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At least 1,009 records · Page 56

Fuel Sensitivity of Gas Emissions, Lean Blowout and Combustion Dynamics for a 9-Point LDI Combustor

Fuel sensitivity of gaseous emissions, approach to lean blowout and combustion dynamics are evaluated in this study. Experiments were conducted at the NASA Glenn Research Center's CE-5 flame tube test facility with a 9-point Swirl-Venturi Lean Direct Injection (SV-LDI) combustor. A reference jet fuel (A2) and two test fuels (C1 and C3) from were provided by the National Jet Fuels Combustion Program (NJFCP). C1 is essentially a 2-component iso-paraffin test fuel with a low cetane number of 17, and C3 is a high viscosity test fuel. Approach to lean blowout was monitored in terms of the rapid increase in CO emissions index as equivalence ratio decreased, but testing did not proceed all the way to lean blowout (LBO). Burning C1 was found to produce lower NOx emissions, but C1 flame temperatures were about 25 K higher relative to A2 at near LBO points (where CO emissions increased very rapidly). The NOx emissions of C3 were similar to A2. At low power conditions where fuel injector performance is not optimized for this 9-point LDI combustor, C3 had higher CO emissions than A2 and C1, likely due to C3's higher viscosity relative to A2 and C1. No discernable difference in combustion dynamics was observed between the three fuels tested in the 9-point LDI combustor. While a systematic ignition test campaign was not conducted, it was observed that C1 required a higher equivalence ratio and inlet air temperature for test rig ignition compared to A2 and C3.

Combustion dynamics↗

Fuel Heating System Design and Thermal Modeling for Aviation Combustion Research

Aviation fuels offer substantial heat-sink capability that can be applied to aircraft thermal-management strategies and advanced propulsion-system concepts. Accurate control of fuel temperature is critical for understanding combustion behavior and supporting high temperature fuel experimental studies. This work describes the modeling and experimental validation of a portable, high temperature fuel-conditioning system designed for multiple NASA Glenn Research Center’s combustion facilities. The system utilizes a circulating-oil heating unit and modular tube-in-tube heat exchangers capable of conditioning Jet-A to temperatures approaching 600 K. A Thermal Desktop model was created to analyze heat exchanger configurations and predict performance across a range of operating conditions. Model predictions were compared with measurements collected in the CE-13C test facility, showing good agreement across the tested flow range except at low fuel flow rate around 2 kg/hr. Results provide guidance for sizing future fuel heating system for combustion research applications.

Jet fuel heating system↗

Model-Based Characterization of High Temperature Oxy-Coal Combustion Systems

Reaction Engineering International (REI) is leading a DOE-funded program focused on characterization of the impacts of high temperatures and pressures in oxy-coal combustion systems. The objective is to produce data and validate mechanisms to describe and predict flame behavior, heat transfer, ash deposition and ash chemistry to enable application of these advanced combustion technologies in full-scale systems. This presentation will provide an overview of accomplishments achieved to date on this project and present modeling results of high temperature oxy-coal combustion using undiluted directed oxygen with minimal flue gas recirculation at atmospheric pressure. Comparisons of model results and experimental data from 100 kW and 1.5 MW test furnaces will be provided for gas and wall temperatures, wall heat flux, carbon on ash, ash deposition rates and ash chemistry.

high temperature, modeling↗

Transforming Energy through Computational Excellence. Exascale Computing: Combustion; Simulating Effects of Fuel Injection Location in Supersonic Jet Engines

Computational tractable simulations using an adaptive-mesh-refinement solverfor compressible reacting flows help researchers understand how variations in fuel injection location within the supersonic flow cavity impacts combustion efficiency. By identifying the important physical determinants of the combustion processes, this study shows a promising pathway to improving flame stability and combustion efficiency, as well as reducing emissions.

