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Mechanistic and Kinetic Analysis of Complete Methane Oxidation on a Practical PtPd/Al2O3 Catalyst

Journal Article · · Catalysts
 [1];  [1];  [2];  [2];  [1];  [3]
  1. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
  2. Johnson Matthey Inc., Wayne, PA (United States)
  3. CONSOL Energy Inc., Canonsburg, PA (United States)
+ Show Author Affiliations
A PtPd/Al2O3 catalyst developed for the complete oxidation of methane from the ventilation air of underground coal mines is compared against a model PdO/Al2O3 catalyst. Although the PtPd/Al2O3 catalyst is substantially more active and stable than the model catalyst, the nature of active sites between the two catalysts is deemed to be fundamentally the same based on their response to different feed gas compositions and the evolution of surface CO adsorption complexes during time-resolved CO adsorption DRIFTS experiment. For both catalysts, coordinatively unsaturated Pd sites are considered the active centers for methane activation and the subsequent oxidation reaction. H2O competes with CH4 for the same active sites, resulting in severe inhibition. Additionally, the CH4 oxidation reaction also causes self-inhibition. Taking both inhibition effects into consideration, a relatively simple kinetic model is developed. The model provides a good fit of the 72 sets of kinetic data collected on the PtPd/Al2O3 catalyst under practically relevant reaction conditions with CH4 concentration in the range of 0.05–0.4%, H2O concentration of 1.0–5.0%, and reaction temperatures of 450–700 °C. Kinetic parameters based on the model suggest that the CH4 activation energy on the PtPd/Al2O3 catalyst is 96.7 kJ/mol, and the H2O adsorption energy is –31.0 kJ/mol. Both values are consistent with the parameters reported in the literature. The model can be used to develop catalyst sizing guidelines and be incorporated into the control algorithm of the catalytic system.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
Grant/Contract Number:
AC05-00OR22725; AR0001532
OSTI ID:
2478726
Alternate ID(s):
OSTI ID: 2483408
Journal Information:
Catalysts, Journal Name: Catalysts Journal Issue: 12 Vol. 14; ISSN 2073-4344
Publisher:
MDPICopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
H2O inhibition effect
Pd-based catalysts
kinetic model
methane oxidation
self-inhibition
surface reconstruction