Gilles Bourque

Ignition and Oxidation of 50/50 Butane Isomer Blends

One of the alkanes found within gaseous fuel blends of interest to gas turbine applications is butane. There are two structural isomers of butane, normal butane and iso-butane, and the combustion characteristics of either isomer are not well known. Of particular interest to this work are mixtures of n-butane and iso-butane. A shock-tube experiment was performed to produce important ignition delay time data for these binary butane isomer mixtures which are not currently well studied, with emphasis on 50–50 blends of the two isomers. These data represent the most extensive shock-tube results to date for mixtures of n-butane and iso-butane. Ignition within the shock tube was determined from the sharp pressure rise measured at the endwall which is characteristic of such exothermic reactions. Both experimental and kinetics modeling results are presented for a wide range of stoichiometry (φ = 0.3–2.0), temperature (1056–1598 K), and pressure (1–21 atm). The results of this work serve as validation for the current chemical kinetics model. Correlations in the form of Arrhenius-type expressions are presented which agree well with both the experimental results and the kinetics modeling. The results of an ignition-delay-time sensitivity analysis are provided, and key reactions are identified. The data from this study are compared with the modeling results of 100% normal butane and 100% iso-butane. The 50/50 mixture of n-butane and iso-butane was shown to be more readily ignitable than 100% iso-butane but reacts slower than 100% n-butane only for the richer mixtures. There was little difference in ignition time between the lean mixtures.Copyright

Ignition and Flame Speed Kinetics of Two Natural Gas Blends With High Levels of Heavier Hydrocarbons

High-pressure experiments and chemical kinetics modeling were performed to generate a database and a chemical kinetic model that can characterize the combustion chemistry of methane-based fuel blends containing significant levels of heavy hydrocarbons (up to 37.5% by volume). Ignition delay times were measured in two different shock tubes and in a rapid compression machine at pressures up to 34 atm and temperatures from 740 K to 1660 K. Laminar flame speeds were also measured at pressures up to 4 atm using a high-pressure vessel with optical access. Two different fuel blends containing ethane, propane, n-butane, and n-pentane added to methane were studied at equivalence ratios varying from lean (0.3) to rich (2.0). This paper represents the most comprehensive set of experimental ignition and laminar flame speed data available in the open literature for CH 4 /C 2 H 6 /C 3 H 8 /C 4 H 10 /C 5 H 12 fuel blends with significant levels of C2 + hydrocarbons. Using these data, a detailed chemical kinetics model based on current and recent work by the authors was compiled and refined. The predictions of the model are very good over the entire range of ignition delay times, considering the fact that the data set is so thorough. Nonetheless, some improvements to the model can still be made with respect to ignition times at the lowest temperatures and for the laminar flame speeds at pressures above 1 atm and at rich conditions.

Ignition Delay Time and Laminar Flame Speed Calculations for Natural Gas/Hydrogen Blends at Elevated Pressures

Applications of natural gas and hydrogen co-firing have received increased attention in the gas turbine market, which aims at higher flexibility due to concerns over the availability of fuels. While much work has been done in the development of a fuels database and corresponding chemical kinetics mechanism for natural gas mixtures, there are nonetheless few if any data for mixtures with high levels of hydrogen at conditions of interest to gas turbines. The focus of the present paper is on gas turbine engines with primary and secondary reaction zones as represented in the Alstom and Rolls Royce product portfolio. The present effort includes a parametric study, a gas turbine model study, and turbulent flame speed predictions. Using a highly optimized chemical kinetics mechanism, ignition delay times and laminar burning velocities were calculated for fuels from pure methane to pure hydrogen and with natural gas/hydrogen mixtures. A wide range of engine-relevant conditions were studied: pressures from 1 to 30 atm, flame temperatures from 1600 to 2200 K, primary combustor inlet temperature from 300 to 900 K, and secondary combustor inlet temperatures from 900 to 1400 K. Hydrogen addition was found to increase the reactivity of hydrocarbon fuels at all conditions by increasing the laminar flame speed and decreasing the ignition delay time. Predictions of turbulent flame speeds from the laminar flame speeds show that hydrogen addition affects the reactivity more when turbulence is considered. This combined effort of industrial and university partners brings together the know-how of applied, as well as experimental and theoretical disciplines.

