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The effect of ethanol on n-heptane oxidation was studied using the reactive molecular dynamics (RMD) method. With different ethanol concentrations, simulations were performed under fuel-rich condit...

We have used laser-photolysis/photoionization mass spectrometry to measure the kinetics of the reaction of 1-methylpropargyl (but-3-yn-2-yl, ) radicals with oxygen molecules as a function of temperature ( T = 200 − 685 K ) and bath gas density ( 1.2 − 15 × 10 16 cm − 3 ). The low temperature (T ≤ 304 K) kinetics is dominated by oxygen addition to the carbon of the radical to form a peroxyl radical, and the measured bimolecular rate coefficient exhibits negative temperature dependence and depends on bath gas density. At slightly higher temperatures ( 335 − 396 K ), where the redissociation rate of the peroxyl is already observable, we measured the equilibrium constant as a function of temperature. At even higher temperatures ( T = 479 − 685 K ), the loss rate of 1-methylpropargyl is determined by the addition of oxygen to the terminal carbon and the reaction is observed to produce methylketene. The high-temperature bimolecular rate coefficient is independent of bath gas density and the temperature dependence is weakly positive. To explain our experimental findings, we performed quantum chemical calculations together with master equation simulations. By using our experimental data to constrain key parameters, the master equation model was able to reproduce experimental results reasonably well. We then extended the conditions of our simulations up to 2000 K and 100 bar. The results of these simulations are provided in ChemKin compatible PLOG format.

The potential of dimethyl ether (DME) and dimethoxymethane (DMM), representatives of the attractive oxymethylene ether (OME) alternative fuel family, are explored here as reactivity enhancers for methane-fueled polygeneration processes. Typically, such processes that can flexibly generate power, heat, or chemicals, operate under fuel-rich conditions in gas turbines or internal combustion engines. To provide a consistent basis for the underlying reaction mechanisms, it is recognized that speciation data for the DME/CH4 fuel combination are available for such conditions while such information for the DMM/CH4 system is largely lacking. In addition, it should be noted that a detailed speciation study in flames, i.e., combustion systems involving chemistry and transport processes over a large temperature range, is still missing in spite of the potential of such systems to provide extended species information. In a systematic approach using speciation with electron ionization molecular-beam mass spectrometry (EI-MBMS), we thus report, as a first step, investigation of six fuel-rich premixed flames of DME and DMM and their blends with methane with special attention on interesting chemicals. Secondly, a comprehensive but compact DME/DMM/CH4 model (PolyMech2.1) is developed based on these data. This model is then examined against available experimental data under conditions from various facilities, focusing preferentially on elevated pressure and fuel-rich conditions. Comparison with existing literature models is also included in this evaluation. Thirdly, an analysis is given on this basis, via the extensively tested PolyMech2.1 model, for assumed polygeneration conditions in a homogeneous charge compression ignition (HCCI) engine environment. The main interest of this model-assisted exploration is to evaluate whether addition of DME or DMM in a polygeneration process can lead to potentially useful conditions for the production of syngas or other chemicals, along with work and heat. The flame results show that high syngas yields, i.e., up to similar to 78% for CO and similar to 35% for H-2, can be obtained in their burnt gases. From the large number of intermediates detected, predominantly acetylene, ethylene, ethane, and formaldehyde show yields of 2.1-4.4% (C-2 hydrocarbons) and 3.4-8.7% (CH2O), respectively. Also, methanol and methyl formate show comparably high yields of up to 0.6-6.7% in the flames with DMM, which is 1-2 orders of magnitude higher than in those with DME as the additive. In the modeling-assisted exploration of the engine process, the PolyMech2.1 model is seen to perform at significantly reduced computational costs compared to a recently validated model without sacrificing the prediction performance. Promising conditions for the assumed polygeneration process using fuel combinations in the DME/DMM/CH4 system are identified with attractive syngas yields of up to 77% together with work and heat output at exergetic efficiencies of up to 89% with DME. (C) 2021 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Modelling internal combustion engines (ICEs) with multidimensional computational fluid dynamics (CFD) is challenging due to the fuel spray, combustion chemistry and moving piston involved. To accur...

Probability density function (PDF) methods are now well established and can be used to accurately simulate flames with strong turbulence chemistry interactions. A pre-partitioned adaptive chemistry...

Ab initio transition state theory-based master equation methodologies for the calculation of rate constants have gained enormous popularity in the past decades. Nevertheless, introducing these rate constants into large kinetic schemes is a non-trivial task when large potential energy surfaces (PESs) are investigated. To determine proper phenomenological rate constants it is in fact necessary to account for the formation of all the thermodynamically stable wells considered in the master equation (ME), even if most wells do not exhibit significant secondary reactivity. Moreover, reactions involving intermediates with lifetimes comparable to the rovibrational relaxation timescale can exhibit discontinuities both in the rate constants and in the number of thermodynamically stable wells across the investigated temperature and pressure ranges. In this work, we address these problems with a “master equation-based lumping” (MEL) approach specifically designed to process the output of ME calculations of multi-well PESs. Simple kinetic simulations allow identifying both intermediate wells with limited lifetime and isomers with similar reactivity. Then, equivalent rate constants for a smaller set of pseudospecies are derived so as to reproduce the kinetics of the detailed mechanism. Our methodology is independent of any experimental data or experience-based assumptions. The power of MEL is demonstrated with three case studies of increasing complexity, namely the PES for CH3COOH decomposition, and the portions of the C5H5OH and C10H10/C10H9 PESs accessed from C5H5 + OH and C5H5 + C5H5 recombination. This work constitutes the first systematic step addressing the robust integration of rate constants derived from ME simulations into global kinetic schemes and provides a useful approach for the entire chemical kinetics community filling the gap between detailed theoretical investigations of complex PESs and the development of detailed kinetic models.