adaptive mesh refinement↗

Enabling Combustion Science Simulations for Future Exascale Machines

Reacting flow simulations for combustion applications require extensive computing capabilities. Leveraging the AMReX library, the Pele suite of combustion simulation tools targets the largest supercomputers available and future exascale machines. We introduce PeleC, the compressible solver in the Pele suite, and detail its capabilities, including complex geometry representation, chemistry integration, and discretization. We present a comparison of development efforts using both OpenACC and AMReX's C++ performance portability framework for execution on multiple GPU architectures. We discuss relevant details that have allowed PeleC to achieve high performance and scalability. PeleC's performance characteristics are measured through relevant simulations on multiple supercomputers. The success of PeleC's design for exascale is exhibited through demonstration of a 160 billion cell simulation and weak scaling onto 100\% of Summit, an NVIDIA-based GPU supercomputer at Oak Ridge National Laboratory. Our results provide confidence that PeleC will enable future combustion science simulations with unprecedented fidelity.

combustion↗

BENCH-SCALE DEVELOPMENT OF A TRANSFORMATIVE MEMBRANE PROCESS FOR PRE-COMBUSTION CO 2 CAPTURE

This final technical report describes work conducted by Membrane Technology and Research, Inc. (MTR) for the Department of Energy, National Energy Technology Laboratory (DOE NETL) on development of the second generation (Gen-2) Proteus™ membrane modules and a pre-combustion membrane process for carbon dioxide (CO 2 ) capture from an Integrated Gasification Combined Cycle (IGCC) plant for power generation (award number DE-FE0031632). The work was conducted from October 1, 2018 through March 30, 2022. The overall goal of this project was to bring a Gen-2 version of the H2-selective Proteus membrane to bench-scale module (component) testing with real syngas. MTR was assisted in this project by Susteon, a technology development company with extensive experience in gasification processes, and the University of North Dakota Energy & Environmental Research Center (EERC), who provided the host site for the slipstream field testing. This report details the work conducted to optimize the Gen-2 Proteus membrane and develop modules capable of operation at 200°C; demonstrate membrane module performance processing coal-derived syngas during a field test at EERC; and optimize integration of a dual-membrane process into an IGCC with carbon capture. Work for this project included membrane optimization and scale-up, module component screening and fabrication of high-temperature lab- and bench-scale modules, design and fabrication of a bench-scale field test membrane skid, operation of the field test skid processing coal-derived syngas at EERC, and a detailed techno-economic analysis (TEA) of the MTR dual-membrane process for IGCC power plant pre-combustion CO 2 capture. This project validated recent membrane technology advancements, mitigates risk in future scale-up activities, and moved the membrane pre-combustion capture technology from TRL-4 to TRL-5. Key results for each major task are discussed in the report.

10 SYNTHETIC FUELS↗

High-Fidelity Simulations of Supercritical CO2 Based Oxy-Combustion with Non-Ideal Equation of State

The supercritical carbon dioxide (sCO2) Allam-Fetvedt cycle employs high-temperature oxy-combustion using sCO2 as the working fluid, leading to a unique and challenging environment for materials. In this cycle, pressurized gaseous fuel is combusted in the presence of a hot oxidant flow containing a mixture of CO2 and oxygen and a hot CO2 diluent recycle stream at approximately 300 bar under lean combustion conditions. We present high-fidelity reacting simulations of this oxy-combustor environment and compare the results when performing simulations with ideal and non-ideal equations of state. By doing so, we identify if the combustor behavior at the regime of interest is sensitive enough to the equation of state to justify the added computational cost incurred with a non-ideal equation of state.

equation of state↗

Solution combustion synthesis of iron-based alumina catalysts for dehydrogenation of fossil fuels

