Detailed kinetic models for the low-temperature auto ignition of gasoline surrogates

In the context of the search for gasoline surrogates for kinetic modeling purpose, this paper describes a new model for the low-temperature auto-ignition of n-heptane/iso-octane/hexene/toluene blends for the different linear isomers of hexene. The model simulates satisfactory experimental results obtained in a rapid compression machine for temperatures ranging from 650 to 850 K in the case of binary and ternary mixtures including iso octane, 1-hexene and toluene. Predictive simulations have also been performed for the autoignition of n heptane/iso octane/hexene/toluene quaternary mixtures: the predicted reactivity is close to that of pure iso octane with a retarding effect when going from 1- to 3-alkene.Comment: European Combustion Meeting 2009 (ECM 2009), Vienne : Autriche (2009

Reaction Mechanisms in Petroleum: From Experimentation to Upgrading and Geological Conditions

Among the numerous questions that arise concerning the exploitation of petroleum from unconventional reservoirs, lie the questions of the composition of hydrocarbons present in deep seated HP-HT reservoirs or produced during in-situ upgrading steps of heavy oils and oil shales. Our research shows that experimental hydrocarbon cracking results obtained in the laboratory cannot be extrapolated to geological reservoir conditions in a simple manner. Our demonstration is based on two examples: 1) the role of the hydrocarbon mixture composition on reaction kinetics (the "mixing effect") and the effects of pressure (both in relationship to temperature and time). The extrapolation of experimental data to geological conditions requires investigation of the free-radical reaction mechanisms through a computed kinetic model. We propose a model that takes into account 52 reactants as of today, and which can be continuously improved by addition of new reactants as research proceeds. This model is complete and detailed enough to be simulated in large ranges of temperature (150-500\degree C) and pressures (1-1500 bar). It is thus adapted to predict the hydrocarbons evolution from upgrading conditions to geological reservoirs.Comment: 8th World Congress of Chemical Engineering, Montr\'eal : Canada (2009

Development of a detailed kinetic model for the combustion of biomass

International audienceIn the context of the growing utilization of biomass to produce energy and of the related need to decrease pollutant emissions from domestic wood combustion devices, this paper presents a new kinetic model of wood combustion considering especially in details the gas-phase reactions related to the combustion of the tars produced by the biomass devolatization. The tar production is predicted using a semi-detailed mechanism of the literature. The tar gas-phase combustion model has been built as a compilation of literature mechanisms already proposed for these species, except for hydroxyacetaldehyde for which a new oxidation mechanism has been written. Experiments on the thermochemical behavior of three types of wood (beech, fir and oak) were also performed in parallel of this work using Thermogravimetric Analysis (TGA). The new detailed kinetic model of wood combustion, BioPOx (Biomass Pyrolysis and Oxidation), has been tested against a wide range of experimental results published in literature. This model fairly reproduces experimental results for pyrolysis and combustion of biomass and its constituents, key produced tars from biomass pyrolysis, and key compounds for Polycyclic Aromatic Hydrocarbons (PAH) formation, for a wide range of experimental devices and operating conditions.

Prediction of Auto-Ignition Temperatures and Delays for Gas Turbine Applications

International audienceGas turbines burn a large variety of gaseous fuels under elevated pressure and temperature conditions. During transient operations like maintenance, start-ups or fuel transfers, variable gas/air mixtures are involved in the gas piping system. Therefore, in order to predict the risk of auto-ignition events and ensure a safe and optimal operation of gas turbines, it is of the essence to know the lowest temperature at which spontaneous ignition of fuels may happen. Experimental auto-ignition data of hydrocarbon-air mixtures at elevated pressures are scarce and often not applicable in specific industrial conditions. AIT data correspond to temperature ranges in which fuels display an incipient reactivity, with time scales amounting in seconds or even in minutes instead of milliseconds in flames. In these conditions, the critical reactions are most often different from the ones governing the reactivity in a flame or in high temperature ignition. Some of the critical paths for AIT, especially those involving peroxy radicals, are similar to those encountered in slow oxidation. Therefore, the main available kinetic models that have been developed for fast combustion, are unfortunately unable to represent properly these low temperature processes.In this context, a numerical approach addressing the influence of process conditions on the minimum auto-ignition temperature of different fuel/air mixtures has been developed. For that purpose, several chemical models available in the literature have been tested, in order to identify the most robust ones. Based on previous works of our group, a model covering a large temperature range has been developed, which offers a fair reconciliation between experimental and calculated AIT data through a wide range of fuel compositions. This model has been validated against experimental auto-ignition delay times (AID) corresponding to high temperature in order to ensure its relevance not only for AIT aspects but also for the reactivity of gaseous fuels over the wide range of gas turbine operation conditions. In addition, the AITs of methane, of pure light alkanes and of various blends representative of several natural gas and process-derived fuels were extensively covered. In particular, among alternative gas turbine fuels, hydrogen-rich gases are called to play an increasing part in the future so that their ignition characteristics have been addressed with particular care. Natural gas enriched with hydrogen, and different CO/H2 syngas fuels originating from a blast furnace (BFG) have namely been studied. Globally, the individual species covered are: H2, CO, CO2, N2, CH4, C2H6, C3H8, C4H10, and C5H12. AIT values have been evaluated in function of the equivalence ratio and pressure. All the results obtained have been fitted by means of a practical mathematical expression. The overall study leads to a simple correlation of AIT versus equivalence ratio/pressure that may be of fruitful use for the engineering community