International audience; Direct Numerical Simulation (DNS) data obtained by Dave and Chaudhuri (2020) from a lean, complex-chemistry, hydrogen-air flame associated with the thin-reaction-zone regime of premixed turbulent burning are analyzed (by adapting five alternative definitions of combustion progress variable c) in order to examine three different models that (i) are based on the flamelet paradigm and (ii) aim at evaluating mean concentrations of various species in applied CFD research into turbulent combustion. Mean mole fractions of all considered species and mean density are predicted if the laminar-flame profiles of species mole fractions and density, respectively, are directly averaged using a Probability Density Function (PDF) P(c). The best predictions are obtained by extracting P(c) from the DNS data and defining c based on hydrogen mass fraction. These predictions suggest that mean mole fractions of various species in a premixed turbulent flame can be evaluated at a post-processing stage of a CFD study by adopting P(c), obtained at the major stage of the simulations, to average a flamelet library. When applied in such a way, the flamelet paradigm is useful even for lean hydrogen-air flames and even at Karlovitz number as large as 13. If the same PDF is applied to average reaction rates from the same flamelet library, the mean rates of production/consumption of species n are poorly predicted, e.g. for radicals H, O, OH, HO2, and H2O2 if c is defined using hydrogen mass fraction. A hypothesis that conditioned rates 〈Wn|c〉 can be predicted using conditioned mole fractions 〈Xn|c〉, temperature 〈T|c〉, and density 〈ρ|c〉 is not supported either, e.g. for radicals O and OH. These differences between predictive capabilities of the first approach (directly averaging concentration profiles) and two other approaches (averaging reaction rates) are attributed to weakly (highly) non-linear dependencies of the concentrations (rates, respectively) on c.

Lead‐based compounds are the current industry‐standard ballistic modifier for double‐base propellants, but there is a pressing need for alternatives as incoming European legislation will soon ban their use. This review article introduces the main concepts and terminologies in the combustion chemistry of double‐base propellants, and critically evaluates the four theories put forward in the literature to account for the ballistic modifier effect, namely (i) photochemical, (ii) chelating/complex, (iii) carbon soot, and (iv) free radical theories. We also review the literature on current trends in ballistic modifier research and note the emerging potential of oxide nanoparticles (in particular Bi2WO6) and Cu/Bi encapsulated in carbon nanotubes as lead‐free ballistic modifier additives.

We report a cascaded group-additivity (CGA) ONIOM method for high-level energy calculations of large aliphatic hydrocarbon molecules by combining the group additivity and two-layer ONIOM methods. This hybrid method is implemented by partitioning the target molecule into individual groups, which are cascaded via the overlapping between them. The energy of the entire molecule is first calculated at a low level of theory such as M06-2x/cc-pVTZ. Then all the groups and their overlappings are treated at the levels of CCSD(T)/CBS and M06-2x/cc-pVTZ to obtain their energy difference to be used as the energy correction. We selected small-to-middle size aliphatic hydrocarbons including 79 C4 C8 molecules as the validation set to demonstrate the feasibility of the CGA-ONIOM method, followed by the calculations of 12 representative C10, C12 and C16 aliphatic hydrocarbons (including normal-, branched-, cyclo- and unsaturated categories). Our calculations agree well with the reference values available in the literature with the modest deviation around 1.0 kcal mol−1. Compared with the conventional CCSD(T)/CBS calculation of the whole molecule, the computational cost can be dramatically reduced by a factor of ∼102 for molecules with 10 carbons and ∼104 for molecules with 16 carbons. Considering its outstanding computational efficiency and accuracy, our proposed CGA-ONIOM method is promising for combustion chemistry studies of large fuel molecules at a high level of theory.

The present work quantifies the impact of fuel chemistry on burning modes using premixed dimethyl ether (DME), ethanol (EtOH) and methane flames in a back-to-burnt opposed jet configuration. The study considers equivalence ratios 0 ≤ Φ ≤ 1, resulting in a Damkohler (Da) number range 0.06 ≤ Da ≤ 5.1. Multi-scale turbulence (Re ≃ 19,550 and Ret ≃ 360) is generated by means of a cross fractal grid and kept constant along with the enthalpy of the hot combustion products (THCP = 1700 K) of the counterflow stream. The mean turbulent rate of strain exceeds the laminar extinction rate for all flames. Simultaneous Mie scattering, OH-PLIF and PIV are used to identify reactants, mixing, weakly reacting, strongly reacting and product fluids. The relative balance between conventional flame propagation and auto-ignition based combustion is highlighted using suitably defined Da numbers and a more rapid transition towards self-sustained (e.g. flamelet type) combustion is observed for DME. The strain rate distribution on the reactant fluid surface for methane remains similar to the (non-reactive) mixing layer ( Φ = 0 ), while DME and EtOH flames gradually detach from the stagnation plane with increasing Φ leading to stabilisation in regions with lower compressive rates of strain. The study further provides information on the conditions leading to burning mode transitions via (i) multi-fluid probabilities, (ii) structural flow field information and turbulence-flame interactions delineated by means of conditional (iii) velocity statistics and (iv) the rate of strain along fluid iso-contours.

We present in this short communication a modification to our previous ethanol reduced combustion chemistry (Millán-Merino, 2018) that eliminates nonphysical values of the species concentrations which we discovered in applying the mechanism to the combustion of an isolated ethanol droplet. This unsteady test is reported here to check the multipurpose character of the reduced mechanism for a problem that combines non-homogeneous autoignition, rich and lean premixed-flame propagation, and the development of a diffusion flame, as well as a the presence of a cold moving boundary at the droplet surface. During the computations, production and consumption rates of the alfa-hydroxyethyl (CH3CHOH) intermediary radical became unbalanced, invalidating its steady-state hypothesis, which was used during the derivation of the reduced scheme. This difficulty is removed here by taking CH3CHOH out of steady state, thereby augmenting slightly the reduced mechanism. This work was supported by the project ENE2015-65852-C2-1-R (MINECO/FEDER,UE).

