An Experimental Study Into The Ignition Of Methane And Ethane Blends In A New Shock Tube Facility

A new shock tube targeting low temperature, high pressure, and long test times was designed and installed at the Turbomachinery Laboratory in December of 2008. The single-pulse shock tube uses either lexan diaphragms or die-scored aluminum disks of up to 4 mm in thickness. The modular design of the tube allows for optimum operation over a large range of thermodynamic conditions from 1 to 100 atm and between 600-4000 K behind the reflected shock wave. The new facility allows for ignition delay time, chemical kinetics, high-temperature spectroscopy, vaporization, atomization, and solid particulate experiments. An example series of ignition delay time experiments was made on mixtures of CH4/C2H6/O2/Ar at pressures from 1 to 30.7 atm, intermediate temperatures from 1082 to 2248 K, varying dilutions (between 75 and 98% diluent), and equivalence ratios ranging from fuel lean (0.5) to fuel rich (2.0) in this new facility. The percentage by volume variation and equivalence ratios for the mixtures studied were chosen to cover a wide parameter space not previously well studied. Results are then used to validate and improve a detailed kinetics mechanism which models the oxidation and ignition of methane and other higher order hydrocarbons, through C4, with interest in further developing reactions important to methane- and ethane-related chemistry.

The combustion behavior of methane and ethane is important to the study of natural gas and other alternative fuels that are comprised primarily of these two basic hydrocarbons. Understanding the transition from methane-dominated ignition kinetics to ethane-dominated kinetics for increasing levels of ethane is also of fundamental interest toward the understanding of hydrocarbon chemical kinetics. Much research has been conducted on the two fuels individually, but experimental data of the combustion of blends of methane and ethane is limited to ratios that recreate typical natural gas compositions (up to ~20% ethane molar concentration). The goal of this study was to provide a comprehensive data set of ignition delay times of the combustion of blends of methane and ethane at near atmospheric pressure.

NOx produced during combustion can persist in the exhaust gases of a gas turbine engine in quantities significant to induce regulatory concerns. There has been much research which has led to important insights into NOx chemistry. One method of NOx reduction is exhaust gas recirculation. In exhaust gas recirculation, a portion of the exhaust gases that exit are redirected to the inlet air stream that enters the combustion chamber, along with fuel. Due to the presence of NOx in the exhaust gases which are subsequently introduced into the burner, knowledge of the effects of NOx on combustion is advantageous. Contrary to general NOx research, little has been conducted to investigate the sensitizing effects of NO2 and N2O addition to methane/oxygen combustion. Experiments were made with dilute and real fuel air mixtures of CH4/O2/Ar with the addition of NO2 and N2O. The real fuel air concentrations were made with the addition of NO2 only. The equivalence ratios of mixtures made were 0.5, 1 and 2. The experimental pressure range was 1 - 44 atm and the temperature range tested was 1177--2095 K. The additives NO2 and N2O were added in concentrations from 831 ppm to 3539 ppm. The results of the mixtures with NO2 have a reduction in ignition delay time across the pressure ranges tested, and the mixtures with N2O show a similar trend. At 1.3 atm, the NO2 831 ppm mixture shows a 65% reduction and shows a 75% reduction at 30 atm. The NO2 mixtures showed a higher decrease in ignition time than the N2O mixtures. The real fuel air mixture also showed a reduction. Sensitivity Analyses were performed. The two most dominant reactions in the NO2 mixtures are the reaction O+H2 = O+OH and the reaction CH3+NO2 = CH3O+NO. The presence of this second reaction is the means by which NO2 decreases ignition delay time, which is indicated in the experimental results. The reaction produces CH3O which is reactive and can participate in chain propagating reactions, speeding up ignition. The two dominant reactions for the N2O mixture are the reaction O+H2 = O+OH and, interestingly, the other dominant reaction is the reverse of the initiation reaction in the N2O-mechanism: O+N2+M = N2O+M. The reverse of this reaction is the direct oxidation of nitrous oxide. The O produced in this reaction can then speed up ignition by partaking in propagation reactions, which was experimentally observed.

