This content is not included in your SAE MOBILUS subscription, or you are not logged in.
Sulfur Poisoning and Regeneration of Pd Catalyst under Simulated Emission Conditions of Natural Gas Engine
ISSN: 0148-7191, e-ISSN: 2688-3627
Published October 29, 2007 by SAE International in United States
Annotation ability available
Palladium-based catalyst can be employed for natural gas exhaust clean up due to its high activity for light hydrocarbon oxidation. Unfortunately, trace amounts of sulfur in the natural gas feed severely deactivate the catalyst.
In this paper, SO2 adsorption over a monolithic Pd/Al2O3 oxidation catalyst is monitored in a time-resolved manner in the presence of 100 ppm SO2 under simulated aging conditions of a natural gas engine, which is correlated with the oxidation activity for CO and hydrocarbons such as CH4, C2H6 and C3H8. The SO2 adsorption is saturated in 0.5 h at 400°C and 100,000 h-1. The molar ratio of adsorbed SO2 and Pd is about 2/1, indicating SO2 molecules adsorbed, or transferred to the Al2O3 support. The oxidation activity gets stabilized upon saturation of sulfur adsorption, and the hydrocarbon oxidation activity cannot recover even when 100 ppm SO2 is completely removed from the stream. The light-off temperatures (T50) of hydrocarbons shift 50-100°C higher after SO2 poisoning.
When the gas stream was switched to the fuel-rich mode, 15% of the adsorbed SO2 molecules were released from the poisoned catalyst at 400°C. No H2S was detected in the outlet stream in the reducing atmosphere. Only traces of SO2 molecules were detected when the regenerating temperature increased to 550°C. The poisoned Pd catalyst was reactivated to some degree, but suffered from a significant deactivation in 30 min even in the absence of SO2, regardless of regenerating temperature. The results revealed the existence of reversible and irreversible sulfur in the reducing atmosphere. A mechanism of sulfur poisoning and regeneration is proposed.
CitationHu, L. and Williams, S., "Sulfur Poisoning and Regeneration of Pd Catalyst under Simulated Emission Conditions of Natural Gas Engine," SAE Technical Paper 2007-01-4037, 2007, https://doi.org/10.4271/2007-01-4037.
SAE 2007 Transactions Journal of Fuels and Lubricants
Number: V116-4; Published: 2008-08-15
Number: V116-4; Published: 2008-08-15
- Samsam Bakhtiari A.M. “The price of natural gas” OPEC Review 25 4 2001 357 368
- Gelin Patrick Primet Michel “Complete oxidation of methane at low temperature over noble metal based catalysts: a review” Applied Catalysis B: Environmental 39 2002 1 37
- Lambert J.K. Kazi M.S. Farrauto R.J. “Methane Emission Abatement form Lean Burn Natural Gas Vehicle Exhaust: Sulfur's Impact on Catalyst Performance” SAE Paper No. 961971
- McCormick Robert L. Newlin Anthony W. Mowery Deborah Graboski Michael S. Ohno T. R. “Rapid Deactivation of Lean-Burn Natural Gas Engine Exhaust Oxidation Catalysts” SAE Paper No. 961976
- Lampert Jordan K. Shahjahan Kazi M. Farrauto Robert J. “Palladium catalyst performance for methane emissions abatement from lean burn natural gas vehicles” Applied Catalysis B: Environmental 14 1997 211 223
- Hoyos Luis Javier Praliaud Helene Primet Michel “Catalytic combustion of methane over palladium supported on alumina and silica in presence of hydrogen sulfide” Applied Catalysis A: General 98 1993 125 138
- Arosio F. Colussi S. Groppi G. Trovarelli A. “Regeneration of S-poisoned Pd/Al 2 O 3 catalysts for the combustion of methane” Catalysis Today 117 2006 569 576
- Leprince Thierry Aleixo Joe Williams Shazam Naseri Mojghan “Regeneration of palladium based catalyst for methane abatment” CIMAC Congress 2004 Paper No. 210
- Williams Shazam Naseri Mojghan Aleixo Joe Sandelin Kristoffer “Field experience and laboratory analysis of oxidation catalyst on dual fuel engines” ASME Conference Paper No. ICES2006-1362
- Mowery Deborah L. Graboski Michael S. Ohno Tim R. McCormick Robert L. “Deactivation of PdO-Al 2 O 3 oxidation catalyst in lean-burn natural gas engine exhaust: aged catalyst characterization and studies of poisoning by H 2 O and SO 2 ” Applied Catalysis B: Environmental 21 1999 157 169
- Heck Ronald M. Farrauto Robert J. Gulati Suresh T. Catalytic Air Pollution Control 2nd New York John Wiley & Sons 2002
- Mowery Deborah L. McCormick Robert L. “Deactivation of alumina supported and unsupported PdO methane oxidation catalyst: the effect of water on sulfate poisoning” Applied Catalysis B: Environmental 34 2001 287 297
- Gelin Patrick Urfels Laetitia Primet Michel Tena Emmanuel “Complete oxidation of methane at low temperature over Pt and Pd catalysts for the abatement of lean-burn natural gas fuelled vehicles emissions: influence of water and sulphur containing compounds” Catalysis Today 83 2003 45 57
- Zou Weiqing Gonzalez Richard D. “Thermal stability of silica supported palladium catalysts prepared by the sol-gel method” Applied Catalysis A: General 126 1995 351 364
- Jones J.M. Dupont A. Brydson R. Fullerton D.J. Nasri N.S. Ross A.B. Westwood A.V.K. “Sulphur poisoning and regeneration of precious metal catalysed methane combustion” Catalysis Today 81 2003 589 601
- Pelovski Y. Petkova V. “Mechanism and kinetics of inorganic sulphates decomposition” Journal of Thermal Analysis 49 1997 1227 1241
- Neyestanaki Ahmad Kalantar Klingstedt Fredrik Salmi Tapio Murzin Dmitry Yu. “Deactivation of postcombustion catalysts, a review” Fuel 83 2004 395 408
- Farrauto R.J. Hobson M.C. Kennelly T. Waterman E.M. “Catalytic chemistry of supported palladium for combustion of methane” Applied Catalysis A: General 81 1992 227 237
- Lapisardi G. Urfels L. Gelin P. Primet M. Kaddouri A. Garbowski E. Toppi S. Tena E. “Superior catalytic behaviour of Pt-doped Pd catalysts in the complete oxidation of methane at low temperature” Catalysis Today 117 2006 564 568