We have measured the kinetics and thermochemistry of the reaction of 3-methylpropargyl radical (but-2-yn-1-yl) with molecular oxygen over temperature (223–681 K) and bath gas density ( 1.2 − 15.0 × 10 16 cm − 3 ) ranges employing photoionization mass-spectrometry. At low temperatures (223–304 K), the reaction proceeds overwhelmingly by a simple addition reaction to the − CH 2 end of the radical, and the measured CH 3 CCCH 2 • + O 2 reaction rate coefficient shows negative temperature dependence and depends on bath gas density. At intermediate temperatures (340–395 K), the addition reaction equilibrates and the equilibrium constant was determined at different temperatures. At high temperatures (465–681 K), the kinetics is governed by O2 addition to the third carbon atom of the radical, and rate coefficient measurements were again possible. The high temperature CH 3 CCCH 2 • + O 2 rate coefficient is much smaller than at low T, shows positive temperature dependence, and is independent of bath gas density. In the intermediate and high temperature ranges, we observe a formation signal for ketene (ethenone). The reaction was further investigated by combining the experimental results with quantum chemical calculations and master equation modeling. By making small adjustments ( 2 − 3 kJ mol − 1 ) to the energies of two key transition states, the model reproduces the experimental results within uncertainties. The experimentally constrained master equation model was used to simulate the CH 3 CCCH 2 • + O 2 reaction system at temperatures and pressures relevant to combustion.

The formulation of reactive flow problems can be both quite challenging and important to the efficiency and robustness of solution algorithms. In this article, we focus on the choice of the thermochemical state vector as it relates to recently-developed computational techniques for complex combustion chemistry problems. We identify over-specification of the state vector as a source of both ambiguity and error in the partial derivatives used in forming analytical forms of the chemical source Jacobian matrix. We review and compare several approaches taken to increase sparsity of the Jacobian matrix, as it relates to the use of Newton–Krylov methods for implicit time integration, and identify proper techniques for achieving sparsity that do not rely on ad-hoc choice of state variables with inconsistent Jacobians. Chemical explosive mode analysis and linearly-implicit methods, such as Rosenbrock methods, are identified as areas where Jacobian accuracy may be critical. The distinction between how Jacobian exactness impacts Rosenbrock and Newton–Krylov methods is demonstrated with a simple example. We demonstrate the errors in conservation obtained from over-specification of the state vector with auto-ignition calculations for hydrogen, ethylene, and n-heptane chemistry with a high-order implicit Runge–Kutta method.

The increasing interest in light alkenes oxidation for the development of detailed kinetic model is mainly due to their relevance in the combustion chemistry of most common fuels and their formation in the oxidation of higher alkanes. This study analyses the detailed kinetic mechanisms for the oxidation of linear lighter alkenes, ethylene, propylene and 1-butene, through the comparison of several combustion kinetic models retrieved from current literature with respect to the experimental data for the laminar burning velocity in air, and for the ignition delay time, by varying either reactant concentration or initial temperature. The mechanisms by University of California, San Diego (UCSD), Konnov group (KOM), University of Southern California (USC), Saudi Aramco 2.0 (SAM), Lawrence Livermore National Laboratory (LLNL), and Politecnico of Milano (CRECK) have been evaluated through a unified statistical analysis. A sensitivity analysis for the laminar burning velocity was also performed to assess and compare the reactions described in the studied models and sort by relevance. Best fits are produced by the LLNL and the UCSD model even if the optimal results can depend on the specific hydrocarbon. We then produced a new mechanism by adding the UCSD for C3 and LLNL for C4 or more, which resulted to work better. © 2018 American Chemical Society.

In this study, a series of ignition delay time (IDT) experiments of 1-butene were performed in a high-pressure shock tube (HPST) and in a rapid compression machine (RCM) under conditions of relevance to practical combustors. This is the first 1-butene IDT data taken at engine relevant conditions, and the combination of HPST and RCM results greatly expands the range of data available for the oxidation of 1-butene to higher pressures (10-50 atm), lower temperatures (670-1350 K) and to a wide range of equivalence ratios (0.5-2.0).A comprehensive chemical kinetic mechanism to describe the combustion of 1-butene has simultaneously been applied. It has been validated using the IDT data measured here in addition to a large variety of literature data: IDTs, speciation data from jet-stirred reactor (JSR), premixed flame, and flow reactor, and laminar flame speed data. Important reactions have been identified via flux and sensitivity analyses including: (a) H-atom abstraction from 1-butene by hydroxyl radicals and molecular oxygen from different carbon sites; (b) addition reactions, including hydrogen atom and hydroxyl radical addition to 1-butene; (c) allylic radical chemistry, including the addition reactions with methyl radical, hydroperoxy radical and self-recombination; (d) vinylic radical chemistry, including the addition reaction with molecular oxygen; (e) alcohol radical chemistry, including the Waddington type propagating reaction pathways and alkyl radical low-temperature branching chemical pathways. (C) 2017 The Combustion Institute. Published by Elsevier Inc. All rights reserved. The authors thank the entire group members at Combustion Chemistry Centre for helpful discussions. This work at NUI Galway was supported by Saudi Aramco under the FUELCOM program. peer-reviewed 2019-04-13

Combustion involves chemical reactions that are often highly exothermic. Combustion systems utilize the energy of chemical compounds released during this reactive process for transportation, to generate electric power, or to provide heat for various applications. Chemistry and combustion are interlinked in several ways. The outcome of a combustion process in terms of its energy and material balance, regarding the delivery of useful work as well as the generation of harmful emissions, depends sensitively on the molecular nature of the respective fuel. The design of efficient, low-emission combustion processes in compliance with air quality and climate goals suggests a closer inspection of the molecular properties and reactions of conventional, bio-derived, and synthetic fuels. Information about flammability, reaction intensity, and potentially hazardous combustion by-products is important also for safety considerations. Moreover, some of the compounds that serve as fuels can assume important roles in chemical energy storage and conversion. Combustion processes can furthermore be used to synthesize materials with attractive properties. A systematic understanding of the combustion behavior thus demands chemical knowledge. Desirable information includes properties of the thermodynamic states before and after the combustion reactions and relevant details about the dynamic processes that occur during the reactive transformations from the fuel and oxidizer to the products under the given boundary conditions. Combustion systems can be described, tailored, and improved by taking chemical knowledge into account. Combining theory, experiment, model development, simulation, and a systematic analysis of uncertainties enables qualitative or even quantitative predictions for many combustion situations of practical relevance. This article can highlight only a few of the numerous investigations on chemical processes for combustion and combustion-related science and applications, with a main focus on gas-phase reaction systems. It attempts to provide a snapshot of recent progress and a guide to exciting opportunities that drive such research beyond fossil combustion. © 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Combustion research still needs more advanced fundamental understanding of combustion chemistry and dynamics from molecule scale to particle. The latter is also needed for soot and nanoparticles fo...