LAMINAR FLAME SPEED MEASUREMENTS AND MODELING OF ALKANE BLENDS AT ELEVATED PRESSURES WITH VARIOUS DILUENTS

Laminar flame speeds at elevated pressure for methane-based fuel blends are important for refining the chemical kinetics that are relevant at engine conditions. The present paper builds on earlier measurements and modeling by the authors by extending the validity of a chemical kinetics mechanism to laminar flame speed measurements obtained in mixtures containing significant levels of helium. Such mixtures increase the stability of the experimental flames at elevated pressures and extend the range of laminar flame speeds. Two experimental techniques were utilized, namely a Bunsen burner method and an expanding spherical flame method. Pressures up to 10 atm were studied, and the mixtures ranged from pure methane to binary blends of CH4 /C2 H6 and CH4 /C3 H8 . In the Bunsen flames, the data include elevated initial temperatures up to 650 K. There is generally good agreement between model and experiment, although some discrepancies still exist with respect to equivalence ratio for certain cases. A significant result of the present study is that the effect of mixture composition on flame speed is well captured by the mechanism over the extreme ranges of initial pressure and temperature covered herein. Similarly, the mechanism does an excellent job at modeling the effect of initial temperature for methane-based mixtures up to at least 650 K.Copyright

Numerical Study on the Effect of Real Syngas Compositions on Ignition Delay Times and Laminar Flame Speeds at Gas Turbine Conditions

Depending on the feedstock and the production method, the composition of syngas can include (in addition to H2 and CO) small hydrocarbons, diluents (CO2, water, and N2), and impurities (H2S, NH3, NOx, etc.). Despite this fact, most of the studies on syngas combustion do not include hydrocarbons or impurities and in some cases not even diluents in the fuel mixture composition. Hence, studies with realistic syngas composition are necessary to help in designing gas turbines. The aim of this work was to investigate numerically the effect of the variation in the syngas composition on some fundamental combustion properties of premixed systems such as laminar flame speed and ignition delay time at realistic engine operating conditions. Several pressures, temperatures, and equivalence ratios were investigated for the ignition delay times, namely 1, 10, and 35 atm, 900–1400 K, and ϕ = 0.5 and 1.0. For laminar flame speed, temperatures of 300 and 500 K were studied at pressures of 1 atm and 15 atm. Results showed that the addition of hydrocarbons generally reduces the reactivity of the mixture (longer ignition delay time, slower flame speed) due to chemical kinetic effects. The amplitude of this effect is, however, dependent on the nature and concentration of the hydrocarbon as well as the initial condition (pressure, temperature, and equivalence ratio).

NOx Emissions Modeling and Uncertainty From Exhaust-Gas-Diluted Flames

Oxides of nitrogen (NOx) are pollutants emitted by combustion processes during power generation and transportation that are subject to increasingly stringent regulations due to their impact on human health and the environment. One NOx reduction technology being investigated for gas-turbine engines is exhaust-gas recirculation (EGR), either through external exhaust-gas recycling or staged combustion. In this study, the effects of different percentages of EGR on NOx production will be investigated for methane–air and propane–air flames at a selected adiabatic flame temperature of 1800 K. The variability and uncertainty of the results obtained by the gri-mech 3.0 (GRI), San-Diego 2005 (SD), and the CSE thermochemical mechanisms are assessed. It was found that key parameters associated with postflame NO emissions can vary up to 192% for peak CH values, 35% for thermal NO production rate, and 81% for flame speed, depending on the mechanism used for the simulation. A linear uncertainty analysis, including both kinetic and thermodynamic parameters, demonstrates that simulated postflame nitric oxide levels have uncertainties on the order of ±50–60%. The high variability of model predictions, and their relatively high associated uncertainties, motivates future experiments of NOx formation in exhaust-gas-diluted flames under engine-relevant conditions to improve and validate combustion and NOx design tools.

Ignition Delay Time Measurements and Modeling of n- Pentane and iso-Pentane at Elevated Pressures

Ignition delay times of n-pentane and iso-pentane in real fuel-air mixtures with oxygen and nitrogen were measured in a shock tube and a rapid compression machine (RCM). Data were then used to improve the current kinetics model. All results were obtained at an equivalence ratio of 1.0 and at pressures near 1, 10, and 20 atm for the shock tube and 10 and 20 atm for the RCM. Experimental temperatures ranged from 641 to 1410 K. When compared to the chemical kinetics model, in general, ignition delay times were well predicted for n-pentane, while iso-pentane predictions were longer than experimental values in the negative temperature coefficient region. To the authors’ knowledge, this study covers conditions not yet present in the literature and will expand fundamental knowledge of npentane and iso-pentane combustion kinetics.

