WO1993001130A1 - Catalyseur servant a la production de monoxyde de carbone - Google Patents

Catalyseur servant a la production de monoxyde de carbone Download PDF

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Publication number
WO1993001130A1
WO1993001130A1 PCT/GB1992/001200 GB9201200W WO9301130A1 WO 1993001130 A1 WO1993001130 A1 WO 1993001130A1 GB 9201200 W GB9201200 W GB 9201200W WO 9301130 A1 WO9301130 A1 WO 9301130A1
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WO
WIPO (PCT)
Prior art keywords
oxide
metal
group
catalyst
methane
Prior art date
Application number
PCT/GB1992/001200
Other languages
English (en)
Inventor
Ashok Kumar Bhattacharya
Original Assignee
University Of Warwick
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB919114323A external-priority patent/GB9114323D0/en
Priority claimed from GB919118163A external-priority patent/GB9118163D0/en
Application filed by University Of Warwick filed Critical University Of Warwick
Publication of WO1993001130A1 publication Critical patent/WO1993001130A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C01B3/40—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • 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
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • 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
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials

Definitions

  • This invention concerns a process for the partial catalytic oxidation of methane to carbon monoxide and either hydrogen or steam or a mixture of hydrogen and steam.
  • Carbon monoxide is a very useful material for organic synthesis. Methane is widely available from natural gas deposits, but until now no practical
  • a method of oxidising methane to carbon monoxide and either hydrogen or steam or a mixture of hydrogen and steam comprises contacting oxygen and excess methane with a catalyst comprising a platinum group metal and/or metal oxide supported on a lanthanide oxide, and/or an oxide of a metal from group IIIA and/or an oxide from a metal from group IVA of the Periodic Table and/or alumina.
  • the platinum-group metal is preferably palladium, others are platinum, rhodium and iridium.
  • One preferred lanthanide oxide is cerium oxide
  • one preferred oxide of a metal from group IIIA of the Periodic Table is yttrium oxide
  • one preferred oxide of a metal from group IVA of the Periodic Table is zirconium oxide.
  • ABO3 where A is an alkaline earth metal and B is another metal such as Ti, Zr, Hf or Ce e.g. Ba may also be used, e.g. BaCeO 3 , SrCeO 3 , BaZrO 3 , SrZrO 3 and SrTiO 3 .
  • the reaction is preferably carried out at around 750°C. At temperatures of around 500-600°C a mixture of CO and CO 2 is obtained . At higher temperatures the proportion of CO increases and at lower temperatures the proportion of CO 2 increases. In the case of CeO 2 almost no CO 2 is produced at a temperature of 750°C. The proportion of hydrogen to steam produced increases with increasing temperature.
  • the palladium or other platinum group metal may preferably be deposited on an oxide as specified above and that metal oxide may, in turn, be coated onto any high surface area thermally-stable support, such as a ceramic material.
  • Fig.1 is a graph showing the amounts of CO and CO 2 obtained from the oxidation of CH 4 using Pd/CeO 2 and CeO 2 catalysts and various temperatures;
  • Fig.2 is a graph showing the percentages of CO and CO 2 at different space velocities using a Pd/CeO 2
  • a thin layer of palladium metal was deposited on a number of catalyst supports. This was done by treating the supports with palladium nitrate and decomposing it by heating to 550°C. The initial decomposition produces a mixture of palladium metal and oxide. This may be used as it is or may be reduced e.g. with hydrogen, to convert some or all of the oxide to the metal.
  • the Ceo 2 , Y 2 O 3 and Zr ⁇ 2 supports used were obtained commercially from
  • TiO 2 was purchased from Tioxide Ltd.
  • Al 2 O 3 was obtained commercially or prepared by standard preparative ceramic techniques or by the known hydroxide precipitation method.
  • the BaCeO 3 and SrCeO 3 were obtained by standard ceramic methods from commercially-available oxides (e.g. those supplied by Johnson Matthey pic) or from nitrates (also available from Johnson Matthey pic).
  • the resulting supported catalysts were then utilised to catalyse the reaction between excess methane and oxygen at 750°C.
  • SiO 2 was particularly unsatisfactory. The use of SiO 2 is outside the scope of this invention.
  • Fig. 1 is a graph comparing the yields of CO 2 and CO obtained by utilising a variety of supports at different temperatures.
  • Fig. 1 shows clearly that as the temperature approaches 750°C, the amounts of CO 2 and CO produced fall and rise respectively, for a supported Pd catalyst as specified in this invention (i.e. Pd/CeO 2 ).
  • Pd/CeO 2 a supported Pd catalyst as specified in this invention
  • the use of the CeO 2 support alone as catalyst is shown by way of comparison only.
  • a mixture of CO, CO 2 , H 2 O and H 2 is useful as such in the synthesis of methanol and other alcohols.
  • a process for the production of methanol comprises passing methane and oxygen over a catalyst as defined above at a temperature such that a mixture of CO, CO 2 , H 2 O, H 2 , and possibly unreacted CH 4 is obtained in
  • the oxygen may be supplied as air and the methane synthesis catalyst may be a commercially available one e.g. a copper oxide/zinc oxide/alumina catalyst, such as that available from ICI.
  • Fig. 2 shows that the conversion to CO rather than CO 2 is favoured by carrying out the reaction at higher space velocities.
  • the catalyst layer was obtained by the decomposition of palladium nitrate.
  • Other known methods can also be used (e.g. decomposition of palladium acetate or chloramines) involving different preparative techniques, and supports from different sources can also be employed having different physical properties.
  • the method of deposition and the exact nature of the support affect both the conversion and the selectivity of the catalyst.
  • Other factors which affect the performance of the catalyst are the space velocity (see Fig. 2),
  • methane:oxygen ratio the partial pressures of methane and oxygen in the gas being treated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Catalysts (AREA)