Microwave-assisted thermocatalytic dehydrogenation of fossil fuels has been proposed as a method for hydrogen production with no CO2 emissions. The byproduct is carbon, which has a commercial value. Iron-based alumina nanocomposites are promising catalysts for this process as they both absorb microwave radiation and catalyze the dehydrogenation. In addition, they may have magnetic properties, which could be used for their separation from the carbon byproduct. Solution combustion synthesis (SCS) is an attractive technique for the fabrication of iron-based alumina nanocomposites because it can produce high specific surface area oxides in a facile manner. However, the effects of the heating mode, the fuel, and the iron/aluminum ratio on the combustion synthesis behavior and the product properties have not been studied yet. In the present work, the iron-based alumina nanocomposites were obtained by SCS using a hotplate, a muffle furnace, and a microwave oven. The initial mixtures were aqueous solutions of iron nitrate, aluminum nitrate, and an organic fuel. The concentrations of the two nitrates were varied in proportion to Fe:Al molar ratios of 1:2, 1:1, and 2:1. Two fuels were tested: citric acid and glycine. The combustion was less vigorous when citric acid was used as the fuel, which is explained by the lower exothermicity of the reaction. X-ray diffraction analysis of the products confirmed the formation of complex oxides of Fe and Al, specifically it detected hercynite and magnetite phases. Brunauer-Emmett-Teller surface area analysis has shown that the powders obtained using citric acid have specific surface areas as high as 276 m2/g, significantly higher than those obtained using glycine. Muffle furnace and hotplate heating led to comparable specific surface areas, while microwave heating resulted in significantly lower specific surface areas. The magnetic properties of the products increase with increasing the Fe/Al molar ratio from 1:2 (no response to a magnetic field) to 1:1 (weak response) and 2:1 (strong response).

solution combustion synthesis, nanoscale oxides, f↗

A multi-chamber model of combustion instabilities and its assessment using kilohertz laser diagnostics in a gas turbine model combustor

A multi-chamber model for the combustion instabilities manifested in a gas turbine model combustor was developed. Here the proposed model was used to explain the dependencies of instability frequency on burner geometry and other flow parameters, some of which could not be reconciled with previous models. The new model was built upon the Helmholtz analysis of two connected resonators. The instability frequency as well as the complex pressure ratio between two chambers were predicted by solving ordinary differential equations. To assess the assumptions and predictions of the proposed model, the spectra and magnitude of the oscillations of pressure, heat release rate, and velocity were measured for four different operating conditions: rich (R1), lean (L1), stoichiometric (S1), and reduced flow rate (R2) with a kilohertz laser diagnostic system. These measurements reconfirmed that the instability is of Helmholtz type. A global equivalence ratio that is consistently greater than unity was identified to be an enabling factor for combustion instability. This is also in agreement with the predictions made by the proposed model. Furthermore, the model was shown to be able to predict the right trend of instability frequency when multiple parameters were changed. It is concluded that the current model is an improvement over previous models, because the acoustic coupling between different chambers of the burner was considered.

42 ENGINEERING↗

Chemical Reactor Network Modeling of Ammonia Rich-Quench-Lean Combustion Using a Partially Stirred Reactor Approach

Ammonia is a promising alternative to hydrogen with high energy density and favorable storage and transport characteristics. However, low flammability and a propensity for high nitrogen oxide (NO x ) emissions make direct utilization challenging. Recently, two-stage rich-quench-lean (RQL) combustion strategies have shown promise in achieving low NO x emissions with ammonia. In this approach, the rich stage serves to oxidize a portion of the fuel while thermally decomposing as much of the remaining ammonia as possible, generating hydrogen. In the second (lean) stage, air is rapidly introduced, burning out the hydrogen and residual ammonia. Two-stage RQL combustion of ammonia has been investigated in the open literature both experimentally and numerically. In general, idealized chemical reactor network (CRN) models predict NO x concentrations below those of 2D/3D computational fluid dynamics models and experiments. The primary drivers of these discrepancies may be largely attributed to finite rate mixing nonadiabatic operation. The typical CRN model is comprised of a perfectly-stirred-reactor (PSR), followed by a plug-flow-reactor (PFR), meant to represent the flame, and postflame zones, respectively. In the two-stage RQL approach two PSR-PFR networks are arranged sequentially, corresponding to the rich and lean stages, with secondary air injection in between. In the authors' past work, this arrangement has demonstrated the significant sensitivity of exit NO x to the rich stage equivalence ratio, while the amount of secondary air injection was shown to be less critical. In this paper, the CRN model is extended to (1) include the impacts of heat loss and (2) utilize a partially-stirred-reactor (PaSR) approach to study the impacts of mixing on emissions performance. Varying amounts of heat loss are applied to the rich relaxation zone to understand emissions performance and changes to optimization of equivalence ratio and residence time. Premixed and nonpremixed configurations are considered in the rich stage PaSR, with varying degrees of mixing intensity to study the interaction between mixing, transport, and kinetic timescales. Critically, the impact of mixing between hot products and secondary air injection is studied to understand practical injector needs. Results show unburnt ammonia leaving the rich stage as a primary contributor to NO x emissions – driven both by increased heat loss and reduced mixing rates. Furthermore, heat losses have been shown to create conditions that are conducive to increased N 2 O formation in the lean stage. In conclusion, the results of this study will be considered in the context of developing optimized two-stage RQL combustors for ammonia.

