WO2001036323A2 - Catalyseurs a base de cobalt et procede de production de gaz de synthese - Google Patents

Catalyseurs a base de cobalt et procede de production de gaz de synthese Download PDF

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WO2001036323A2
WO2001036323A2 PCT/US2000/031451 US0031451W WO0136323A2 WO 2001036323 A2 WO2001036323 A2 WO 2001036323A2 US 0031451 W US0031451 W US 0031451W WO 0136323 A2 WO0136323 A2 WO 0136323A2
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Prior art keywords
cobalt
catalyst device
catalyst
reactant gas
gas mixture
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PCT/US2000/031451
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WO2001036323A3 (fr
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Anne M. Gaffney
Roger Song
Robert Oswald
David Corbin
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Conoco Inc.
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Priority to AU17679/01A priority Critical patent/AU1767901A/en
Priority to CA002392106A priority patent/CA2392106A1/fr
Priority to EP00980414A priority patent/EP1230146A2/fr
Publication of WO2001036323A2 publication Critical patent/WO2001036323A2/fr
Publication of WO2001036323A3 publication Critical patent/WO2001036323A3/fr

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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/75—Cobalt
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • 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
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
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    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1023—Catalysts in the form of a monolith or honeycomb
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1029—Catalysts in the form of a foam
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention generally relates to catalysts and processes for converting a light hydrocarbon (e.g., natural gas) and oxygen to a product containing a mixture of carbon monoxide and hydrogen, also referred to as synthesis gas or syngas. More particularly, the invention relates to supported cobalt-containing catalysts and syngas production processes employing them. Description of Related Art
  • methane the main component of natural gas
  • natural gas is predicted to outlast oil reserves by a significant margin.
  • most natural gas is situated in areas that are geographically remote from population and industrial centers.
  • the costs of compression, transportation, and storage make its use economically unattractive.
  • methane is typically carried out in two steps. In the first step, methane is reformed with water to produce carbon monoxide and hydrogen (i.e., synthesis gas or syngas). In a second step, the syngas is converted to hydrocarbons, for example, using the Fischer-Tropsch process to provide fuels that boil in the middle distillate range, such as kerosene and diesel fuel, and hydrocarbon waxes.
  • oxidation reactions are typically much faster than reforming reactions, and therefore, allow the use of much smaller reactors.
  • the selectivities of catalytic partial oxidation to the desired products are controlled by several factors.
  • One of the most important of these factors is the choice of catalyst composition. Choosing an economical catalyst that is efficient and provides excellent selectivities for CO and H is a problem.
  • catalyst compositions have included precious metals and/or rare earths. The large volumes of expensive catalysts required in most conventional catalytic partial oxidation processes have placed these processes generally outside the limits of economic justification.
  • the catalytic partial oxidation process must be able to achieve a high conversion of the methane feedstock at high gas hourly space velocities, and the selectivity of the process to the desired products of carbon monoxide and hydrogen must be high.
  • Such high conversion and selectivity must be achieved without detrimental effects to the catalyst, such as the formation of carbon deposits ("coke") on the catalyst, which severely reduces catalyst performance. Accordingly, substantial effort has also been devoted in the art to the development of catalysts allowing sustainable commercial performance without coke formation.
  • EP303438 describes one method for the catalytic partial oxidation of methane using a high temperature, high pressure mixture of methane and oxygen at GHSV (gas hourly space velocity) of up to 5 x 10 5 .
  • GHSV gas hourly space velocity
  • 5,149,464 discloses a method for selectively converting methane to syngas at 650°C to 950°C by contacting the methane/oxygen mixture with a solid catalyst comprising a supported d-Block transition metal, transition metal oxide, or a compound of the formula M x M' y O z wherein M' is a d-Block transition metal and M is Mg, B, Al, Ga, Si, Ti, Xr, Hf or a lanthanide.
  • U.S. Pat. No. 5,500,149 discloses various transition metals that can act as catalysts in the reaction CO 2 + CH 4 -» 2CO + 2H , and demonstrates how reaction conditions can affect the product yield.