Butenes are intermediates ubiquitously formed by decomposition and oxidation of larger hydrocarbons (e.g. alkanes) or alcohols present in conventional or reformulated fuels. In this study, a series of novel igni-tion delay time (IDT) experiments of trans-2-butene were performed in a high-pressure shock tube (HPST) and in a rapid compression machine (RCM) under conditions of relevance to practical combustors. This is the first IDT data of trans-2-butene taken at engine relevant conditions, and the combination of HPST and RCM results greatly expands the range of data available for the oxidation of trans-2-butene to higher pressures (10-50 atm), lower temperatures (670-1350 K) and a wide range of equivalence ratios (0.5-2.0). A comprehensive chemical kinetic mechanism has simultaneously been developed to describe the combustion of trans-2-butene. It has been validated using the IDT data measured here in addition to a large variety of literature data: jet-stirred reactor (JSR) speciation data, premixed flame speciation data, flow reactor speci-ation data and laminar flame speed data. Moreover, the reactivity of trans-2-butene is compared to that of the other two isomers, 1-butene and isobutene, and these comparisons are discussed. Important reactions are highlighted via flux and sensitivity analyses and help explain the differences in reactivity among the butene isomers. (C) 2016 by The Combustion Institute. Published by Elsevier Inc. The authors thank the entire group members at Combustion Chemistry Centre for helpful discussions. This work at NUI Galway was supported by Saudi Aramco under the FUELCOM program. peer-reviewed 2018-06-16

Over the last 20 to 25 years theoretical chemistry (particularly theoretical chemical kinetics) has played an increasingly important role in developing chemical kinetics models for combustion. Theoretical methods of obtaining rate parameters are now competitive in accuracy with experiment, particularly for small molecules. Moreover, theoretical methods can deal with conditions that experiments frequently cannot. In addition to increased accuracy, theory has rejuvenated methods and discovered phenomena that were completely unappreciated, or at least underappreciated, in the 20th century. Our primary interest here is in molecular-level issues, i.e. in calculating rate and transport parameters. However, dealing with kinetics models that involve thousands of reactions and hundreds of species is important for practical applications and is relatively new to the 21st century. Theory, in a general sense, and theoretical methods development have a role to play here too. We discuss in this review all these topics in some detail with an emphasis on issues and methods that have emerged in the last 20 years or so. Even so, our review is selective, rather than comprehensive, out of necessity.

This contribution combines results of experiments with kinetic modelling to probe the unusual behaviour of carbonyl sulfide (COS), a sulfur species that frequently arises in fuel systems. The experiments identified CO and SO2 as the primary oxidation products, with no formation of CO2. The low ignition temperature (

Small esters represent an important class of high octane biofuels for advanced spark ignition engines. They qualify for stringent fuel screening standards and could be synthesized through various pathways. In this work, we performed a detailed investigation of the combustion of two small esters, MA (methyl acetate) and EA (ethyl acetate), including quantum chemistry calculations, experimental studies of combustion characteristics and kinetic model development. The quantum chemistry calculations were performed to obtain rates for H-atom abstraction reactions involved in the oxidation chemistry of these fuels. The series of experiments include: a shock tube study to measure ignition delays at 15 and 30 bar, 1000-1450 K and equivalence ratios of 0.5, 1.0 and 2.0; laminar burning velocity measurements in a heat flux burner over a range of equivalence ratios [0.7-1.4] at atmospheric pressure and temperatures of 298 and 338 K; and speciation measurements during oxidation in a jet-stirred reactor at 800-1100 K for MA and 650-1000 K for EA at equivalence ratios of 0.5, 1.0 and at atmospheric pressure. The developed chemical kinetic mechanism for MA and EA incorporates reaction rates and pathways from recent studies along with rates calculated in this work. The new mechanism shows generally good agreement in predicting experimental data across the broad range of experimental conditions. The experimental data, along with the developed kinetic model, provides a solid groundwork towards improving the understanding the combustion chemistry of smaller esters. (C) 2018 The Combustion Institute. Published by Elsevier Inc. All rights reserved. The authors at KAUST acknowledge funding support from the Office of Sponsored Research under the Future Fuels Program. The authors at NUI Galway recognize funding support from Science Foundation Ireland via their Principal Investigator Program through project number 15/IA/3177. Cavallotti acknowledges the financial support of the Chemical Sciences and Engineering Division of Argonne National Laboratories for his sabbatical. The work by authors at LLNL was performed under the auspices of the U.S. Department of Energy (DOE), Contract DE-AC52-07NA27344 and was conducted as part of the Co-Optimization of Fuels & Engines (Co-Optima) project sponsored by the U.S. Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies and Vehicle Technologies Offices. The authors at Lund University acknowledge financial support from the Centre for Combustion Science and Technology (CECOST), and Swedish Research Council (VR) via project 2015-04042. Part of this material is based on work at Argonne supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract No. DE-AC02-06CH11357. The NREL research was conducted as part of the Co-Optimization of Fuels & Engines (Co-Optima) project sponsored by the U.S. Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies and Vehicle Technologies Offices. peer-reviewed 2020-07-17

The combustion chemistry of formaldehyde in fuel-rich flames has been studied by numerical modeling and sensitivity analysis. It has been shown that the wide flammability limits of CH2O/air mixtures are due to features of the combustion chemistry of formaldehyde at high equivalence ratios rather than to the superadiabatic temperature effect. In this case, the thermal decomposition reaction of hydrogen peroxide H2O2 plays a key role in the conventional branching reactions.