Combustion↗

Development and Testing of Pulse Guns for Combustion Instability Testing

To test liquid rocket engines (LREs) for combustion instabilities, devices such as bombs are often used to create pressure wave disturbances. Bombs, while effective, are inherently dangerous, expensive, and difficult to procure. Over the years, pulse guns have been used as a safer and more cost-effective way to generate controlled pressure disturbances in engine chambers. In anticipation of the need for stability testing of prototype LREs at NASA Marshall Space Flight Center (MSFC), a set of pulse guns have been designed, fabricated, tested, and characterized. The pulse gun program is funded by the RS-25 Engine Program managed out of MSFC and funded by NASA’s Space Launch System (SLS) through the MSFC Liquid Engines Office (LEO). A pulse gun is a simple device – like a traditional gun, it has a breech and barrel section. However, unlike a traditional gun, there is no bullet, as the purpose of the pulse gun is strictly to fire a high pressure pulse. Instead of a firing pin and primer that would normally be used in a traditional gun, an initiator is used to activate the gun powder. The initiator is a highly reliable pyrotechnic initiator. For this study, clone versions of the NASA Standard Initiator (NSI) were used. The initiator is used to ignite a pre-measured amount of gun powder loaded into the breech. When the pressure of the burnt gun powder exceeds the set point of a downstream burst disk, the disk ruptures, allowing the high pressure pulse to travel downstream through the barrel section. A ballistic pressure transducer located in the breech section is used to measure the short duration, high pressure pulse. Some configurations of the pulse gun have barrel sections that include one or more additional ballistic pressure transducers. These additional pressure measurements help track the degradation and damping of the pulse as it travels out of the barrel section. The measurements may also be used to determine the velocity of pulse. The objective of this paper is to present the different variants of this newly-developed pulse gun and characterize performance over a range of parameters. The parameters include breech diameter, barrel length, amount of gun powder used, the way the gun powder is packed, and the pressure setting of the burst disk. There are a total of six pulse guns: three with the 0.25 inch breech and three different length barrels, and three with the 0.40 inch breech and three different length barrels. For both breech sizes, the associated barrels are referred to as standard, one-port, and two-port barrels. The standard barrel has no instrumentation and is likely the barrel that will be used for engine stability testing. The one- and two-port barrels were designed specifically for pulse gun component testing to allow measurements of the magnitude and timing of the high pressure pulse as it makes its way through the pulse gun. The burst disks tested were commercially-available burst disks designed to rupture at 8,000, 16,000, and 24,000 psid. Testing was accomplished by firing the pulse gun into a test chamber pressurized with nitrogen at about 2300 psig. A total of four Model 113B23 High frequency ICP® pressure sensors (10k psi) were mounted in the test chamber, in the same plane as the pulse gun. Two of the sensors had “trimmed” adapters, and two did not. Given the symmetrical configuration of the sensors within the test chamber, different amplitudes of pressure measurements are attributed to the use of trimmed versus untrimmed adapters. The untrimmed adapters, with their narrower passages, tended to amplify the pressure amplitudes by as much as 50%. In total, 41 pulse gun tests have been conducted.Data are still being analyzed, but some trends are apparent. For example, measurements taken within the pulse gun are shown in Figures 3 and 4 for Hot-fires (HFs) # 11 and 39, respectively. Both tests were identical in that the 0.40 inch ID breech, two-port barrel, 8,000 psid burst disk, and same amount of gunpowder (6.639 grains for HF# 11, and 6.576 grains for HF# 39) were used, and the back pressure in the nitrogen test chamber