IGNITION DELAY TIME EXPERIMENTS FOR NATURAL GAS/HYDROGEN BLENDS AT ELEVATED PRESSURES

Applications of natural gases that contain high levels of hydrogen have become a primary interest in the gas turbine market. While the ignition delay times of hydrogen and of the individual hydrocarbons in natural gases can be considered well known, there have been few previous experimental studies into the effects of different levels of hydrogen on the ignition delay times of natural gases at gas turbine conditions. To examine the effects of hydrogen content at gas turbine conditions, shocktube experiments were performed on nine mixtures of an L9 matrix. The L9 matrix was developed by varying four factors: natural gas higher-order hydrocarbon content of 0, 18.75, or 37.5%; hydrogen content of the total fuel mixture of 30, 60, or 80%; equivalence ratios of 0.3, 0.5, or 1; and pressures of 1, 10, or 30 atm. Temperatures ranged from 1092 K to 1722 K, and all mixtures were diluted in 90% Ar. Correlations for each mixture were developed from the ignition delay times and, using these correlations, a factor sensitivity analysis was performed. It was found that hydrogen played the most significant role in the ignition delay times of a mixture. Pressure was almost as important as hydrogen content, especially as temperature increased. Equivalence ratio was slightly more important than hydrocarbon content of the natural gas, but both were less important than pressure or hydrogen content. Comparison with a modern chemical kinetic model demonstrated that the model captures well the relative impacts of H2 content, temperature, and pressure, but some improvements are still needed in terms of absolute ignition delay times.

Ignition and Combustion of Heavy Hydrocarbons Using an Aerosol Shock-Tube Approach

Results from a heterogeneous shock-tube approach recently demonstrated at Texas A&M University, wherein a hydrocarbon fuel is introduced in liquid phase with gaseous oxidizer, are presented. The shock tube has been designed for controlled measurement of ignition delay times, sooting phenomena, radical species concentrations, time-dependent species profiles, and nanoparticle-aided combustion using heavy hydrocarbons which are difficult to study using the traditional shock tube approach. Aerosol is generated in a high-vacuum manifold positioned 4-m from the endwall where optical and pressure-based diagnostics are stationed. The approach reduces the propensity for fuel-film deposition near the endwall avoiding optical and/or kinetic disturbances that could result. The aerosol enters the shock tube initially as a two-phase flow of liquid fuel and gaseous oxidizer/inert gas. Liquid droplets partially evaporate while resident in the shock tube, prior to shock wave generation, and are then completely vaporized behind the incident shock wave. Behind the reflected shock wave, then, resides a pure gas-phase fuel and oxidizer mixture. The primary benefit of the aerosol shock tube approach is the ability to inject fuels of low vapor pressure at high or low concentrations. The classic shock-tube approach introduces gas-phase constituents only, and has difficulty accommodating low vapor-pressure liquids, except when component partial pressures are much lower than what is usually required. In the present work, n-heptane aerosol (C7 H16 , Pvap, 20 °C ∼ 35 torr), was generated with O2 /Ar carrier gas and dispersed in the shock tube in a uniform manner. Stoichiometric ignition delay times with temperature varied from 1240 K to 1600 K and pressure maintained near 2.0 atm are compared to gas-phase data at similar conditions and a chemical kinetic model for heptane combustion. Excellent agreement was found between the two-phase aerosol approach and the classical method involving vapor-phase n-heptane and pre-mixed gases. The measured activation energy for the stoichiometric mixture at 2.0 atm (EA = 42.3 kcal /mol), obtained with the two-phase technique, compares well with the literature value.Copyright

Effect of Higher-Order Hydrocarbons on Methane-Based Fuel Chemistry at Gas Turbine Pressures

A chemical kinetics mechanism designed for the oxidation of methane-hydrocarbon blends at elevated pressures was used to study the effect of higher-order hydrocarbons on ignition delay time and flame speed at gas turbine conditions. The mechanism was developed from recent data and modeling conducted by the authors, including pressures above 30 atm, temperatures as low as 700 K, and alkane additives from C2 H6 through C5 H12 . Calculations focused on three target natural gas mixtures containing CH4 mole fractions from 62.5 to 98%. The results show the effects that pressure, temperature, and hydrocarbon content have on the combustion chemistry of the fuel-air mixtures. For example, autoignition times exhibit nonlinear trends with increasing pressure and decreasing temperature. Experiments in the authors’ laboratories are ongoing, and an overview of the related facilities is provided.Copyright