Methane-Air mixture in Argon heat bath is ignited by shock, reflected from the endwall of shock tube. Experiments are compared with numerical prediction based on Bowman's reaction scheme including Zel'dovich mechanism. Agreement between experimental density profiles and numerical prediction is very good. Methane absorption outside the boundary layer agrees well with computation based on isobaric combustion. Measurements in the boundary layer, albeit with insufficient space resolution, are in accord with the predicted trends.

High-pressure experiments and chemical kinetics modeling were performed for laminar spherically expanding flames for methane/air, ethane/air, methane/ethane/air and propane/air mixtures at pressures between 1 and 10 atm and equivalence ratios ranging from 0.7 to 1.3. All experiments were performed in a new flame speed facility capable of withstanding initial pressures up to 15 atm. The facility consists of a cylindrical pressure vessel rated up to 2200 psi. Vacuums down to 30 mTorr were produced before each experiment, and mixtures were created using the partial pressure method. Ignition was obtained by an automotive coil and a constant current power supply capable of reducing the spark energy close to the minimum ignition energy. Optical cine-photography was provided via a Z-type schlieren set up and a high-speed camera (2000 fps). A full description of the facility is given including a pressure rating and a computational conjugate heat transfer analysis predicting temperature rises at the walls. Additionally, a detailed uncertainty analysis revealed total uncertainty in measured flame speed of approximately +-0.7 cm/s. This study includes first-ever measurements of methane/ethane flame speeds at elevated pressures as well as unique high pressure ethane flame speed measurements. Three chemical kinetic models were used and compared against measured flame velocities. GRI 3.0 performed remarkably well even for high-pressure ethane flames. The C5 mechanism performed acceptably at low pressure conditions and under-predicted the experimental data at elevated pressures. Measured Markstein lengths of atmospheric methane/air flames were compared against values found in the literature. In this study, Markstein lengths increased for methane/air flames from fuel lean to fuel rich. A reverse trend was observed for ethane/air mixtures with the Markstein length decreasing from fuel lean to fuel rich conditions. Flame cellularity was observed for mixtures at elevated pressures. For both methane and ethane, hydrodynamic instabilities dominated at stoichiometric conditions. Flame acceleration was clearly visible and used to determine the onset of cellular instabilities. The onset of flame acceleration for each high-pressure experiment was recorded.

Supercritical carbon dioxide (sCO2) cycles are being investigated for the future of power generation. These cycles will contribute to a carbon-neutral future to combat the effects of climate change. These direct-fired closed cycles will produce power without adding significant pollutants to the atmosphere. For these cycles to be efficient, they will need to operate at significantly higher pressures (e.g., 300 atm for Allam Cycle) than existing systems (typically less than 40 atm). There is limited knowledge on combustion at these pressures or at the high dilution of carbon dioxide. Nominal fuel choices for gas turbines include natural gas and syngas (mixture of CO and H2). Shock tubes study these problems in order to understand the fundamentals and solve various challenges. Shock tube experiments have been studied by the author in the sCO2 regime for various fuels including natural gas, methane and syngas. Using the shock tube to take measurements, pressure and light emissions time-histories measurements were taken at a 2-cm axial location away from the end wall. Experiments for syngas at lower pressure utilized high-speed imaging through the end wall to investigate the effects of bifurcation. It was found that carbon dioxide created unique interactions with the shock tube compared to tradition bath gasses such as argon. The experimental results were compared to predictions from leading chemical kinetic mechanisms. In general, mechanisms can predict the experimental data for methane and other hydrocarbon fuels; however, the models overpredict for syngas mixtures. Reaction pathway analysis was evaluated to determine where the models need improvements. A new shock tube has been designed and built to operate up to 1000 atm pressures for future high-pressure experiments. Details of this new facility are included in this work. The experiments in this work are necessary for mechanism development to design an efficient combustor operate these cycles.

