A detailed chemical kinetic mechanism for methanol combustion in laminar flames

On the basis of existing detailed kinetic schemes a general and consistent mechanism of the oxidation of methanol was compiled for computational studies covering a wide range of lean to rich flames. The proposed model, featuring 21 species and 115 reactions, has been validated using three data sets and the computed reactants, products and intermediates mole fractions. This scheme was compared to those by Held-Dryer, Egolfopolous and Pauwels under the same conditions. The developed mechanism predicts well the concentrations of the major reactants, intermediates, and products at all the studied equivalence ratios and it gives the best calculated values, as compared to the other used models, as well. The production rates analysis of selected species allowed the identification of the major formation and depletion pathways. A reaction path analysis snowed that the main channels in methanol consumption involved H, OH and O attack and the resulting radicals CH₂OH and CH₃O produced formaldehyde.     

Benzene combustion: A detailed chemical kinetic modeling in laminar flames conditions

Models resulting from the merging of validated kinetic schemes were used to compile a new detailed mechanism for benzene combustion in laminar flames. The proposed model, featuring 215 species and 1313 reactions, has been validated using fuel-rich, low-pressure, premixed benzene-oxygen-argon flames available in the literature. Good agreement between simulated and experimental data is achieved for the major reactants, intermediates, and products. However, computed maxima for some polyaromatic hydrocarbons were lower than experimental ones.     

The comparison of detailed chemical kinetic mechanisms: Application to the combustion of methane

Detailed chemical kinetic mechanisms of complex chemical phenomena may be composed of hundreds of species and thousands of individual elementary reactions. It can be an extremely laborious and error‐prone procedure to compare two of these mechanisms, particularly if they come from different sources. We have created software tools which help to highlight the differences between mechanisms written in a Chemkin format and demonstrate their applicability to five literature mechanisms describing the high temperature oxidation of methane. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36:467–471, 2004     

Automotive fuels and internal combustion engines: a chemical perspective

Commercial transportation fuels are complex mixtures containing hundreds or thousands of chemical components, whose composition has evolved considerably during the past 100 years. In conjunction with concurrent engine advancements, automotive fuel composition has been fine-tuned to balance efficiency and power demands while minimizing emissions. Pollutant emissions from internal combustion engines (ICE), which arise from non-ideal combustion, have been dramatically reduced in the past four decades. Emissions depend both on the engine operating parameters (e.g. engine temperature, speed, load, A/F ratio, and spark timing) and the fuel. These emissions result from complex processes involving interactions between the fuel and engine parameters. Vehicle emissions are comprised of volatile organic compounds (VOCs), CO, nitrogen oxides (NO(x)), and particulate matter (PM). VOCs and NO(x) form photochemical smog in urban atmospheres, and CO and PM may have adverse health impacts. Engine hardware and operating conditions, after-treatment catalysts, and fuel composition all affect the amount and composition of emissions leaving the vehicle tailpipe. While engine and after-treatment effects are generally larger than fuel effects, engine and after-treatment hardware can require specific fuel properties. Consequently, the best prospects for achieving the highest efficiency and lowest emissions lie with optimizing the entire fuel-engine-after-treatment system. This review provides a chemical perspective on the production, combustion, and environmental aspects of automotive fuels. We hope this review will be of interest to workers in the fields of chemical kinetics, fluid dynamics of reacting flows, atmospheric chemistry, automotive catalysts, fuel science, and governmental regulations.     

A detailed chemical kinetic model for high temperature ethanol oxidation

A detailed chemical kinetic model for ethanol oxidation has been developed and validated against a variety of experimental data sets. Laminar flame speed data (obtained from a constant volume bomb and counterflow twin‐flame), ignition delay data behind a reflected shock wave, and ethanol oxidation product profiles from a jet‐stirred and turbulent flow reactor were used in this computational study. Good agreement was found in modeling of the data sets obtained from the five different experimental systems. The computational results show that high temperature ethanol oxidation exhibits strong sensitivity to the fall‐off kinetics of ethanol decomposition, branching ratio selection for C₂H₅OH + OH ↔ Products, and reactions involving the hydroperoxyl (HO₂) radical. The multichanneled ethanol decomposition process is analyzed by RRKM/Master Equation theory, and the results are compared with those obtained from earlier studies. The ten‐parameter Troe form is used to define the C₂H₅OH(+M) ↔ CH₃ + CH₂OH(+M) rate expression as k^∞ = 5.94E23 T^−1.68 exp(−45880 K/T) (s⁻¹) k^o = 2.88E85 T^−18.9 exp(−55317 K/T) (cm³/mol/sec) F_cent = 0.5 exp(−T/200 K) + 0.5 exp(−T/890 K) + exp(−4600 K/T) and the C₂H₅OH(+M) ↔ C₂H₄ + H₂O(+M) rate expression as k^∞ = 2.79E13 T^0.09 exp(−33284 K/T) (s⁻¹) k^o = 2.57E83 T^−18.85 exp(−43509 K/T) (cm³/mol/sec) F _cent = 0.3 exp(−T/350 K) + 0.7 exp(−T/800 K) + exp(−3800 K/T) with an applied energy transfer per collision value of <ΔE_down> = 500 cm⁻¹. An empirical branching ratio estimation procedure is presented which determines the temperature dependent branching ratios of the three distinct sites of hydrogen abstraction from ethanol. The calculated branching ratios for C₂H₅OH + OH, C₂H₅OH + O, C₂H₅OH + H, and C₂H₅OH + CH₃ are compared to experimental data. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 183–220, 1999     