Abstract

Procédé d'oxydation partielle de méthane en monoxyde de carbone comprenant la mise en contact de l'oxygène et du métal en surplus avec un catalyseur comprenant un métal du groupe platine et/ou un oxyde de métal supporté sur un oxyde de lanthanide et/ou un oxyde d'un métal du groupe IIIA et/ou un oxyde d'un métal du groupe IVA du tableau périodique et/ou de l'oxyde d'aluminium. Le métal du groupe platine est, de préférence, du palladium, les autres sont du platine, du rhodium et de l'iridium. Un oxyde de lanthanide préféré est l'oxyde de cérium, un oxyde préféré d'un métal du groupe IIIA du tableau périodique est l'oxyde d'yttrium et un oxyde préféré d'un métal du groupe IVA du tableau périodique est l'oxyde de zirconium.
PCT/GB1992/001200 1991-07-02 1992-07-02 Catalyseur servant a la production de monoxyde de carbone WO1993001130A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9114323.0 1991-07-02
GB919114323A GB9114323D0 (en) 1991-07-02 1991-07-02 Palladium catalyst for methane oxidation
GB9118163.6 1991-08-22
GB919118163A GB9118163D0 (en) 1991-08-22 1991-08-22 Palladium catalyst for methane oxidation

Publications (1)

Publication Number Publication Date
WO1993001130A1 true WO1993001130A1 (fr) 1993-01-21

Family

ID=26299176

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1992/001200 WO1993001130A1 (fr) 1991-07-02 1992-07-02 Catalyseur servant a la production de monoxyde de carbone

Country Status (2)

Country Link
EP (1) EP0546152A1 (fr)
WO (1) WO1993001130A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2274284A (en) * 1992-12-23 1994-07-20 Snam Progetti Catalytic process for producing synthesis gas
EP0640561A1 (fr) * 1993-08-24 1995-03-01 Shell Internationale Researchmaatschappij B.V. Procédé pour l'oxydation partielle d'hydrocarbures
WO1995018062A1 (fr) * 1993-12-27 1995-07-06 Shell Internationale Research Maatschappij B.V. Procede d'oxydation catalytique partielle d'hydrocarbures
WO1995018063A1 (fr) * 1993-12-27 1995-07-06 Shell Internationale Research Maatschappij B.V. Procede de preparation de monoxyde de carbone et/ou d'hydrogene
US5753385A (en) * 1995-12-12 1998-05-19 Regents Of The University Of California Hybrid deposition of thin film solid oxide fuel cells and electrolyzers
US5753143A (en) * 1996-03-25 1998-05-19 Northwestern University Process for the CO2 reforming of methane in the presence of rhodium zeolites
EP1134188A2 (fr) * 2000-03-02 2001-09-19 The Boc Group, Inc. Oxydation partielle catalytique d'hydrocarbures
US6458334B1 (en) * 2000-03-02 2002-10-01 The Boc Group, Inc. Catalytic partial oxidation of hydrocarbons
US6572787B1 (en) 1998-01-20 2003-06-03 Shell Oil Company Evacuation of hydrogen and carbon monoxide from a hydrocarbonaceous feedstock
GB2363380B (en) * 1999-03-24 2004-05-19 Univ Lehigh Production of formaldehyde from CH4 and H2S
US6946114B2 (en) 2000-09-05 2005-09-20 Conocophillips Company Lanthanide-promoted rhodium catalysts and process for producing synthesis gas
US7066984B2 (en) 2003-09-25 2006-06-27 The Boc Group, Inc. High recovery carbon monoxide production process
US7090826B2 (en) 2002-12-23 2006-08-15 The Boc Group, Inc. Monolith based catalytic partial oxidation process for syngas production
SG129247A1 (en) * 2002-05-09 2007-02-26 Boc Group Inc Metal catalyst and method of preparation and use
US7214331B2 (en) 2004-02-26 2007-05-08 The Boc Group, Inc. Catalyst configuration and methods for syngas production
US7230035B2 (en) 2002-12-30 2007-06-12 Conocophillips Company Catalysts for the conversion of methane to synthesis gas
US7351275B2 (en) 2004-12-21 2008-04-01 The Boc Group, Inc. Carbon monoxide production process

