Shock tube study of the fuel structure effects on the chemical kinetic mechanisms responsible for soot formation

Soot formation in toluene-, benzene-, and acetylene-oxygen-argon mixtures was investigated to study soot formation in a combustion environment. High concentrations of oxygen completely suppress soot formation. The addition of oxygen at relatively low concentrations uniformly suppresses soot formation at high pressures, while at relatively lower pressures it suppresses soot formation at higher temperatures while promoting soot production at lower temperatures. The observed behavior indicates that oxidation reactions compete with ring fragmentation. The main conclusion to be drawn from the results is that the soot formation mechanism is probably the same for the pyrolysis and oxidation of hydrocarbons. That is, the addition of oxygen does not alter the soot route but rather promotes or inhibits this route by means of competitive reactions. An approach to empirical modeling of soot formation during pyrolysis of aromatic hydrocarbons is also presented

Shock tube study of the fuel structure effects on the chemical kinetic mechanisms responsible for soot formation, part 2

Soot formation in oxidation of allene, 1,3-butadiene, vinylacetylene and chlorobenzene and in pyrolysis of ethylene, vinylacetylene, 1-butene, chlorobenzene, acetylen-hydrogen, benzene-acetylene, benzene-butadiene and chlorobenzene-acetylene argon-diluted mixtures was studied behind reflected shock waves. The results are rationalized within the framework of the conceptual models. It is shown that vinylacetylene is much less sooty than allene, which indicates that conjugation by itself is not a sufficient factor for determining the sooting tendency of a molecule. Structural reactivity in the context of the chemical kinetics is the dominant factor in soot formation. Detailed chemical kinetic modeling of soot formation in pyrolysis of acetylene is reported. The main mass growth was found to proceed through a single dominant route composed of conventional radical reactions. The practically irreversible formation reactions of the fused polycyclic aromatics and the overshoot by hydrogen atom over its equilibrium concentration are the g-driving kinetic forces for soot formation

Extended Simulations of Graphene Growth with Updated Rate Coefficients

New simulations of graphene growth in flame environments are presented. The simulations employ a kinetic Monte Carlo (KMC) algorithm coupled to molecular mechanics (MM) geometry optimization to track individual graphenic species as they evolve. Focus is given to incorporation of five-member rings and resulting curvature and edge defects. The model code has been re-written to be more computationally efficient enabling a larger set of simulations to be run, decreasing stochastic fluctuations in the averaged results. The model also includes updated rate coefficients for graphene edge reactions recently published in the literature. The new simulations are compared to results from the previous model as well as to hydrogen to carbon ratios recorded in experiment and calculated with alternate models

Influence of in-bed catalysis by ash-coated olivine on tar formation in steam gasification of biomass

The use of catalytic bed materials has become a state-of-the-art solution to control the concentration of tar in fluidized bed biomass steam gasifiers. Ash-coated olivine is commonly applied as bed material, owing to its relatively high catalytic activity towards tar species. However, the mechanisms and conversion pathways influenced by the ash-coated olivine when applied as an in-bed catalyst are still not well understood. The present work aims at proving that the ash-layered olivine prevents the formation of biomass-derived tar at an early stage of their formation. Tests with olivine at different stages of activation and at different temperatures are carried out in the Chalmers 2-4MWth DFB gasifier. Detailed characterization of the tar and light hydrocarbon fractions are presented and discussed in relation to the sources of aromatic species. It is concluded that the ash-coated olivine prevents the formation of aromatic tar species by promoting the steam reforming of early tar precursors. Gas-phase interactions of the early tar precursors and bed material contribute to the tar reduction observed. The results indicate that olivine interferes the cyclization routes involving C2H2 and C3 hydrocarbons

Uncertainty Quantification in Chemical Modeling

A module of PrIMe automated data-centric infrastructure, Bound-to-Bound Data Collaboration (B2BDC), was used for the analysis of systematic uncertainty and data consistency of the H2/CO reaction model (73/17). In order to achieve this purpose, a dataset of 167 experimental targets (ignition delay time and laminar flame speed) and 55 active model parameters (pre-exponent factors in the Arrhenius form of the reaction rate coefficients) was constructed. Consistency analysis of experimental data from the composed dataset revealed disagreement between models and data. Two consistency measures were applied to identify the quality of experimental targets (Quantities of Interest, QoI): scalar consistency measure, which quantifies the tightening index of the constraints while still ensuring the existence of a set of the model parameter values whose associated modeling output predicts the experimental QoIs within the uncertainty bounds; and a newly-developed method of computing the vector consistency measure (VCM), which determines the minimal bound changes for QoIs initially identified as inconsistent, each bound by its own extent, while still ensuring the existence of a set of the model parameter values whose associated modeling output predicts the experimental QoIs within the uncertainty bounds. The consistency analysis suggested that elimination of 45 experimental targets, 8 of which were self- inconsistent, would lead to a consistent dataset. After that the feasible parameter set was constructed through decrease uncertainty parameters for several reaction rate coefficients. This dataset was subjected for the B2BDC framework model optimization and analysis on. Forth methods of parameter optimization were applied, including those unique in the B2BDC framework. The optimized models showed improved agreement with experimental values, as compared to the initiallyassembled model. Moreover, predictions for experiments not included in the initial dataset were investigated. The results demonstrate benefits of applying the B2BDC methodology for development of predictive kinetic models

Polycyclic aromatic hydrocarbon processing in interstellar shocks

Context: PAHs appear to be an ubiquitous interstellar dust component but the effects of shocks waves upon them have never been fully investigated. Aims: To study the effects of energetic (~0.01-1 keV) ion (H, He and C) and electron collisions on PAHs in interstellar shock waves.Methods: We calculate the ion-PAH and electron-PAH nuclear and electronic interactions, above the threshold for carbon atom loss from a PAH, in 50-200 km/s shock waves in the warm intercloud medium. Results: Interstellar PAHs (Nc = 50) do not survive in shocks with velocities greater than 100 km/s and larger PAHs (Nc = 200) are destroyed for shocks with velocities greater/equal to 125 km/s. For shocks in the ~75 - 100 km/s range, where destruction is not complete, the PAH structure is likely to be severely denatured by the loss of an important fraction (20-40%) of the carbon atoms. We derive typical PAH lifetimes of the order of a few x10^8 yr for the Galaxy. These results are robust and independent of the uncertainties in some key parameters that have yet to be well-determined experimentally. Conclusions: The observation of PAH emission in shock regions implies that that emission either arises outside the shocked region or that those regions entrain denser clumps that, unless they are completely ablated and eroded in the shocked gas, allow dust and PAHs to survive in extreme environments.Comment: 19 pages, 11 figures, 3 tables, typos corrected and PAH acronym in the title substituted with full name to match version published in Astronomy and Astrophysic

Soot surface growth and oxidation in laminar unsaturated-hydrocarbon/air diffusion flames

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/77246/1/AIAA-2002-1116-550.pd