g-catalyst for all the examples in Table 3.
  • Ethanol 141.72 mL was combined with titanium n-butoxide (31.5412 g) in an inert atmosphere N 2 drybox.
  • ruthenium trichloride 1.5196 g was combined with water (6.678 g) and additional ethanol (141.72 mL).
  • Glacial acetic acid 0.795 mL
  • nitric acid 0.621 mL, 70 wt. % were added to the water mixture.
  • the aqueous acidic solution containing the ruthenium chloride was added, in a dropwise fashion, to the titanium alkoxide solution.
  • the apparatus was blanketed in nitrogen.
  • EXAMPLE 39 In an inert atmosphere drybox, titanium n-butoxide (115.72 g) was added to ethanol (240 mL) along with a 1 M CoCl 2 (39.806 mL) in ethanol solution. This mixture was loaded into a 1 L resin kettle. In a dropping funnel, H 2 0 (25.50 mL) was combined with ruthenium trichloride (4.508 g) and ethanol (240 mL). This aqueous solution was slowly added to the alkoxide solution. The entire assembly was under nitrogen purge during this addition. A gel point was rapidly realized. The material was dark brown in color, was aged for 3 days and dried under vacuum at 120°C for 5 hours. The final xerogel had a nominal composition of Co (0.1)/Ru (0.05)/Ti (0.85).

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé relatif à l'élaboration d'hydrocarbures, qui consiste à mettre en contact dans une zone de réaction un catalyseur avec un flux d'alimentation comprenant de l'hydrogène et du monoxyde de carbone. On maintient dans ladite zone des conditions favorables à la conversion qui sont efficaces pour la production d'un flux d'effluents renfermant des hydrocarbures. Le catalyseur utilisé est élaboré selon un procédé qui consiste au moins (1) à former un gel catalyseur par mélange entre (a) au moins un composé de métal catalytique dissous pour les réactions du procédé Fischer-Tropsch (par exemple, composé(s) de fer, cobalt, nickel et/ou ruthénium dissous dans de l'eau et/ou de l'éthanol); (b) (i) au moins un alcoxyde de titane, zirconium et/ou tantale dissous, et éventuellement (ii) au moins un composé d'aluminium dissous (les éléments alcoxyde et composé d'aluminium (i) et (ii) étant dissous dans un solvant non aqueux; au moins, le cas échéant, on hydrolyse l'alcoxyde (i) et le composé d'aluminium (ii); et (c) un supplément d'eau; enfin, (2), le procédé consiste à sécher le gel.
PCT/US1999/018962 1998-08-20 1999-08-19 Procede fischer-tropsch a base de catalyseurs en xerogel et aerogel Ceased WO2000010705A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU55751/99A AU5575199A (en) 1998-08-20 1999-08-19 Fischer-tropsch processes using xerogel and aerogel catalysts

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
US9719498P 1998-08-20 1998-08-20
US9719298P 1998-08-20 1998-08-20
US9719398P 1998-08-20 1998-08-20
US60/097,194 1998-08-20
US60/097,193 1998-08-20
US60/097,192 1998-08-20
US37700799A 1999-08-18 1999-08-18
US09/377,008 US6235677B1 (en) 1998-08-20 1999-08-18 Fischer-Tropsch processes using xerogel and aerogel catalysts by destabilizing aqueous colloids
US09/376,873 1999-08-18
US09/376,873 US6319872B1 (en) 1998-08-20 1999-08-18 Fischer-Tropsch processes using catalysts on mesoporous supports
US09/377,008 1999-08-18
US09/377,007 1999-08-18

Publications (1)

Publication Number Publication Date
WO2000010705A1 true WO2000010705A1 (fr) 2000-03-02

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Application Number Title Priority Date Filing Date
PCT/US1999/018962 Ceased WO2000010705A1 (fr) 1998-08-20 1999-08-19 Procede fischer-tropsch a base de catalyseurs en xerogel et aerogel
PCT/US1999/018895 Ceased WO2000010704A1 (fr) 1998-08-20 1999-08-19 Procedes fischer-tropsch utilisant des catalyseurs a base de xerogel ou d'aerogel formes par la destabilisation de colloides aqueux
PCT/US1999/018994 Ceased WO2000010698A2 (fr) 1998-08-20 1999-08-19 Synthese de fischer-tropsch utilisant des catalyseurs sur des supports mesoporeux

