Mixtures of light alkanes and oxygen can be converted into useful products
by catalytic partial oxidation in excess fuel at moderate temperature. The
relative importance of homogeneous chemistry in the reactions is still a su
bject of active debate, and, in this paper, the gas-phase partial oxidation
of methane was simulated using detailed chemical reaction mechanisms. The
sensitivity of homogeneous chemistry to the addition of trace amounts of ra
dical and molecular species was analyzed to evaluate both the possibility o
f heterogeneous assistance to gas-phase reactions and the effectiveness of
different species which might be added as promoters of particular product s
electivities. Seeding of reaction mixtures with 2% of radicals reduced the
homogeneous ignition delay time by only 50% at 1400 K. The delay was fairly
insensitive to particular radical seeds because the radical pool adjusts r
apidly. Seeding does not alter the product selectivity to CO and H-2 except
at low conversion. (C) 1999 by The Combustion Institute.