Development and testing of a detailed kinetic mechanism of natural gas combustion in internal combustion engine

A detailed chemical mechanism to describe the combustion of natural gas in internal combustion (IC) engine has been developed,which is consisting of 233 reversible reactions and 79 species.This mechanism accounts for the oxidation of methane,ethane,propane and nitrogen.It has been tested using IC engine model of CHEMKIN 4.1.1 and experimental measurements.The performance of the proposed mechanism was evaluated at various equivalence ratios (φ=0.6 to φ=1.3),initial reactor conditions (Tini=500 to 3500 ℃;Pini...     

Automatic reduction of detailed mechanisms of combustion of alkanes by chemical lumping

This article presents an automatic method for reducing a detailed primary mechanism of combustion of any single alkane. Free radicals having the same molecular formula and the same functional groups are lumped into one single species. The number of free radicals of the primary mechanism is divided by a factor 16 in the case of n‐heptane. The kinetic parameters of lumped reactions are computed as weighted means of individual rate constants without any fitting process. The simulations of lumped and detailed mechanisms of combustion of isooctane and n‐heptane show a good agreement in a wide temperature range (600–1200 K). © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 36–51, 2000     

Automatic comparison of thermodynamic data for species in detailed chemical kinetic modeling

This article describes the performance of an automatic comparator of thermochemical databases and demonstrates the use of a hypertext preprocessor to link chemical names with a three‐dimensional molecular viewer thus providing an unambiguous identification of species in a facile manner over the Internet. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 341–345, 2005     

Efficient chemical kinetic modeling through neural network maps

An approach to modeling nonlinear chemical kinetics using neural networks is introduced. It is found that neural networks based on a simple multivariate polynomial architecture are useful in approximating a wide variety of chemical kinetic systems. The accuracy and efficiency of these ridge polynomial networks (RPNs) are demonstrated by modeling the kinetics of H(2) bromination, formaldehyde oxidation, and H(2)+O(2) combustion. RPN kinetic modeling has a broad range of applications, including kinetic parameter inversion, simulation of reactor dynamics, and atmospheric modeling.     

The comparison of detailed chemical kinetic mechanisms; forward versus reverse rates with CHEMRev

The computation of the reverse rate of an elementary reaction given the forward rate and requisite thermodynamic data is well established. Nevertheless the procedure is extremely laborious and error prone, in particular, when large numbers of such calculations must be performed and the results fitted to traditional or extended forms of the Arrhenius rate constant equation. We have developed a software application, CHEMRev, which automatically performs such computations for Chemkin‐style reaction mechanisms. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 119–125, 2005     

Reduction of large detailed chemical kinetic mechanisms for autoignition using joint analyses of reaction rates and sensitivities

This study describes a new technique of reduction of detailed mechanisms for autoignition. It is based on two analysis methods. An analysis of reaction rates is coupled to an analysis of reaction sensitivity for the detection of redundant reactions. Thresholds associated with the two analyses have a great influence on the size and efficiency of the reduced mechanism. Rules of selection of the thresholds are defined. The reduction technique has been successfully applied to detailed autoignition mechanisms of two reference hydrocarbons: n‐heptane and isooctane. The efficiency of the technique and the ability of the reduced mechanisms to reproduce well the results generated by the full mechanism are discussed. A speedup of calculations by a factor of 5.9 for n‐heptane mechanism and by a factor of 16.7 for isooctane mechanism is obtained without losing accuracy of the prediction of autoignition delay times and concentrations of intermediate species. © 2007 Wiley Periodicals, Inc. 39: 181–196, 2007     