Family Applications After (2)

Application Number Title Priority Date Filing Date
PCT/US1999/018895 Ceased WO2000010704A1 (fr) 1998-08-20 1999-08-19 Procedes fischer-tropsch utilisant des catalyseurs a base de xerogel ou d'aerogel formes par la destabilisation de colloides aqueux
PCT/US1999/018994 Ceased WO2000010698A2 (fr) 1998-08-20 1999-08-19 Synthese de fischer-tropsch utilisant des catalyseurs sur des supports mesoporeux

Country Status (4)

Country Link
EP (2) EP1109622A4 (fr)
AU (3) AU757374B2 (fr)
CA (2) CA2341174A1 (fr)
WO (3) WO2000010705A1 (fr)

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US6727289B2 (en) 2001-01-12 2004-04-27 Conocophillips Company Boron promoted catalysts and fischer-tropsch processes
US6730708B2 (en) 2000-07-03 2004-05-04 Conocophillips Company Fischer-Tropsch processes and catalysts using aluminum borate supports
CN112517019A (zh) * 2020-12-17 2021-03-19 大唐国际化工技术研究院有限公司 一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用
CN112588292A (zh) * 2020-12-17 2021-04-02 大唐国际化工技术研究院有限公司 一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用
CN114671452A (zh) * 2022-03-03 2022-06-28 滁州学院 一种以环氧化合物为凝胶促进剂制备块状氧化铈气凝胶的方法

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EP1380341B1 (fr) 2001-03-29 2008-02-06 Idemitsu Kosan Co., Ltd. Procede catalytique de reformage d'hydrocarbures mettant en oeuvre ledit catalyseur
US7067453B1 (en) 2001-07-13 2006-06-27 Innovatek, Inc. Hydrocarbon fuel reforming catalyst and use thereof
EP2666540A1 (fr) * 2012-05-22 2013-11-27 Karlsruher Institut für Technologie Procédé d'hydrodésoxygénation catalytique de dérivés de furane et/ou d'huiles de pyrolyse, le catalyseur correspondant et son procédé de préparation.
US9290425B2 (en) * 2013-06-20 2016-03-22 Standard Alcohol Company Of America, Inc. Production of mixed alcohols from synthesis gas
US10875820B2 (en) 2013-06-20 2020-12-29 Standard Alcohol Company Of America, Inc. Catalyst for converting syngas to mixed alcohols
FR3018810B1 (fr) * 2014-03-20 2017-06-09 Ifp Energies Now Procede fischer-tropsch utilisant un catalyseur a base d'un metal du groupe viiib et d'un support d'oxydes comprenant de l'alumine, de la silice et du phosphore
CN111375439B (zh) * 2020-04-22 2022-09-20 陕西延长石油（集团）有限责任公司 一种液相丙烯一步制备环氧丙烷的方法及催化剂

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US6730708B2 (en) 2000-07-03 2004-05-04 Conocophillips Company Fischer-Tropsch processes and catalysts using aluminum borate supports
US6727289B2 (en) 2001-01-12 2004-04-27 Conocophillips Company Boron promoted catalysts and fischer-tropsch processes
CN112517019A (zh) * 2020-12-17 2021-03-19 大唐国际化工技术研究院有限公司 一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用
CN112588292A (zh) * 2020-12-17 2021-04-02 大唐国际化工技术研究院有限公司 一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用
CN114671452A (zh) * 2022-03-03 2022-06-28 滁州学院 一种以环氧化合物为凝胶促进剂制备块状氧化铈气凝胶的方法
CN114671452B (zh) * 2022-03-03 2023-09-01 滁州学院 一种以环氧化合物为凝胶促进剂制备块状氧化铈气凝胶的方法

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CA2341175A1 (fr) 2000-03-02
AU5681899A (en) 2000-03-14
EP1109622A4 (fr) 2002-01-23
AU757374B2 (en) 2003-02-20
AU5572199A (en) 2000-03-14
AU746882B2 (en) 2002-05-02
WO2000010698A2 (fr) 2000-03-02
WO2000010704A1 (fr) 2000-03-02
CA2341174A1 (fr) 2000-03-02
AU5575199A (en) 2000-03-14
EP1109622A2 (fr) 2001-06-27
WO2000010698A3 (fr) 2000-10-26
EP1128905A1 (fr) 2001-09-05

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