The present work focuses on new measurement of laminar burning velocities of ethanol-air mixtures at 1 atm pressure and elevated mixture temperatures using an externally heated meso-scale diverging channel technique. The burning velocity measurements were carried out for a temperature range of 350–620 K and equivalence ratio range of 0.7–1.3. Various detailed kinetic models available in literature were used for assessment and comparison with experimental results. The experimental results show a good match at lower mixture temperatures across all equivalence ratios. However, at higher temperatures, the difference between the measurements and predictions of different kinetic models is considerably higher, particularly for rich mixture regime. The effect of mixture temperature on laminar burning velocity was assessed using power law correlation, S u = S u , 0 ( T u / T u , 0 ) α . The variation of temperature exponent, α with equivalence ratio, Φ showed a minimum value for slightly rich mixtures. This variation of the measured laminar burning velocity and temperature exponent at elevated mixture temperatures and predictions using various kinetic mechanisms shows a good match for lean mixtures.

This paper presents a detailed investigation of 2-methylbutanol combustion chemistry in low-pressure premixed flames. This chemistry is of particular interest to study because this compound is potentially a lignocellulosic-based, next-generation biofuel. The detailed chemical structure of a stoichiometric low-pressure (25 Torr) flame was determined using flame-sampling molecular-beam mass spectrometry. A total of 55 species were identified and subsequently quantitative mole fraction profiles as function of distance from the burner surface were determined. In an independent effort, a detailed flame chemistry model for 2-methylbutanol was assembled based on recent knowledge gained from combustion chemistry studies for butanol isomers ([Sarathy et al. Combust. Flame 159 (6) (2012) 2028-2055]) and iso- pentanol (3-methylbutanol) [Sarathy et al. Combust. Flame 160 (12) (2013) 2712-2728]. Experimentally determined and modeled mole fraction profiles were compared to demonstrate the model’s capabilities. Examples of individual mole fraction profiles are discussed together with the most significant fuel consumption pathways to highlight the combustion chemistry of 2-methylbutanol. Discrepancies between experimental and modeling results are used to suggest areas where improvement of the kinetic model would be needed.

The effects of the ester moiety on soot formation and species concentrations in a laminar coflow diffusion flame of a surrogate for a B100 biodiesel are investigated. The surrogate is a mixture of 50% n-decane/50% methyl-octanoate (molar) to represent methyl-oleate. The combustion chemistry and soot formation are solved using a mechanism with 288 species and 2073 reactions coupled with a sectional soot model, respectively. Soot volume fraction (fv) and temperature profiles are compared to the experimentally measured values for this biodiesel surrogate. In addition, the effects of the ester moiety on soot formation and flame chemistry are studied by numerically comparing the biodiesel surrogate flame with a pure n-decane flame. The model predicts both temperature and fv profiles with a good accuracy. Some discrepancies for fv on the flame centerline are observed between the model and the experiments; it is suggested that these discrepancies are because the model and the experiment cannot distinguish nascent transparent soot from mature soot and because the mechanism under-predicts PAH formation rates. Both n-decane and B100 surrogate flames have similar fv and temperature profiles when both flames have the same energy input. This suggests that the ester moiety does not have a major impact on soot formation. In addition, early production of CO and higher concentrations of some oxygenated species such as formaldehyde are observed in the predicted concentration contour plots of the B100 surrogate flame when they are compared to the n-decane flame. Reaction pathway analysis reveals that the higher peak concentrations of formaldehyde and the early production of CO from CH2CO and CH3CO2 that come directly from the ester moiety in the B100 surrogate are much more pronounced than other species in the B100 surrogate flame and are recognized as the main differentiating characteristics of the B100 surrogate flame from the n-decane flame.

The development of reduced chemical mechanisms in a systematic way has emerged as a potential solution to the problem of incorporating the increasingly large chemical mechanisms into turbulent combustion CFD codes. In this work, a methodology is proposed for developing reduced mechanisms with Rate-Controlled Constrained Equilibrium (RCCE) via a Computational Singular Perturbation (CSP) analysis of counterflow non-premixed flamelets. An ordering of species for variable strain rates is derived by integrating over mixture fraction space a modified CSP pointer that depends on the timescale and mass fraction of each chemical species. Subsequently, a global set of kinetically controlled species is identified from weighting the local ordering for each strain rate. RCCE simulations with the derived reduced mechanisms for methane with 16 species and for propane with 27 species are compared with the integration of the detailed mechanisms GRI 1.2 and USC-Mech-II, respectively. The applicability of the methodology is demonstrated in non-premixed flames for several strain rates, in non-premixed flames ignited with a pilot in order to test the dynamics and ignition of the reduced schemes, in premixed flames for different equivalence ratios and subsequently in perfectly stirred reactors for ignition delay times for varying temperature, pressure and equivalence ratio. Overall very good agreement is obtained, indicating that the methodology can produce reliable mechanisms for different fuels and for a wide range of conditions, including dynamical behaviour and conditions different from those employed for the derivation of the mechanism.

A detailed numerical investigation of combustion of unsupported and fiber supported n-heptane droplets in reduced gravity is presented. The primary focus is on the effects of support fibers on the droplet burning rates and flame structure. A 21-step n-heptane reaction mechanism consisting of 20 species is employed to model the combustion chemistry. The volume-of-fluid (VOF) method is employed to capture the liquid-gas interface while allowing for time-dependent two-phase multidimensional flows. Computed burning rates and flame stand-off ratios are compared with the experimental results of Jackson. Predicted flame structures are also validated with the experimental results of Mikami. The present computational results agree well with the experimental results. The results indicate that the support fibers can have significant impact on droplet burning rates and flame structure.