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0291857A2 (fr) * 1987-05-18 1988-11-23 Air Products And Chemicals, Inc. Méthode de production d'oxyde de carbone

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0291857A2 (fr) * 1987-05-18 1988-11-23 Air Products And Chemicals, Inc. Méthode de production d'oxyde de carbone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, unexamined applications, C field, vol. 7, no. 118, May 21, 1983 THE PATENT OFFICE JAPANESE GOVERNMENT, *

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2274284B (en) * 1992-12-23 1996-08-07 Snam Progetti Catalytic process for producing synthesis gas
GB2274284A (en) * 1992-12-23 1994-07-20 Snam Progetti Catalytic process for producing synthesis gas
EP0640561A1 (fr) * 1993-08-24 1995-03-01 Shell Internationale Researchmaatschappij B.V. Procédé pour l'oxydation partielle d'hydrocarbures
WO1995018062A1 (fr) * 1993-12-27 1995-07-06 Shell Internationale Research Maatschappij B.V. Procede d'oxydation catalytique partielle d'hydrocarbures
WO1995018063A1 (fr) * 1993-12-27 1995-07-06 Shell Internationale Research Maatschappij B.V. Procede de preparation de monoxyde de carbone et/ou d'hydrogene
US5486313A (en) * 1993-12-27 1996-01-23 Shell Oil Company Process for the preparation of carbon monoxide and/or hydrogen
AU682239B2 (en) * 1993-12-27 1997-09-25 Shell Internationale Research Maatschappij B.V. Process for the catalytic partial oxidation of hydrocarbons
CN1044354C (zh) * 1993-12-27 1999-07-28 国际壳牌研究有限公司 烃类催化部分氧化工艺方法
US5753385A (en) * 1995-12-12 1998-05-19 Regents Of The University Of California Hybrid deposition of thin film solid oxide fuel cells and electrolyzers
US5753143A (en) * 1996-03-25 1998-05-19 Northwestern University Process for the CO2 reforming of methane in the presence of rhodium zeolites
US6572787B1 (en) 1998-01-20 2003-06-03 Shell Oil Company Evacuation of hydrogen and carbon monoxide from a hydrocarbonaceous feedstock
GB2363380B (en) * 1999-03-24 2004-05-19 Univ Lehigh Production of formaldehyde from CH4 and H2S
EP1134188A2 (fr) * 2000-03-02 2001-09-19 The Boc Group, Inc. Oxydation partielle catalytique d'hydrocarbures
US6551959B2 (en) * 2000-03-02 2003-04-22 The Boc Group, Inc. Catalytic monolith substrate made of ceria and titania
US6458334B1 (en) * 2000-03-02 2002-10-01 The Boc Group, Inc. Catalytic partial oxidation of hydrocarbons
EP1134188A3 (fr) * 2000-03-02 2004-06-09 The Boc Group, Inc. Oxydation partielle catalytique d'hydrocarbures
US6946114B2 (en) 2000-09-05 2005-09-20 Conocophillips Company Lanthanide-promoted rhodium catalysts and process for producing synthesis gas
SG129247A1 (en) * 2002-05-09 2007-02-26 Boc Group Inc Metal catalyst and method of preparation and use
US7090826B2 (en) 2002-12-23 2006-08-15 The Boc Group, Inc. Monolith based catalytic partial oxidation process for syngas production
US7230035B2 (en) 2002-12-30 2007-06-12 Conocophillips Company Catalysts for the conversion of methane to synthesis gas
US7066984B2 (en) 2003-09-25 2006-06-27 The Boc Group, Inc. High recovery carbon monoxide production process
US7214331B2 (en) 2004-02-26 2007-05-08 The Boc Group, Inc. Catalyst configuration and methods for syngas production
US7351275B2 (en) 2004-12-21 2008-04-01 The Boc Group, Inc. Carbon monoxide production process

Also Published As

Publication number Publication date
EP0546152A1 (fr) 1993-06-16

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