was ~2300 psig. Despite keeping all these variables constant, the results from these two tests look quite different. For both tests, the first pressure peak shown in the P2111 trace within the breech is the firing of the initiator. The second peak and any subsequent peaks are from the combustion of the gunpowder. It should be noted that because the sensors are dynamic, the ~2300 psig baseline static pressure is not shown in the figures. For HF# 11, the burst disk clearly ruptured in a little over 0.1 ms from the time the initiator was fired. This is evident from the abrupt rise in pressure for P2112 followed by another abrupt rise in pressure for P2113. The sensors track the movement of the high pressure pulse through the pulse gun. For HF# 39, however, there was nearly 1 ms delay between the initiator firing and the burst disk rupturing. The only difference between these two tests was the way in which the gunpowder was packed within the breech. For HF# 11, the gunpowder was poured directly into the breech, atop the initiator, and held in place with a vegetable fiber wad appropriately sized for the barrel diameter. Once in place, the wad firmly held the gunpowder in place. For HF# 39, the gunpowder was rolled within cigarette paper with the ends of the paper twisted. The rolled gunpowder was gently pushed down into the breech, toward the initiator, and no wad was used. This method of loading the gunpowder consistently produced longer delays in the rupture of the burst disk, presumably because there was a steady, fuller burning of the gunpowder. The burst disk was rated for 8,000 psid, which means that the burst disk should not have opened until the pressure in the breech reached ~10,300 since there was ~2300 psig back pressure in the test chamber. In the case of HF# 11, the breech pressure only reached roughly 4200 psi before there was leakage either through or past the burst disk, but for HF#39, the breech pressure reached 10,600 psi prior to the burst disk opening. The temperature of the burst disk is certainly a factor in determining when the burst disk will rupture. A sharp rise in the burst disk temperature could weaken it and cause it to stray from the designed set point burst pressure. The burst disks are manufactured of Inconel to try to reduce their sensitivity to temperature, but how the burst disks perform above 900°F is not documented. All burst disks were engineered and tested by the manufacturer for ambient temperature conditions. One theory for why rolling the gunpowder in cigarette paper may produce better results is related to a more controlled temperature environment. The cigarette paper may act as a sheath that protects the burst disk from excessive temperatures during the rapid buildup of pressure in the breech. The ultimate benefit of not breeching the burst disk prematurely is shown in Figures 5 and 6, which graphs the resultant pressure pulse produced in the test chamber. For HF #11, the peak pressure on the P2123 trimmed adapter is about 270 psi, while for HF# 39 it is 343 psi, which is about 1.27 times greater in magnitude. In either case, the pressure pulse is ~20 μs in width once it reaches the test chamber. Another pressure rise about 100 μs later can be seen on the sensors located across from the pulse gun port, P2124 and P2121. These pressures are lower due to attenuation of the pressure wave as it moves across the test chamber. After the wave encounters the wall, it reflects back and forth within the chamber until it completely dissipates.

Pulse Gun↗

Combustion Properties of Amino-Substituted Guanidinium 4,4',5,5'-Tetranitro-2,2'-biimidazolate(N4BIM) Salts

This paper describes the combustion properties of the amino-substituted guanidinium 4,4’,5,5’-tetranitro-2,2’-biimidazolate (N4BIM) series, including the bis-mono, di and triaminoguanidinium salts. These salts are of interest as propellant ingredient additives, and in particular, the bis-triaminoguanidinium salt of N4BIM displays excellent burn rate and combustion behavior. Our combustion studies have shown that TAGN4-BIM displays a fast burning rate and has the lowest pressure dependence exponent yet measured for a triaminoguanidinium salt.

