Investigation of the partial oxidation of methane/n-heptane-mixtures and the interaction of methane and n-heptane under ultra-rich conditions

The homogeneous partial oxidation of methane is an interesting approach to obtain useful chemicals like synthesis gas, higher hydrocarbons, aldehydes or alcohols. Because of the low reactivity of methane, the homogeneous conversion needs high temperatures to proceed at reasonable reaction rates. Additives like n-heptane form reactive intermediates at comparatively low temperatures and initiate the conversion. To study the kinetics of doped conversion reactions, fuel-rich diluted methane/n-heptane/oxygen/argon-mixtures (2 <= Phi <= 20) were investigated in a plug-flow reactor at a pressure of 6 bar, at intermediate temperatures between 423 and 973K and at relatively long residence times (7 <= tau <= 14s). The product composition at the reactor outlet is analyzed by gas chromatography and mass spectrometry. Species profiles as a function of equivalence ratio and temperature are compared with simulations, and serve as validation data for different reaction mechanisms. Rates of production and reaction paths are analyzed to investigate the interaction of methane and n-heptane during the oxidation process. They show that the chemical interaction of the oxidation products of both fuels has a promoting effect on the formation of different useful products like carbon monoxide, methanol or ethane. To prove this observation, mole fraction profiles as a function of temperature were compared between experiments with an equivalence ratio of Phi = 8 using neat methane, neat n-heptane and methane/n-heptane mixtures as fuels. The results show that the yields of these species are much higher in case of the methane/n-heptane mixture compared to the yields obtained in the neat methane and neat n-heptane conversions or the sum of both. (C) 2019 The Combustion Institute. Published by Elsevier Inc. All rights reserved.