  • 5,447,705 discloses another catalyst having a perovskite crystalline structure and the general composition: Ln x A ⁇ _ y B y O 3 , wherein Ln is a lanthanide and A and B are different metals chosen from Group IVb, Vb, VIb, Vllb or VIII of the Periodic Table of the Elements.
  • Lago et al. (1997 J Catalysis 167:198-209; and in Grasselli, et al. (eds.) 3 rd World Congress on Oxidation Catalysis, Elsevier Science B.V., 1997, pp. 721-730) also describe certain perovskite catalyst precursors containing cobalt and lanthanide oxides for the partial oxidation of methane to synthesis gas.
  • U.S. Pat. No. 5,338,488 describes a process for the production of synthesis gas by oxidative conversion of methane using composite catalysts containing certain transitional and alkaline earth metal oxides.
  • the transition metals include Ni, Co, Pd, Ru, Rh, Ir and mixtures thereof; and the alkaline earth metals include Mg, Ca, Ba, Sr and mixtures thereof.
  • U.S. Pat. No. 5,368,835, U.S. Pat. No. 5,411, 927 and U.S. Pat. No. 5,756,421 describe the oxidative conversion of methane to synthesis gas using catalysts containing certain transition and non- transition metal oxides.
  • 1130150A discloses a cobalt- alkaline earth-lanthanide-containing catalyst used to convert CH 4 to CO and H 2 at 300- 900°C.
  • Japanese Pat. No. 1-52055 describes a cobalt-alumina-magnesia spinel catalyst and a cobalt oxide-barium aluminate catalyst for catalyzing the partial oxidation of hydrocarbons.
  • Others have employed certain cobalt-containing catalysts in hydrocarbon reforming processes.
  • U.S. Pat. No. 4,024,075 (Russ et al.) describes a supported cobalt catalyst for reforming hydrocarbons with steam and carbon dioxide. Wang, et al. (1998
  • U.S. Patent No. 5,989,457 describes a process for making synthesis gas by methane reforming with carbon dioxide using a Co, Ni, Pt or Pd catalyst on a thermally stabilized oxidic support containing an oxide of Y, La, Al, Ca, Ce or Si.
  • U.S. Patent No. 6,060,420 describes a catalyst for purifying exhaust gas comprising an alumina or zirconia catalyst carrier substrate and a composite oxide of A-site defect perovskite structure represented by the general formula: A ⁇ BO ⁇ where A is an alkali metal, alkaline earth metal, rare earth element, Y or Pb. B is Mn, Co, Ti, Fe, Ni, Cu and Al and ⁇ is from 0.12-0.15 and ⁇ is up to 1.
  • the present invention provides processes for preparing synthesis gas using cobalt- containing catalysts for the catalytic partial oxidation of any gaseous hydrocarbon having a low boiling point (e.g. C]-C 5 hydrocarbons, particularly methane, or methane containing feeds).
  • a gaseous hydrocarbon having a low boiling point e.g. C]-C 5 hydrocarbons, particularly methane, or methane containing feeds.
  • cobalt catalysts of the process is that they retain a high level of activity and selectivity to carbon monoxide and hydrogen under conditions of high gas space velocity and elevated pressure.
  • Another advantage of the new catalytic processes is that they are economically feasible for use in commercial-scale conditions.
  • the supported catalysts contain cobalt metal and/or one or more cobalt containing compound(s) including the various oxides of cobalt, cobalt containing spinels, mixed metal oxides or metals of cobalt with magnesia, nickel, LaZrO 2 , lanthanum oxide, alumina, zirconia, ceria, and calcium oxide.
  • the spinels and mixed metal oxides include CoAl O , MgCo O 4 , Co AlO 4 , LaAl 8 Co 2 O 3 , CaCo 2 O 4 , ZnCo 2 O 4 , and NiCo O 4 .
  • the catalyst may be comprised of a cobalt-containing hydrotalcite, including the hydrotalcite Co 6 Al 2 (OH) ⁇ 6 CO 3 • 4 H 2 O.