33 ADVANCED PROPULSION SYSTEMS↗

Investigation of Cycle-to-Cycle Variations in Internal Combustion Engine Using Proper Orthogonal Decomposition

The understanding, modeling and control of the cycle-to-cycle variation (CCV) in the modern internal combustion engine (ICE) is a key scientific challenge to achieve stable engine operation. High CCV in the engine combustion chamber may contribute to partial burn, misfire and knock, which adversely affects the engine performance and may potentially damage the engine. The objective of the current study is to leverage high-fidelity numerical simulations to improve the understanding of the causes of CCV. Using the massively parallel code, Nek5000, multi-cycle, wall-resolved large-eddy simulations (LES) were performed for the General Motors (GM), Transparent Combustion Chamber (TCC-III) optical engine under motored operating conditions. Further, the large-scale structures of the in-cylinder flow were investigated using a triple proper orthogonal decomposition (POD) technique to explore the characteristics of different parts of the flow and their contributions to CCV. The kinetic energy of the subset of flow structures were determined and correlated between the intake and compression strokes. The insights from the analysis of the large-scale flow structures will be used to assist the development of improved engine designs with reduced CCV and enhance the engine performance.

33 ADVANCED PROPULSION SYSTEMS↗

Kinetics of the reduction of hematite (Fe{sub 2}O{sub 3}) by methane (CH{sub 4}) during chemical looping combustion: A global mechanism

Chemical-looping combustion (CLC) has emerged as a promising technology for fossil fuel combustion which produces a sequestration ready concentrated CO{sub 2} stream in power production. A CLC system is composed with two reactors, an air and a fuel reactor. An oxygen carrier such as hematite (94%Fe{sub 2}O{sub 3}) circulates between the reactors, which transfers the oxygen necessary for the fuel combustion from the air to the fuel. An important issue for the CLC process is the selection of metal oxide as oxygen carrier, since it must retain its reactivity through many cycles. The primary objective of this work is to develop a global mechanism with respective kinetics rate parameters such that CFD simulations can be performed for large systems. In this study, thermogravimetric analysis (TGA) of the reduction of hematite (Fe{sub 2}O{sub 3}) in a continuous stream of CH{sub 4} (15, 20, and 35%) was conducted at temperatures ranging from 700 to 825{degrees}C over ten reduction cycles. The mass spectroscopy analysis of product gas indicated the presence of CO{sub 2} and H{sub 2}O at the early stage of reaction and H{sub 2} and CO at the final stage of reactions. A kinetic model based on two parallel reactions, 1) first-order irreversible rate kinetics and 2) Avrami equation describing nucleation and growth processes, was applied to the reduction data. It was found, that the reaction rates for both reactions increase with, both, temperature and the methane concentration in inlet gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CH 4 combustion over a commercial Pd/CeO 2 -ZrO 2 three-way catalyst: Impact of thermal aging and sulfur exposure

Thermal aging and sulfur poisoning are major problems influencing the efficiency and lifetime of natural gas three-way catalysts (TWCs) during real-world operation. In the present study, thermal aging and sulfur-induced deactivations on CH 4 combustion were investigated over commercial monolithic honeycombs, i.e., Pd/CexZr 1-x O 2 (CZ)-based TWCs that are thermally aged in the bench (HTA), followed by being operated behind the stoichiometric natural gas engine in high sulfur fuel (HTA + S). In this work, both HTA and HTA + S samples show degraded performance in CH 4 combustion relative to the fresh one, which are caused by the reconstruction of Pd species induced by thermal aging and the decreased reducibility of the support. The 18 O 2 labelling experiments show that in all cases CH 4 combustion proceeds via a MvK mechanism in which lattice O (OL) plays a key role. The sulfation aging (HTA + S sample) promotes the activation of CH 4 and O 2 by forming Pd δ+ -(SO$_4^{2-}$) δ- and Ce 3+ -VO couples at the interface as compared to HTA sample. However, such a promotion effect could be compromised by the blocking effect of sulfate on the exchange of O L from the bulk to the surface and across the surface. The fundamental understanding of thermal and S deactivation mechanisms from this study could help to predict a real-world lifetime use curve of natural gas TWCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An experimental and kinetic modeling study on dimethyl carbonate (DMC) pyrolysis and combustion

