Pierre Alexandre Glaude

Experimental Confirmation of the Low-Temperature Oxidation Scheme of Alkanes†

The control of auto-ignition can allow to increase the efficiency of internal combustion engines with clear potential positive effects on the problem of global warming.[1] The design of internal combustion engines,[2] as well as the improvement of safety in oxidation processes,[3] rely on a good understanding of the kinetic mechanism of the auto-ignition of organic compounds. Here we experimentally demonstrate a key assumption of this mechanism, which has been accepted for more than 20 years but never proven.[4-6] A detailed speciation of the hydroperoxides responsible for the gas-phase auto-ignition of organic compounds has been achieved for the first time, thanks to the development of a new system coupling a jet stirred reactor to a molecular-beam mass spectrometer combined with tunable synchrotron vacuum ultraviolet (SVUV) photoionization. The formation of alkylhydroperoxides (ROOH) and of carbonyl compounds including a hydroperoxide function (ketohydroperoxide) has been observed under conditions close to those actually observed before the auto-ignition. This result gives the experimental confirmation of an assumption made in all the detailed kinetic mechanisms developed to model auto-ignition phenomena.

Towards cleaner combustion engines through groundbreaking detailed chemical kinetic models

In the context of limiting the environmental impact of transportation, this critical review discusses new directions which are being followed in the development of more predictive and more accurate detailed chemical kinetic models for the combustion of fuels. In the first part, the performance of current models, especially in terms of the prediction of pollutant formation, is evaluated. In the next parts, recent methods and ways to improve these models are described. An emphasis is given on the development of detailed models based on elementary reactions, on the production of the related thermochemical and kinetic parameters, and on the experimental techniques available to produce the data necessary to evaluate model predictions under well defined conditions (212 references).

Products from the oxidation of linear isomers of hexene.

The experimental study of the oxidation of the three linear isomers of hexene was performed in a quartz isothermal jet-stirred reactor (JSR) at temperatures ranging from 500 to 1100 K including the negative temperature coefficient (NTC) zone, at quasi-atmospheric pressure (1.07 bar), at a residence time of 2 s and with dilute stoichiometric mixtures. The fuel and reaction product mole fractions were measured using online gas chromatography. In the case of 1-hexene, the JSR has also been coupled through a molecular-beam sampling system to a reflectron time-of-flight mass spectrometer combined with tunable synchrotron vacuum ultraviolet photoionization. A difference of reactivity between the three fuels, which varies with the temperature range has been observed and is discussed according to the changes in the possible reaction pathways when the double bond is displaced. An enhanced importance of the reactions via the Waddington mechanism and of those of allylic radicals with HO2 radicals can be noted for 2- and 3-hexenes compared to 1-hexene.

Ethanol as an Alternative Fuel in Gas Turbines: Combustion and Oxidation Kinetics

Some research is currently carried out in order to limit CO2 emissions in power generation. Among alternative fuels to natural gas and gasoil in gas turbines, ethanol offers some advantages. However, while the studies dealing with the combustion of methanol are numerous, the research devoted to ethanol flames is rather scarce, in particular with regard to the use in gas turbines. The combustion of ethanol has been theoretically studied by means of a detailed kinetic model well validated in flame conditions. Thanks to quantum chemistry calculations, the reactions necessary to represent low temperature oxidation have been identified and incorporated in the mechanism and their rate parameters have been determined. Several key parameters, such as auto-ignition temperature (AIT), ignition delay times, laminar burning velocities of premixed flames, adiabatic flame temperatures, and formation of pollutants such as CO and NOx have been investigated in an effort to covers gas turbine applications. One has also explored conditions close to ambient in order to address the related safety aspects (leakages of ethanol). To take into account the potential presence of water in ethanol based fuels, similar studies have been performed for ethanol-water-air mixtures. At last, the data have been compared with those calculated for methane combustion. In the low pressure range, the calculated minimum ignition temperatures have been found to be very sensitive to the pressure and the equivalence ratio for lean mixtures. For pressures above 5 bar and moderately lean or rich mixtures, AITs tend to remain close to 440K. Ignition delay times have been calculated in adiabatic conditions at constant pressure. Surprisingly the addition of limited water contents has a very low influence on these results. The addition of water in the ethanol-air mixture decreases slightly the flame temperatures. In the low temperature range, water increases slightly the auto ignition delay times whereas an opposite effect is observed at high temperature. Calculated flame speed has been compared to that deduced from empirical relations found in the literature and the agreement is satisfactory. The formation of CO in pure ethanol flame was always higher than in methane flame while NO formation showed no difference between the amount calculated in ethanol flame and in methane flame. This result is consistent with the slight difference observed between the adiabatic flame temperatures for the two fuels. When increasing the water content up to 10% in ethanol, the laminar velocities become close to those calculated for methane.Copyright

DME as a Potential Alternative Fuel for Gas Turbines: A Numerical Approach to Combustion and Oxidation Kinetics

Many investigations are currently carried out in order to reduce CO2 emissions in power generation. Among alternative fuels to natural gas and gasoil in gas turbine applications, dimethyl ether (DME; formula: CH3 -O-CH3 ) represents a possible candidate in the next years. This chemical compound can be produced from natural gas or coal/biomass gasification. DME is a good substitute for gasoil in diesel engine. Its Lower Heating Value is close to that of ethanol but it offers some advantages compared to alcohols in terms of stability and miscibility with hydrocarbons. While numerous studies have been devoted to the combustion of DME in diesel engines, results are scarce as far as boilers and gas turbines are concerned. Some safety aspects must be addressed before feeding a combustion device with DME because of its low flash point (as low as −83°C), its low auto-ignition temperature and large domain of explosivity in air. As far as emissions are concerned, the existing literature shows that in non premixed flames, DME produces less NOx than ethane taken as parent molecular structure, based on an equivalent heat input to the burner. During a field test performed in a gas turbine, a change-over from methane to DME led to a higher fuel nozzle temperature but to a lower exhaust gas temperature. NOx emissions decreased over the whole range of heat input studied but a dramatic increase of CO emissions was observed. This work aims to study the combustion behavior of DME in gas turbine conditions with the help of a detailed kinetic modeling. Several important combustion parameters, such as the auto-ignition temperature (AIT), ignition delay times, laminar burning velocities of premixed flames, adiabatic flame temperatures, and the formation of pollutants like CO and NOx have been investigated. These data have been compared with those calculated in the case of methane combustion. The model was built starting from a well validated mechanism taken from the literature and already used to predict the behavior of other alternative fuels. In flame conditions, DME forms formaldehyde as the major intermediate, the consumption of which leads in few steps to CO then CO2 . The lower amount of CH2 radicals in comparison with methane flames seems to decrease the possibility of prompt-NO formation. This paper covers the low temperature oxidation chemistry of DME which is necessary to properly predict ignition temperatures and auto-ignition delay times that are important parameters for safety.Copyright