  • the support structure comprises a spinel, a perovskite, magnesium oxide, a hydrotalcite, LaZrO 2 , lanthanum oxide, a pyrochlore, a brownmillerite, zirconium phosphate, magnesium stabilized zirconia, zirconia stabilized alumina, silicon carbide, yttrium stabilized zirconia, calcium stabilized zirconia, yttrium aluminum garnet, alumina, cordierite, ZrO 2 , ZnO, LaAlO 3 , MgAl 2 O 4 , SiO 2 or TiO 2 .
  • the cobalt metal and/or cobalt containing compound(s) are disposed on or within the support structure.
  • the catalyst support structure is a hydrotalcite, spinel, a perovskite, a pyrochlore or a brownmillerite, and the cobalt metal and/or cobalt containing compound(s) are incorporated into the support structure.
  • the support structure comprises a refractory oxide, which may be in the form of a foam structure.
  • a foam structure comprises about 12-60 pores per centimeter of structure.
  • the support structure is in the form of a honeycomb monolith structure.
  • the catalyst comprises the cobalt metal and/or cobalt containing compound(s) on a support structure comprising Al 2 O 3 .
  • Some embodiments comprise a Co containing hydrotalcite.
  • the catalyst comprises mixtures of cobalt metal and/or oxides with magnesia in the form of solid solution.
  • Another catalyst embodiment comprises cobalt spinels and mixed metal oxides including CoAl 2 O 4 , MgCo 2 O 4 , Co AlO 4 , LaAl 8 Co 2 O 3 , CaCo 2 O 4 , ZnCo 2 O 4 , and NiCo 2 O 4 .
  • others comprise cobalt metal and/or oxides on LaZrO 2 , alumina, lanthanum oxide, and zirconia.
  • a syngas catalyst device comprises cobalt metal and/or cobalt oxide, a promoter chosen from the group consisting of Mn, Ni, La, Cu, Sm, Yb, Eu, Pr, Ce, Y, Pt, Rh and Re, and a support structure comprising partially stabilized zirconia.
  • the catalyst device comprises cobalt metal and/or cobalt oxide, manganese metal and/or manganese oxide, magnesium oxide and a partially stabilized zirconia support.
  • the catalyst comprises 0.15 wt% Pt, about 6.5 wt% Co and about 6.1 wt% Mg by catalyst weight.
  • a syngas catalyst is prepared by impregnating a refractory metal oxide support, such as a PSZ foam, with a solution of an oxidizable magnesium salt and then calcining the resulting magnesium impregnated support.
  • the magnesium impregnated support is then re-impregnated with a solution of an oxidizable cobalt salt to provide a cobalt/magnesium oxide intermediate, which is then calcined and reduced.
  • this (cobalt/magnesium) oxide loaded support is then coated with a promoter by impregnating with a solution of an oxidizable metal salt, such as a nitrate or an acetate.
  • Suitable promoter metals include Mn, Ni, La, Cu, Sm, Yb, Eu, Pr, Ce, Y, Pt, Rh and Re.
  • the promoter/(cobalt/magnesium) oxide coated support is then calcined and reduced to provide a supported catalyst that is active for catalyzing the net partial oxidation of methane in the presence of O 2 to CO and H under partial oxidation promoting conditions in a short contact time reactor.
  • Also provided by the present invention is a process for the net partial oxidization of a
  • the process comprises passing a reactant gas mixture comprising a Ci- C 5 hydrocarbon and an O 2 -containing gas over a supported catalyst, or catalyst device, as described above, in a millisecond contact time reactor.
  • the contact time of a portion of reactant gas mixture in contact with the catalyst device does not exceed about 10 milliseconds.
  • the process also includes maintaining net catalytic partial oxidation promoting conditions during operation of the reactor. Such reaction-promoting conditions include maintaining a favorable hydrocarbomoxygen molar ratio in the reactant gas mixture, maintaining a favorable catalyst temperature, maintaining a favorable reactant gas preheat temperature and reactant flow rate.
  • the process includes maintaining the reactant gas mixture and the catalyst at a temperature of about 600-l,200°C during contact. In some embodiments the temperature is maintained at about 700-l,100°C.
  • maintaining net catalytic partial oxidation promoting conditions includes mixing a methane-containing feedstock and an oxygen- containing feedstock to provide a reactant gas mixture feedstock having a carbomoxygen molar ratio of about 1.25:1 to about 3.3:1.
