Comprehensive mechanisms for combustion chemistry: An experimental and numerical study with emphasis on applied sensitivity analysis. Technical progress report, February 15, 1991--February 14, 1992

摘要

This research program is an integrated effort to determine the reaction mechanisms responsible for the oxidation of small molecule hydrocarbon structures under conditions representative of combustion environments. The experimental aspects of the work are conducted in an atmospheric pressure flow reactor (APFR) as well as in a new variable pressure flow reactor (VPFR) facility which extends the ranges of parameters available in the APFR, particularly the pressure, (1--15 atm.), the temperature (600 K to 1200 K), and the observation time (10 to 5000 milli-seconds). Gas sampling of stable reactant, intermediate, and product species concentrations provide substantial definition of not only the phenomenology of reaction mechanisms, but a much more constrained set of pure kinetic information than can be derived in flames, or shock tubes. Analytical techniques used for detecting hydrocarbons and carbon oxides include gas chromatography, gas chromatography/mass spectrometry for off-time analyses. Non-dispersive infrared and Fourier transform. Infrared methods are utilized for continuous on-line sample detection of light hydrocarbons, carbon oxides, and oxygenated species. The modeling aspects of the program emphasize the use of hierarchical mechanistic construction along with path and elemental gradient sensitivity analyses in developing detailed kinetic mechanisms. Modeling using a well defined and validated mechanism for the CO/H(sub 2)/Oxidant systems and perturbations of experimental oxidations by small amounts of additives are also used to derive absolute reaction rates and to investigate the compatibility of elementary kinetic rate information.