Recent advances in laser absorption and shock tube methodologies for studies of combustion chemistry are reviewed. First the principles of shock tube operation are discussed, and then an overview of shock tube diagnostic methods and experiments is covered. Recent shock tube developments include the use of driver inserts to counteract the small pressure gradient seen in conventional reflected shock wave experiments and the use of a constrained-reaction-volume strategy to enable the implementation of near-constant-pressure gasdynamic test conditions during energetic processes. Recent laser absorption developments include the use of a CO2 laser absorption sensor to accurately monitor temperature during shock wave experiments, the use of multi-wavelength laser absorption strategies to simultaneously monitor multiple species time-histories, and the used of isotopic labeling strategies to identify individual reaction sites during the measurement of elementary reaction rate constants. The improved ability to accurately constrain the test conditions in shock tube experiments, combined with non-intrusive, species-sensitive and quantitative laser absorption diagnostics, is enabling experimenters to provide a new generation of high-quality experimental kinetics targets for combustion chemistry model validation and refinement. The paper concludes with a brief discussion of newly emerging laser-diagnostic techniques and a summary of future research directions.

The state of the art and the further challenges of combustion chemistry research in laminar flames are reviewed. Laminar flames constitute an essential part of kinetic model development as the rates of elementary reactions are studied and/or validated in the presence of temperature and species concentration gradients. The various methods considered in this review are the flat, low-pressure, burner-stabilized premixed flame for chemical speciation studies, and the stagnation, spherically expanding, and burner-stabilized flames for determining the global flame properties. The data derived using these methods are considered at present as the most reliable ones for three decades of pressures ranging from about 50 mbar to over 50 bar. Furthermore, the attendant initial and/or boundary conditions and physics are in principle well characterized, allowing for the isolation of various physical parameters that could affect the flame structure and thus the reported data. The merits of each approach and the advances that have been made are outlined and the uncertainties of the reported data are discussed. At the same time, the potential sources of uncertainties associated with the experimental methods and the hypotheses for data extraction using each method are discussed. These uncertainties include unquantified physical effects, inherent instrument limitations, data processing, and data interpretation. Recommendations to reduce experimental uncertainties and increase data fidelity, essential for accurate kinetic model development, are given.

International audience; Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has - to the best of our knowledge - not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (phi = 1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combust. Flame 158 (2011)756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the predominant furan consumption pathway is initiated by H-addition on the carbon atom neighboring the O-atom with acetylene as one of the dominant products.

In this communication, we describe the development of a new plasma/flame facility and burner platform that appears promising for directly investigating the effects of high-voltage, nanosecond-duration, repetitively pulsed plasma discharges on moderate- and high-temperature reaction chemistry. Such a configuration is ideal for identifying key processes and key species that can alter fuel oxidation, hydrocarbon intermediate formation, and radical formation/heat-release under combusting conditions. Initial results using emission spectroscopy demonstrate that the excited-state species such as OH*, CH*, and are significantly enhanced in the presence of repetitive nanosecond pulse discharges. This new plasma-flame facility also lends itself to kinetic modeling due to its simple quasi-one-dimensional geometry and uniformity of the nanosecond pulse discharge.

The pyrolysis and oxidation of benzene occupies a critical role in the combustion chemistry of practical fuels. Despite numerous experimental and numerical investigations, uncertainties still exist...

Computational calculations of combustion problems involving large numbers of species and reactions with a detailed description of the chemistry can be very expensive. Numerous dimension reduction techniques have been developed in the past to reduce the computational cost. In this paper, we consider the rate controlled constrained-equilibrium (RCCE) dimension reduction method, in which a set of constrained species is specified. For a given number of constrained species, the ‘optimal’ set of constrained species is that which minimizes the dimension reduction error. The direct determination of the optimal set is computationally infeasible, and instead we present a greedy algorithm which aims at determining a ‘good’ set of constrained species; that is, one leading to near-minimal dimension reduction error. The partially-stirred reactor (PaSR) involving methane premixed combustion with chemistry described by the GRI-Mech 1.2 mechanism containing 31 species is used to test the algorithm. Results on dimension re...

Two detailed gas-phase chemical mechanisms for RDX – Yetter and coworkers, herein ‘Y2’ [K. Prasad, R.A. Yetter, M.D. Smooke, Combust. Sci. Technol. 124 (1997) p. 35.]; Cal. Tech. group, herein ‘CTM’ [(a) A.D. Chakraborty, R.P. Muller, S. Dasgupta, W.A. Goddard, III, J. Phys. Chem. A 104 (2000) 2261. (b) D. Chakraborty, R.P. Muller, S. Dasgupta, W.A. Goddard, III, J. Comput. Aided Mater. Des. 8 (2001) 203. (c) D. Chakraborty, R.P. Muller, S. Dasgupta, W.A. Goddard, III, Available from: http://www.wag.caltech.edu/home/rpm/projects/hedm /] – have been tested using a recently developed combustion model. The results are compared with each other and experimental data. Burning rates predicted using CTM are about 15% higher than Y2, but both compare well with experimental data across a wide pressure range. Also, majority species profiles are in reasonable agreement with data from a 0.5 atm pressure experiment. However, comparison of predicted trace species profiles to experiments indicates neither mechanism reproduces all measured trace species well; furthermore, most of these trace species occur along main reaction pathways. Detailed chemical analysis indicates the main initial RDX reaction is surprisingly very different for the two mechanisms. NO2 scission dominates using Y2, but HONO elimination dominates using CTM, in spite of the NO2 scission reaction having by far the largest RDX decomposition rate coefficient in each mechanism. Analysis shows the unexpected result using CTM is due to a curious global kinetics phenomenon arising in the product pathway: the ring-opening reaction, RDXR → RDXRO, where RDXR is the cyclic radical formed upon NO2 scission, has a much smaller rate coefficient in CTM compared to Y2. This causes the reaction to be a bottleneck, and so the NO2 scission reaction goes into partial equilibrium rather than being forwards. Tests were performed to see how the predicted burning rates would be affected by changes in some of the most sensitive rate parameters. Some of the key parameters leading to the differing predictions have been identified. These results will help guide future efforts to understand and develop an accurate representation of the actual RDX combustion chemistry.