  • the mixing step is such that it yields a reactant gas mixture feed having a carbomoxygen ratio of about 1.3:1 to about 2.2:1, or preferably about 1.5:1 to about 2.2:1.
  • the mixing step provides a reactant gas mixture feed having a carbon:oxygen ratio of about 2:1.
  • the oxygen-containing gas that is mixed with the hydrocarbon also contains steam or CO 2 , or both.
  • the Cj-C 5 hydrocarbon comprises at least about 50 % methane by volume, and in some of the preferred embodiments the C]-C 5 hydrocarbon comprises at least about 80 % methane by volume.
  • Some embodiments of the process include preheating the reactant gas mixture, to facilitate catalyst activation for the reaction.
  • Some embodiments of the processes comprise passing the reactant gas mixture over the catalyst at a space velocity of about 20,000 to about 100,000,000 normal liters of gas per kilogram of catalyst per hour (NL/kg/h). In certain of these embodiments, the gas mixture is passed over the catalyst at a space velocity of about 50,000 to about 50,000,000 NL/kg/h.
  • the reactor is operated at a pressure of about 100-12,500 kPa during the contacting, and in some of the more preferred embodiments the pressure is maintained at about 130-10,000 kPa.
  • catalysts, or catalyst devices, useful for catalytically converting C]-C 5 hydrocarbons to CO and H contain cobalt metal and/or cobalt-containing compound(s) have been developed which include support materials such as hydrotalcites, spinels, perovskites, magnesium oxide, lanthanum oxide, LaZrO , pyrochlores, brownmillerites, zirconium phosphate, magnesium stabilized zirconia, zirconia stabilized alumina, silicon carbide, yttrium stabilized zirconia, calcium stabilized zirconia, yttrium aluminum garnet, alumina, cordierite, mullite, ZrO 2 , ZnO, LaAlO 3 , MgAl 2 O 4 , SiO 2 or TiO 2 .
  • support materials such as hydrotalcites, spinels, perovskites, magnesium oxide, lanthanum oxide, LaZrO , pyrochlores, brownmillerites, zirconium phosphate, magnesium
  • the cobalt metal and/or cobalt-containing compound(s) are incorporated into the structure of a hydrotalcite, spinel, perovskite, pyrochlore or brownmillerite.
  • representative catalysts comprised of cobalt metal and/or one or more cobalt- containing compounds are prepared utilizing conventional techniques such as impregnation, wash coating, adso ⁇ tion, ion exchange, precipitation, co-precipitation, deposition precipitation, sol-gel method, slurry dip-coating, microwave heating, and the like, all of which are well known in the field.
  • Preferred techniques are wash coating, impregnation, sol- gel methods and co-precipitation.
  • some of the more active supported catalysts include a promoter and are prepared using a multi-step support loading process and defined calcining and reducing program.
  • the catalyst components with or without a ceramic support material are extruded to prepare a three-dimensional form or structure such as a honeycomb, foam, or other suitable tortuous-path structure.
  • the catalyst components may be added to the powdered ceramic composition and then extruded to prepare the foam or honeycomb.
  • a suitable foam catalyst structure has from 30 to 150 pores per inch (12 to 60 pores per centimeter).
  • Alternative forms for the catalyst include refractory oxide honeycomb monolith structures, or other configurations having longitudinal channels or passageways permitting high space velocities with a minimal pressure drop. Such configurations and their manner of making are described, for example, in Structured Catalysts and Reactors, A. Cybulski and J.A.
  • spinel-like refers to a mixed metal oxide that conforms to the molecular formula AB 2 O , where A and B represent the two metals forming the mixed metal oxide.
  • Chemical analysis by inductively coupled plasma spectrometry gave 51.95% Co and 17.2%Mg.
  • Example 14 2%Co/Al 2 O 3 8.47 g of CoCl 2 -6H 2 O were dissolved in 184 mL H 2 O. 105 g gamma-alumina (dried at 110°C overnight) were added with stirring to the CoCl 2 solution. The water was evaporated off by heating on a hot plate at approximately 90°C. The catalyst was stirred every 10 to 15 minutes until dry.