Because of the absence of C–C bonds and the large oxygen content in its molecular structure, dimethyl carbonate (DMC) is a promising oxygenated additive or substitute for hydrocarbon fuels. In order to understand its chemical oxidation and combustion kinetics, flow reactor pyrolysis at different pressures (40, 200 and 1040 mbar) and low-pressure laminar premixed flames with different equivalence ratios (1.0 and 1.5) were investigated. Mole fraction profiles of many reaction intermediates and products were obtained within estimated experimental uncertainties. From theoretical calculations and estimations, a detailed kinetic model for DMC pyrolysis and high-temperature combustion consisting of 257 species and 1563 reactions was developed. The performance of the kinetic model was then analyzed using detailed chemical composition information, primarily from the present measurements. In addition, it was examined against the chemical structure of an opposed-flow diffusion flame, relying on global combustion properties such as the ignition delay times and laminar burning velocities. Furthermore, these extended comparisons yielded overall satisfactory agreement, demonstrating the applicability of the present model over a wide range of high-temperature conditions.

09 BIOMASS FUELS↗

A further experimental and modeling study of acetaldehyde combustion kinetics

Acetaldehyde is an important intermediate and a toxic emission in the combustion of fuels, especially for biofuels. To better understand its combustion characteristics, a detailed chemical kinetic model describing the oxidation of acetaldehyde has been developed and comprehensively validated against various types of literature data including laminar flame speeds, oxidation and pyrolysis in shock tubes, chemical structure of premixed flames, and low-temperature oxidation in jet-stirred reactors. To extend the validation range, the chemical structure of a counterflow flame fueled by acetaldehyde at 600 Torr has been measured using vacuum ultra-violet photoionization molecular-beam mass spectrometry. In addition, ignition delay times at 10 atm and 700-1100 K were measured in a rapid compression machine, and a negative temperature coefficient (NTC) behavior was observed. Here, the present kinetic model well reproduces the results of various acetaldehyde combustion experiments covering wide ranges of temperatures (300–2300 K) and pressures (0.02–10 atm), and explains well the observed NTC behavior based on the competition between multiple oxidation pathways for the methyl radicals and their self-recombination forming ethane, a relatively stable species at temperatures below 1000 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen shift isomerizations in the kinetics of the second oxidation mechanism of alkane combustion. Reactions of the hydroperoxypentylperoxy OOQOOH radical

Hydroperoxyalkylperoxy species are important intermediates that are generated during the autoignition of transport fuels. In combustion, the fate of hydroperoxyalkylperoxy is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the hydroperoxyalkylperoxy is a 1,5 H-shift, for which kinetics data are experimentally unavailable. In the present work, we study 1-hydroperoxypentan-3-yl)dioxidanyl (CH 3 CH 2 CH(OO)CH 2 CH 2 OOH) as a model compound to clarify the kinetics of 1,5 H-shift of hydroperoxyalkylperoxy species, in particular α-H isomerization and alternative competitive pathways. With a combination of electronic structure calculations, we determine previously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunneling (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity, we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for these competitive reactions are computed using system-specific quantum RRK theory. The calculated temperature range is 298–1500 K, and the pressure range is 0.01–100 atm. The accurate thermodynamic and kinetics data determined in this work are indispensable in the detailed understanding and prediction of ignition properties of hydrocarbons and alternative fuels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