Prediction of auto-ignition temperatures and delays for gas turbine applications

International audienceGas turbines burn a large variety of gaseous fuels under elevated pressure and temperature conditions. During transient operations, variable gas/air mixtures are involved in the gas piping system. In order to predict the risk of auto-ignition events and ensure a safe operation of gas turbines, it is of the essence to know the lowest temperature at which spontaneous ignition of fuels may happen. Experimental auto-ignition data of hydrocarbon–air mixtures at elevated pressures are scarce and often not applicable in specific industrial conditions. Auto-ignition temperature (AIT) data correspond to temperature ranges in which fuels display an incipient reactivity, with timescales amounting in seconds or even in minutes instead of milliseconds in flames. In these conditions, the critical reactions are most often different from the ones governing the reactivity in a flame or in high temperature ignition. Some of the critical paths for AIT are similar to those encountered in slow oxidation. Therefore, the main available kinetic models that have been developed for fast combustion are unfortunately unable to represent properly these low temperature processes. A numerical approach addressing the influence of process conditions on the minimum AIT of different fuel/air mixtures has been developed. Several chemical models available in the literature have been tested, in order to identify the most robust ones. Based on previous works of our group, a model has been developed, which offers a fair reconciliation between experimental and calculated AIT data through a wide range of fuel compositions. This model has been validated against experimental auto-ignition delay times corresponding to high temperature in order to ensure its relevance not only for AIT aspects but also for the reactivity of gaseous fuels over the wide range of gas turbine operation conditions. In addition, the AITs of methane, of pure light alkanes, and of various blends representative of several natural gas and process-derived fuels were extensively covered. In particular, among alternative gas turbine fuels, hydrogen-rich gases are called to play an increasing part in the future so that their ignition characteristics have been addressed with particular care. Natural gas enriched with hydrogen, and different syngas fuels have been studied. AIT values have been evaluated in function of the equivalence ratio and pressure. All the results obtained have been fitted by means of a practical mathematical expression. The overall study leads to a simple correlation of AIT versus equivalence ratio/pressure

Primary reactions of the thermal decomposition of tricyclodecane

In order to better understand the thermal decomposition of polycyclanes, the pyrolysis of tricyclodecane has been studied in a jet-stirred reactor at temperatures from 848 to 933 K, for residence times between 0.5 and 6 s and at atmospheric pressure, in order to obtain a conversion between 0.01 and 25 %. The main products of the reaction are hydrogen, methane, ethylene, ethane, propene, 1,3-cyclopentadiene, cyclopentene, benzene, 1,5-hexadiene, toluene and 3-cyclopentyl-cyclopentene. A primary mechanism containing all the possible initiation steps, including those involving diradicals, as well as propagation reactions has been developed and allows experimental results to be satisfactorily modeled. The main reaction pathways of consumption of tricyclodecane and of formation of the main products have been derived from flow rate and sensitivity analyses

Reactive Transport and Its Implications on Heavy Oil HTGC Analysis – A Coupled Thermo-Hydro-Chemical (THC) Multiphysics Modelling Approach

This chapter provides an insight into the reactive transport in a capillary column which heavy-oil hydrocarbons undergo when analysed by high temperature gas chromatography (HTGC), and their implications on characterisation outcomes, namely thermal cracking of the injected sample; and incomplete or non-elution of heavy components from the column, by using a coupled Thermo-Hydro-Chemical (THC) multiphysics modelling approach. For this purpose, a computational coupled THC, multicomponent, multi-physics model is developed, accounting for: multiphase equilibrium using an in-house, extended thermodynamics distribution factors dataset, up to nC98H198; transport and fluid flow in COMSOL and MATLAB; and chemical reactions using kinetics and mechanisms of the thermal cracking, in CHEMKIN. The determination of the former extended dataset is presented using two complementary HTGC modes: i) High-Efficiency mode, with a long column operated at low flow rate; and ii) true SimDist mode, with a short column operated at high flow rate and elution up to nC100H202