  • Example 15 Co/Zn/O In a 2 L Roto-Vap flask was mixed, 291.04 g of Co(NO 3 ) 2 -6H 2 O, 148.74 g of
  • the catalysts were evaluated in a laboratory scale short contact time reactor, a 25 cm long x 4 mm i.d. quartz tube reactor equipped with a co-axial quartz thermocouple well. The void space within the reactor was packed with quartz chips. The catalyst bed was positioned with quartz wool at about the mid-length of the reactor. The catalyst bed was heated with a 4 inch (10.2 cm) 600 watt band furnace at 90% electrical output. All runs were done at a CH 4 :O 2 molar ratio of 2:1 and at a pressure of 5 psig (136 kPa). The reactor effluent was analyzed using a gas chromatograph equipped with a thermal conductivity detector. The C, H and O mass balance were all between 98% and 102%. The runs were conducted over two operating days with 6 hours of run time each day. The comparative results of these runs are shown in Table 1, wherein gas hourly space velocity is indicated by "GHSV.” As shown in Table 1, no evidence of catalyst deactivation occurred after 12 hours.
  • GHSV gas hourly space velocity
  • Comparative Examples A and B serve as comparative examples demonstrating that the Co oxides, themselves, are not as effective in catalyzing the partial oxidation of methane to syngas. As the data entries in Table 1 indicate, methane conversion and syngas selectivity are significantly lower for those runs which were catalyzed by Co 3 O 4 and CoO.
  • Example 18 12%(Co/Al/O)/PSZ
  • the powder catalyst prepared in Example 3 was first ground to less than 325 mesh, then 1.3909g of H 2 O was added to the powder (0.3173 g) in a glass vial to form a slurry.
  • a PSZ foam (12mm OD x 10mm of 80ppi) from Vesuvius Hi-Tech Inc. was dipped into the slurry and saturated for 5 minutes. The foam was removed from the vial and the slurry remained in the pores of the foam was removed by blowing some compressed air. Finally, the foam was dried at 100°C for 2 hours.
  • Example 19 9% (Co/Mg/O)/PSZ
  • the powder catalyst prepared in Example 4 was first ground to less than 325 mesh, then 1.2370g of H O was added to the powder (0.3067g) in a glass vial to form a slurry.
  • a PSZ foam (12mm OD x 10mm of 80ppi) from Vesuvius Hi-Tech Inc. was dipped into the slurry and saturated for 5 minutes. The foam was removed from the vial and the slurry remained in the pores of the foam was removed by blowing some compressed air. Finally, the foam was dried at 100°C for 2 hours
  • Example 20 12%(Co/Al/O), 4%MgO/PSZ
  • Example 3 The powder catalyst prepared in Example 3 was first ground to less than 325 mesh, then 1.3026g of H 2 O was added to the powder (0.2965g) in a glass vial to form a slurry.
  • the MgO coated PSZ foam was dipped into the slurry and saturated for 5 minutes. The foam was removed from the vial and the slurry remained in the pores of the foam was removed by blowing some compressed air. Finally, the foam was dried at 100°C for 2 hours.
  • Example 21 14%(Co-AI-Substituted hydrotalcite) /PSZ
  • the powder catalyst prepared in Example 5 was first ground to less than 325 mesh, then 1.2271g of H 2 O was added to the powder (0.2800g) in a glass vial to form a slurry.
  • a PSZ foam (12mm OD x 10mm of 80ppi) from Vesuvius Hi-Tech Inc. was dipped into the slurry and saturated for 5 minutes. The foam was removed from the vial and the slurry remained in the pores of the foam was removed by blowing some compressed air. Finally, the foam was dried at 100°C for 2 hours.
  • Test Procedure for Examples 18-21
  • the partial oxidation reactions were done with a conventional flow apparatus using a 19 mm O.D. x 13 mm I.D. and 12" long quartz reactor.
  • a ceramic foam of 99% Al 2 O 3 (12 mm OD x 5 mm of 45 ppi) were placed before and after the catalyst as radiation shields.
  • the inlet radiation shield also aided in uniform distribution of the feed gases.
  • An Inconel sheathed, single point K-type (Chromel/Alumel) thermocouple (TC) was placed axially inside the reactor touching the top (inlet) face of the radiation shield.