This is the first volume of a two volume set which presents the results of the 31st International Symposium on Shock Waves (ISSW31), held in Nagoya, Japan in 2017. It was organized with support from the International Shock Wave Institute (ISWI), Shock Wave Research Society of Japan, School of Engineering of Nagoya University, and other societies, organizations, governments and industry. The ISSW31 focused on the following areas: Blast waves, chemical reacting flows, chemical kinetics, detonation and combustion, ignition, facilities, diagnostics, flow visualization, spectroscopy, numerical methods, shock waves in rarefied flows, shock waves in dense gases, shock waves in liquids, shock waves in solids, impact and compaction, supersonic jet, multiphase flow, plasmas, magnetohyrdrodynamics, propulsion, shock waves in internal flows, pseudo-shock wave and shock train, nozzle flow, re-entry gasdynamics, shock waves in space, Richtmyer-Meshkov instability, shock/boundary layer interaction, shock/vortex interaction, shock wave reflection/interaction, shock wave interaction with dusty media, shock wave interaction with granular media, shock wave interaction with porous media, shock wave interaction with obstacles, supersonic and hypersonic flows, sonic boom, shock wave focusing, safety against shock loading, shock waves for material processing, shock-like phenomena, and shock wave education. These proceedings contain the papers presented at the symposium and serve as a reference for the participants of the ISSW 31 and individuals interested in these fields.

This thesis describes a new facility and method of experimentation, which can be used to study the combustion chemistry of low-volatility fuels in the gas phase. Two main goals are described: first, the development of the aerosol shock tube and procedures; and second, a demonstration of its capabilities. There is a lack of high-quality, accurate chemical kinetics data for the oxidation of large hydrocarbons, which are important for modeling diesel, rocket, or jet engines among other combustion systems. While conventional shock tubes are very effective reactor vessels for low-molecular-weight gaseous fuels (n-alkanes up to five carbon atoms), larger fuel molecules exist as low-volatility liquids/solids, and the vapor-pressures of these fuels are not large enough for high or even moderate fuel loadings. Heating the shock tube has extended the use of shock tubes to carbon numbers of 10 to 12, but beyond that, the high temperatures prior to the shock initiation can decompose the fuel, and (for fuel mixtures like diesel) can cause fractional distillation. The question is then: how can we study low-vapor-pressure fuels in a shock tube? The solution presented here, which avoids the problems associated with heating, is called the aerosol shock tube. In the aerosol shock tube, the fuel is injected as an aerosol of micron-size droplets. Then a series of shock waves first evaporate the fuel and subsequently raise the resultant purely gas-phase mixture to combustion-relevant temperatures. With proper selection of the shock strength and timing, this process effectively decouples the mass and heat transfer processes associated with evaporation from the chemical mechanism of combustion. This enables the study of extremely low-volatility fuels, never before studied in a purely gas-phase form in a shock tube. The first application of this new facility was to measure the ignition delay time for many previously inaccessible fuels in the gas-phase. In this thesis, we have measured ignition delay times for the pure surrogate fuel components n-decane, n-dodecane, n-hexadecane, and methyl decanoate as well as for multi-component fuels such as JP-7 and multiple different blends of diesel fuel. Taken over a range of conditions, these measurements provide sensitive validation targets for their respective chemical mechanisms. These data showed agreement with past heated shock tube experiments for fuels in which premature fuel decomposition is not an issue (n-decane and low concentration n-dodecane). However, when comparing heated and aerosol shock tube ignition delay times for fuels that require significant heating, like n-hexadecane, the existing heated shock tube data demonstrated evidence of premature decomposition. The second application to the study of chemical kinetics was to measure the concentration of important species during the decomposition and oxidation of select low-vapor-pressure fuels. These species time-histories provide much more information for kinetic mechanism refinement. Experiments were performed to measure the important OH radical and the stable intermediate C2H4 for both n-hexadecane and diesel. The number of important low-vapor-pressure fuels that require high-quality validation targets is large, and our new method for providing this data has proven very effective. This work enables the development of the next generation of accurate chemical mechanisms and will be essential to their success.

Experimental data for ignition delay times and species time-histories (CH4) were obtained in mixtures diluted with CO2. Experiments were performed behind reflected shockwaves from temperatures of 1200 to 2000 K for pressures ranging from 1 to 11 atm. Ignition times were obtained from emission and laser absorption measurements. Current experimental data were compared with the predictions of detailed chemical kinetic models (available from literature) that will allow for accurate design and modeling of combustion systems.