A theoretical study on combustion of JA2, RPD-380, and RPD-351, which are modified double-base propellants composed primarily of three identical nitrate ester ingredients, is presented. A one-dimensional, two-phase model was used [M.S. Miller, W.R. Anderson, in: V. Yang, T.B. Brill, W.Z. Ren (Eds.), Solid Propellant Combustion Chemistry, Combustion and Motor Interior Ballistics, Progress in Astronautics and Aeronautics, vol. 185, AIAA, Reston, VA, 2000, pp. 501–531, (a) M.S. Miller, W.R. Anderson, J. Propul. Power 20 (3) (2004) 440–454. (b) M.S. Miller, W.R. Anderson, CYCLOPS, A Breakthrough Code to Predict Solid-Propellant Burning Rates, U.S. Army Research Laboratory Technical Report, 1987 ARL-TR-2910.]. This approach has been shown to give good agreement between predicted and experimental results for several nitrate ester propellants, including JA2 [(a) M.S. Miller, W.R. Anderson, J. Propul. Power 20 (3) (2004) 440–454. (b) M.S. Miller, W.R. Anderson, CYCLOPS, A Breakthrough Code to Predict Solid-Propellant Burning Rates, U.S. Army Research Laboratory Technical Report, 1987 ARL-TR-2910.]. Extension of the model to the two RPD variants yields results in good agreement with existing experimental data. Comparisons of the response of predicted burning rates to experimental formulation changes at gun pressures, and to the initial propellant temperature are particularly encouraging. Our results show the burning rate ordering of these propellants is JA2

Large and complex (nonlinear) models of chemical kinetics are one of the major obstacles in simulations of reacting flows. In the present work a new approach for an automatic reduction of chemical kinetics models, the so-called Global Quasi-Linearization (GQL) method is presented. The method is similar to the ILDM and CSP approaches in the sense that it is based on a decomposition into fast/slow motions and on slow invariant manifolds, but has a global character which allows us to overcome difficulties with the application of slow invariant manifolds and significantly simplifies the construction procedure for approximation of the slow invariant system manifold. The method is implemented within the standard ILDM method and applied to a number of model examples and to a meaningful combustion chemistry model.

There is much interest in the combustion mechanism of organophosphorus compounds (OPCs) due to their role as potential halon replacements in fire suppression. A continuing investigation of the inhibition activity of organophosphorus compounds under a range of equivalence ratios was performed experimentally and computationally, as measured by the burning velocity. Updates to a previous mechanism were made by the addition and modification of reactions in the mechanism for a more complete description of the inhibition reactions. Reaction pathways for HOPO 2 + H and HOPO + H are analyzed using the BAC-G2 approach. A new reaction pathway for HOPO 2 + H = PO 2 + H 2 O has been identified which results in a higher rate constant than that reported in the literature. In this work, the laminar flame speed is measured experimentally and calculated numerically for a premixed propane/air flame at 1 atm, under a range of equivalence ratios, undoped and doped with dimethyl methylphosphonate (DMMP). A detailed investigation of the catalytic cycles involved in the recombination of key flame radicals is made for two equivalence ratios, fuel lean and fuel rich. From this, the importance of different catalytic cycles involved in the lean versus rich case is discussed. The chemical kinetic model indicates that the HOPO 2 ⇔ PO 2 inhibition cycle is more important in the lean flame than the rich. The OPCs are similarly effective across the range, demonstrating the robustness of OPCs as flame suppressants. In addition, it is shown that the phosphorus compounds are most active in the high-temperature region of the flame. This may, in part, explain their high level of inhibition effectiveness.

A new general method to combine computational fluid dynamics tools and detailed chemical kinetic mechanisms is presented. The method involves post-processing of data extracted from computational fluid dynamics (CFD) simulations obtained by using a simple reaction model to generate an overall estimate of the temperature and flow field in the computational domain. In post-processing of the data, the individual cells in the computational domain are treated as partially stirred reactors, which are modeled using a CHEMKIN formated chemical-kinetic mechanism. As proof-of-principle, the method was applied to a CFX-4 CFD simulation of a laboratory swirl burner using a DCK mechanism comprising 159 chemical species in 773 reactions. The method successfully describes the detailed combustion chemistry of the swirl burner.

Combustion mechanisms of higher hydrocarbons are governed by a hierarchical structure. This structure is reflected in reduced mechanisms based on intrinsic low dimensional manifolds (ILDM). Based on the mathematical analysis we present in this work a hierarchical concept where the ILDMs of higher hydrocarbons are generated on the basis of existing ILDMs of simpler reaction mechanisms. It is based on a numerical method which allows to estimate, how well an ILDM can be represented by an ILDM of a simpler subsystem. If the conditions for a good representation of the ILDM by the simpler subsystem are met, then the ILDM of the simpler system can be used directly. If not, then the ILDM of the simpler subsystem is used as a starting estimate for the generation of the ILDM which reduces the computational effort considerably. The example of a syngas ILDM which is used as a generic ILDM for n-heptane combustion validates the approach.

International audience; Flame ignition, stabilization and extinction or pollutant predictions are crucialissues in Large Eddy Simulations (LES) of turbulent combustion. These phenomenaare strongly influenced by complex chemical effects. Unfortunately, despite the rapid increase in computational power, performing turbulent simulations of industrial configurations including detailed chemical mechanisms will still remain out of reach for a long time. This article proposes a review of commonly-used approaches to address fluid/chemistry interactions at a reduced computational cost. Several chemistry modeling routes are first examined with a focus on tabulated chemistry techniques. The problem of coupling chemistry with LES is considered in a second step. Examples of turbulent combustion simulations are presented in the final part of the article. Three LES applications are analyzed: a lean swirled combustor, a non-adiabatic turbulent stratified flame and a combustion chamber where internal recirculations promote the dilution of fresh gases by burnt gases.