  • a high temperature S- Type (Pt/Pt 10% Rh) bare-wire TC was positioned axially touching the bottom face of the catalyst and was used to indicate the reaction temperature.
  • the catalyst and the two radiation shields were sealed tight against the walls of the quartz reactor by wrapping them radially with a high purity (99.5%) alumina paper.
  • a 600 watt band heater set at 90% electrical output was placed around the quartz tube, providing heat to light off the reaction and to preheat the feed gases. The bottom of the band heater corresponded to the top of the upper radiation shield.
  • the reactor also contained two axially positioned, triple-point TCs, one before and another after the catalyst. These triple-point thermocouples were used to determine the temperature profiles of reactants and products subjected to preheating and quenching, respectively.
  • a Co-MgO solid solution catalyst supported on PSZ was prepared according to the following procedure (amounts given are for laboratory-scale batches): 4.3024 grams of Mg(NO 3 ) 2 .6H 2 O (Aldrich 23,717-5) was dissolved in 4.1652 grams of distilled and deionized (DDI) water at about 50°C. This solution was added to a PSZ foam 12-mm diameter x 10-mm long, weighing 1.9245 grams. The wet PSZ foam was dried at about 70°C and calcined in air according to the following schedule: 10°C/min ramp up to 500°C; hold at 500°C for 2 hours; 10°C/min ramp down to room temperature.
  • the wet MgO-loaded PSZ foam was dried at about 70°C and calcined in air according to the following schedule: 5°C/min ramp up to 200°C; hold at 200°C for 1 hour; 5°C/min ramp up to 400°C; hold at 400°C for 1 hour; 5°C/min ramp up to 800°C; hold at 800°C for 12 hours; 10°C/min ramp down to room temperature.
  • the resulting material contained a Co oxide loading of 0.1684 gram or 8.75 wt% based on the weight of PSZ foam.
  • the catalyst was reduced with H 2 using 1 : 1 by volume flow of N 2 :H 2 mixture at 0.3 standard liter per minute (SLPM) measured at 0°C and 1 atm pressure, using the following schedule: 5°C/min ramp up to 125°C; hold at 125°C for 0.5 hour; 5°C/min ramp up to 500°C; hold at 500°C for 3 hours; 5°C/min ramp down to room temperature.
  • This catalyst had an estimated loading of 0.0687 g. Mg and 0.0626 g. Co based on the respective oxide weights. Calculated as metal wt% based on the final catalyst weight, the final catalyst had 5.7 wt% Co, 6.4 wt% Mg.
  • a Co-MgO solid solution catalyst supported on PSZ was prepared according to the following procedure (amounts given are for laboratory-scale batches): 6.0664 grams of Mg(NO 3 ) 2 .6H 2 O (Aldrich 23,717-5) was dissolved in 5.2249 grams of distilled and deionized (DDI) water at about 50°C. One-third of this solution was added to a PSZ foam 12- mm diameter x 10-mm long, weighing 0.8628 gram. The wet PSZ foam was dried at about 70°C and calcined in air according to the following schedule: 5°C/min ramp up to 500°C; hold at 500°C for 2 hours; 10°C/min ramp down to room temperature.
  • the resulting material contained a Pt oxide loading of 0.0022 g., corresponding to a loading of 0.25% based on the weight of PSZ foam. Based on the total weight of the catalyst after calcination, the composition was: 0.15%) Pt, 6.5 % Co and 6.1%) Mg.
  • the catalyst was reduced with H 2 using a 1 :1 (by volume) flow of N 2 :H 2 mixture at 0.2 standard liters per minute (SLPM) measured at 0°C and 1 atm pressure, using the following schedule: 3°C/min. ramp up to 125°C; hold at 125°C for 0.5 hr; 3°C/min. ramp up to 500°C; hold at 500°C for 3 hrs; 5°C/min. ramp down to room temperature.
  • Other promoters including Ni, Mn, La, Cu, Sm, Yb, Eu, Pr, Ce, Y, Rh, and Re may be substituted for Pt in the procedure to provide additional active syngas catalysts.
  • catalysts are made as described above, but substituting the corresponding metal salt solution for the Pt(NH 3 ) 4 (NO 3 ) 2 solution.
  • Other refractory catalyst support materials may be substituted for PSZ, such as cordierite honeycomb or alpha-alumina foam having about 40-400 pores per inch (ppi) density.
  • Preferred syngas catalysts comprise catalytically active cobalt-containing components supported on a ceramic monolith porous carrier such as partially stabilized zirconia (PSZ) foam (stabilized with Mg, Y or Ca).
  • PSZ foams have been described in the literature (e.g., U.S. Patent No. 4,835,123 (Bush et al.)) and are commercially available from suppliers such as Vesuvius Hi-Tech Ceramics Inc., Alfred Station, New York.
  • the catalyst support may be ⁇ -alumina foam (also stabilized with Zr) or "honeycomb" straight channel extrudate made of cordierite or mullite.
  • the catalyst support was a laboratory-scale ceramic monolith comprising porous PSZ foam with approximately 6,400 channels per square inch (80 pores per linear inch).
  • the monolith was cylindrical overall, with a diameter corresponding to the inside diameter of the reactor tube and the length varying from 1/8" to 1-1/2".
  • These catalysts were tested substantially as described in the section entitled Test Procedure for Examples 18-21, using a feed containing natural gas or methane and oxygen in the molar ratio of from 1.7:1 to 2.3:1 (CH 4 :O 2 ratio) at a total GHSV of from 61,000 1/h to 1,000,000 1/h in the laboratory-scale reactor (at 5-15 psig) and pilot unit (at 15-400 psig) testing.
  • the laboratory-scale tests used methane and oxygen feed, while the pilot unit tests used natural gas and oxygen feed. Reacted gases were analyzed for content of CFL*, O 2 , CO, H 2 , CO 2 , and, optionally, other components. The results of those tests are shown in Table 3.
  • Example Composition CH ⁇ :0 2 Combined Pressure Preheat Catalyst %CH 4 .%0- %CO/%H 2 H 2 :CO molar feed ratio Flowrate Temp. Temp. Conv. Sel. in GHSV
  • Example 19 Compared to the performance of the catalyst of Example 19, it can be seen that an unpromoted Co-MgO catalyst prepared by the multi-step loading procedure and having a composition as in Example 22 resulted in higher levels of CH4 conversion and selectivity for CO and H 2 products operating at higher space velocities than in Example 19. Inclusion of very small amounts of Pt in the catalyst, prepared as described in Example 23, has the effect of lowering the light off temperature while not increasing the reaction temperature, at pressures as high as 45 psig and flow rates as high as 1.3 million GHSV. In addition, this catalyst showed excellent resistance to coking and Co metal loss by volatilization over 9 days, normally observed with unpromoted Co-based catalysts at higher flowrates.
  • CH 4 + CO 2 ⁇ 2 CO + 2H 2 (3) may also occur to some extent during the production of syngas, in which case the molar ratio of the H 2 and CO products is somewhat less than the preferred Fischer-Tropsch stoichiometric molar ratio of 2:1 H 2 :CO.
  • the reactants are contacted with the catalyst in a fixed bed configuration in the reaction zone of a millisecond contact time reactor. Particles of the catalyst or supported catalyst are retained in the reaction zone using fixed bed techniques well known in the art.
  • a catalyst device, or impregnated monolith, prepared as described above, is employed.
  • the catalyst or catalyst device preferably has sufficient permeability or porosity to permit a stream of said reactant gas mixture to pass over it at a gas hourly space velocity of at least about 20,000 NL/kg/hr, when the reactor is operated to produce synthesis gas.
  • a feed stream comprising a hydrocarbon feedstock and an oxygen-containing gas is contacted with one of the above-described catalysts comprised of cobalt metal and or cobalt containing compound(s) in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising carbon monoxide and hydrogen.
  • the hydrocarbon feedstock is any gaseous hydrocarbon having a low boiling point, such as methane, natural gas, associated gas, or other sources of light hydrocarbons having from 1 to 5 carbon atoms.
  • the hydrocarbon feedstock may be a gas arising from naturally occurring reserves of methane, and may also contain carbon dioxide.