Quantitative species data for the development and critical examination of combustion mechanisms are in high demand regarding the need for predictive combustion models that may assess the emission potential of current and emerging fuels. Mass spectrometric investigation is one of the often-used techniques to provide mole fractions of stable and reactive intermediates including radicals from specifically designed laboratory experiments. Molecular-beam mass spectrometry (MBMS) has been coupled with electron ionization (EI) and photoionization (PI) to determine the species compositions, and combinations of these techniques have been successful in the investigation of the combustion pathways in flames of numerous hydrocarbon, oxygenated and nitrogenated fuels. Photoelectron/photoion coincidence spectroscopy (PEPICO) has recently emerged as a novel diagnostics to be combined with flame-sampling mass spectrometry, and its potential as a complement of existing techniques is just about being explored. In a multi-laboratory investigation, the present study has thus combined four different MBMS spectrometers (in Bielefeld, Germany, the Advanced Light Source in Berkeley, USA, the Swiss Light Source in Villigen, Switzerland, and the SOLEIL synchrotron in St. Aubin, France) to study a rich premixed argon-diluted low-pressure (40 mbar) ethylene-oxygen flame under comparable conditions. This was done with the aim of illustrating the respective properties and capabilities of the methods under these conditions, with an emphasis on the power offered by the synchrotron-based techniques, including PEPICO, for combustion chemistry studies. Examples include comparisons of selected species quantification as well as PEPICO spectra measured at different instruments. (C) 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

The flame structure of a fuel-rich (ϕ = 2.4), laminar premixed, and lightly sooting acetylene flame at 40 mbar and the influence of ethanol addition on the species pool was investigated. Special emphasis was put on the analysis of important soot precursors like propargyl, benzene, and the polyynes. The mole fractions of more than 50 stable and radical species up to m/z = 170 are obtained experimentally in the flames by molecular-beam mass spectrometry (MBMS) in combination with single-photon ionization (SPI) by vacuum ultraviolet (VUV) radiation from the Advanced Light Source (ALS) in Berkeley, CA, USA. For the neat acetylene flame, successful measurements were performed with a combination of MBMS and imaging photoelectron photoion coincidence spectrometry (iPEPICO) at the VUV beamline at the Swiss Light Source (SLS) in Villigen, Switzerland and adding additional species information to the data set. Some interesting isomers (C3H2, C4H5, C4H2O) can be clearly identified by comparison of measured photoionization efficiency (PIE) curves or threshold photoelectron (TPE) spectra with Franck–Condon simulations or literature spectra, respectively. Because of apparatus improvements, the chemical resolution in this study goes beyond prior work and provides a high-quality data set for the development of reaction mechanisms at fuel-rich, low-pressure conditions.

Combustion characteristics and related chemical processes were investigated for a HAN-based liquid propellant, XM46, and its ingredients, HAN and TEAN. Experiments were conducted over the pressure range of 0.1 to 1 atmosphere and at the heat fluxes from 50 to 400 W/cm2 in air and inert gas environments. Flame behavior was observed using a high magnification video system. A triple quadruple mass spectrometer (TQMS) and micro-thermocouples were applied for the temporal measurements of gas-phase species and temperature profiles. Species in the XM46 residue left after burning were analyzed using a gas chromatograph/mass spectrometer (GC/MS). No visible flame was observed from XM46 or its ingredients at 1 ATM and 100 W/cm2. However, at 1 ATM and 400 W/cm2, HAN and TEAN showed distinctive flame behaviors, and XM46 exhibited three flames in sequence with the white HAN flame appearing first, followed by the blue and yellow TEAN flames. Gaseous products evolved from HAN and TEAN exhibited a distinctive set of spec...

International audience; This is Part II of a series of three papers which jointly address the combustion chemistry of furan and its alkylated derivatives 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) under premixed low-pressure flame conditions. Some of them are considered to be promising biofuels. With furan as a common basis studied in Part I of this series, the present paper addresses two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of MF which were studied with electron ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) for equivalence ratios phi = 1.0 and 1.7, identical conditions to those for the previously reported furan flames. Mole fractions of reactants, products as well as stable and reactive intermediates were measured as a function of the distance above the burner. Kinetic modeling was performed using a comprehensive reaction mechanism for all three fuels given in Part I and described in the three parts of this series. A comparison of the experimental results and the simulation shows reasonable agreement, as also seen for the furan flames in Part I before. This set of experiments is thus considered to be a valuable additional basis for the validation of the model. The main reaction pathways of MF consumption have been derived from reaction flow analyses, and differences to furan combustion chemistry under the same conditions are discussed.

Alternative transportation fuels, preferably from renewable sources, include alcohols with up to five or even more carbon atoms. They are considered promising because they can be derived from biological matter via established and new processes. In addition, many of their physical-chemical properties are compatible with the requirements of modern engines, which make them attractive either as replacements for fossil fuels or as fuel additives. Indeed, alcohol fuels have been used since the early years of automobile production, particularly in Brazil, where ethanol has a long history of use as an automobile fuel. Recently, increasing attention has been paid to the use of non-petroleum-based fuels made from biological sources, including alcohols (predominantly ethanol), as important liquid biofuels. Today, the ethanol fuel that is offered in the market is mainly made from sugar cane or corn. Its production as a first-generation biofuel, especially in North America, has been associated with publicly discussed drawbacks, such as reduction in the food supply, need for fertilization, extensive water usage, and other ecological concerns. More environmentally friendly processes are being considered to produce alcohols from inedible plants or plant parts on wasteland. While biofuel production and its use (especially ethanol and biodiesel) in internal combustion engines have been the focus of several recent reviews, a dedicated overview and summary of research on alcohol combustion chemistry is still lacking. Besides ethanol, many linear and branched members of the alcohol family, from methanol to hexanols, have been studied, with a particular emphasis on butanols. These fuels and their combustion properties, including their ignition, flame propagation, and extinction characteristics, their pyrolysis and oxidation reactions, and their potential to produce pollutant emissions have been intensively investigated in dedicated experiments on the laboratory and the engine scale, also emphasizing advanced engine concepts. Research results addressing combustion reaction mechanisms have been reported based on results from pyrolysis and oxidation reactors, shock tubes, rapid compression machines, and research engines. This work is complemented by the development of detailed combustion models with the support of chemical kinetics and quantum chemistry. This paper seeks to provide an introduction to and overview of recent results on alcohol combustion by highlighting pertinent aspects of this rich and rapidly increasing body of information. As such, this paper provides an initial source of references and guidance regarding the present status of combustion experiments on alcohols and models of alcohol combustion.