  • the feed comprises at least 50% by volume methane, more preferably at least 75% by volume, and most preferably at least 80% by volume methane.
  • the hydrocarbon feedstock is in the gaseous phase when contacting the catalyst.
  • the hydrocarbon feedstock is contacted with the catalyst as a mixture with an oxygen-containing gas, preferably pure oxygen.
  • the oxygen- containing gas may also comprise steam and or CO 2 in addition to oxygen.
  • the hydrocarbon feedstock is contacted with the catalyst as a mixture with a gas comprising steam and/or CO 2 .
  • autothermal means that after catalyst ignition, no additional heat is supplied to the catalyst in order for the production of synthesis gas to continue. Autothermal reaction conditions are promoted by optimizing the concentrations of hydrocarbon and O in the reactant gas mixture.
  • the methane-containing feed and the oxygen-containing gas are mixed in such amounts to give a carbon to oxygen (i.e., O 2 ) molar ratio from about 1.25:1 to about 3.3:1, more preferably, from about 1.3:1 to about 2.2:1, and most preferably from about 1.5:1 to about 2.2:1, especially the stoichiometric ratio of 2:1.
  • the hydrocarbomoxygen (i.e., O 2 ) molar ratio of the reactant gas mixture is an important variable for maintaining the partial oxidation reaction and the desired product selectivities. Residence time, amount of feed preheat and amount of nitrogen dilution, if used, also affect the selectivity and yield of reaction products.
  • the dwell time or residence time of the portion of gas mixture in contact with the catalyst is preferably maintained at no more than about 10 milliseconds.
  • This ultra short contact time is accomplished by passing the reactant gas mixture over or through one or more of the above-described cobalt-containing catalyst devices at a space velocity of about 20,000 to about 100,000,000 normal liters of gas per kilogram of catalyst per hour (NL/kg/h).
  • the space velocity is about 50,000 to about 50,000,000 NL/kg/h.
  • the process is operated at atmospheric or superatmospheric pressures, the latter being preferred.
  • the pressures may be from about 100 kPa to about 12,500 kPa, preferably from about 130 kPa to about 10,000 kPa.
  • the process is preferably operated at temperatures of from about 60°C to about 1,200°C, preferably from about 700°C to about 1,100°C.
  • the hydrocarbon feedstock and the oxygen-containing gas are preferably pre-heated at about 60°C - 700°C, preferably from about 100°C to about 500°C, before contact with the catalyst.
  • the hydrocarbon feedstock and the oxygen-containing gas are passed over the catalyst at any of a variety of space velocities.
  • the product gas mixture emerging from the reactor is collected and may be routed to a syngas-consuming process such as a Fischer-Tropsch operation. While the preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention.

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Abstract

L'invention concerne un procédé d'oxydation catalytique partielle d'hydrocarbures légers tels que le méthane. Ledit procédé consiste à convertir une charge d'hydrocarbure en mettant en contact un courant d'alimentation comprenant la charge d'hydrocarbure et un gaz contenant de l'oxygène avec un catalyseur dans une zone de réaction maintenue dans des conditions favorisant la conversion dans un réacteur, avec un temps de contact d'une milliseconde, afin d'obtenir un courant d'effluent contenant essentiellement du monoxyde de carbone et de l'hydrogène. Certains catalyseurs préférés de l'invention comprennent du métal de cobalt et/ou des composés contenant du cobalt, un promoteur, et un support réfractaire pouvant produire de façon efficace un gaz de synthèse à haute sélectivité pour les produits de CO et de H2.
PCT/US2000/031451 1999-11-17 2000-11-15 Catalyseurs a base de cobalt et procede de production de gaz de synthese WO2001036323A2 (fr)

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EP1386665A1 (fr) * 2002-08-01 2004-02-04 Conoco Phillips Company Prétraitement hydrothermal pour augmenter la taille moyenne des pores de supports de catalyseurs
US6958309B2 (en) 2002-08-01 2005-10-25 Conocophillips Company Hydrothermal pretreatment for increasing average pore size in a catalyst support
US7041621B2 (en) 2003-01-17 2006-05-09 Conocophillips Company Sulfided catalysts for improved performance in hydrocarbon processing
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