Screening gas-phase chemical kinetic models: Collision limit compliance and ultrafast timescales

Detailed gas-phase chemical kinetic models are widely used in combustion research, and many new mechanisms for different fuels and reacting conditions are developed each year. Recent works have highlighted the need for error checking when preparing such models, but a useful community tool to perform such analysis is missing. In this work, we present a simple online tool to screen chemical kinetic mechanisms for bimolecular reactions exceeding collision limits. The tool is implemented on a user-friendly website, cloudflame.kaust.edu.sa, and checks three different classes of bimolecular reactions; (ie, pressure independent, pressure-dependent falloff, and pressure-dependent PLOG). In addition, two other online modules are provided to check thermodynamic properties and transport parameters to help kinetic model developers determine the sources of errors for reactions that are not collision limit compliant. Furthermore, issues related to unphysically fast timescales can remain an issue even if all bimolecular reactions are within collision limits. Therefore, we also present a procedure to screen ultrafast reaction timescales using computational singular perturbation. For demonstration purposes only, three versions of the rigorously developed AramcoMech are screened for collision limit compliance and ultrafast timescales, and recommendations are made for improving the models. Larger models for biodiesel surrogates, tetrahydropyran, and gasoline surrogates are also analyzed for exemplary purposes. Numerical simulations with updated kinetic parameters are presented to show improvements in wall-clock time when resolving ultrafast timescales.     

A detailed chemical kinetic model for the supercritical water oxidation of methylamine: The importance of imine formation

A detailed chemical kinetic model has been developed for supercritical water oxidation (SCWO) of methylamine, CH₃NH₂, providing insight into the intermediates and final products formed in this process as well as the dominant reaction pathways. The model was adapted from previous mechanisms, with a revision of the peroxyl radical chemistry to include imine formation, which has recently been identified as the dominant gas-phase pathway in amine oxidation. The developed model can reproduce previous experimental data on methylamine consumption and major product formation to reasonable accuracy, although with deficiencies in describing the induction time. Our simulations indicate that oxidation of the ^•CH₂NH₂ radical to methanimine, CH₂NH, is the major channel in methylamine SCWO, with subsequent hydrolysis of CH₂NH providing the experimentally observed reaction products ammonia and formaldehyde. Integral-averaged reaction rates were used to identify major reaction pathways, and a first-order sensitivity analysis indicated that the concentration of CH₃NH₂ is most sensitive to OH radical kinetics. Overall, this work clarifies the importance of imine chemistry in the oxidation of nitrogen-containing compounds and indicates that they are necessary to model these compounds in SCWO processes.     

Evaluation of models for the low temperature combustion of alkanes through interpretation of pressure-temperature ignition diagrams

The purpose of this paper is to show the application of global uncertainty analysis to comprehensive and reduced kinetic models as a tool to identify important thermochemical and reaction rate parameters as determinants of the conditions leading to autoignition. Propane oxidation is taken as the test case. The simulation of experimental investigations of the cool flames and two-stage ignitions, via the pressure-temperature ignition diagram, show that existing kinetic models for the low temperature combustion of propane at sub-atmospheric pressures reflect a greater reactivity than seems to be appropriate. That is, the models lead to a prediction of two-stage ignition at pressures somewhat lower and with ignition delays shorter than is found experimentally. The inconsistency between experiment and numerical simulation seems not to be an inherent problem of the qualitative structure of the models, but may derive from uncertainties in the parameters within the mechanism. By use of "brute force", Morris-one-at-a-time and Monte-Carlo simulations, we show that uncertainties in only a small number of parameters, and falling well within the errors that may reasonably be assigned, can shift the response appropriately. Moreover, it appears that in the low temperature combustion regime, thermochemistry is at least as, if not more, important than the reaction rates, yet usually receives less attention within sensitivity studies. In the present case, the main factors controlling the temperature reached in the first stage of two-stage ignition and the time to ignition appear to be connected with the thermochemistry of three specific hydroperoxyalkyl radicals and their derivatives. Other factors, such as heat and mass transport are also addressed, and their effects are mitigated to some extent by evaluation of initial and revised models against experimental data for ignition delay obtained under microgravity. The results highlight more general issues that pertain to the numerical simulation of the combustion of higher hydrocarbons and contribute to the development of the protocol necessary for testing kinetic models before they are ready for use in a predictive capacity.     

Emission and performance analysis of DI diesel engines fueled by biodiesel blends via CFD simulation of spray combustion and different spray breakup models: a numerical study

Journal of Thermal Analysis and Calorimetry - In the current study, computational fluid dynamics code was used to perform 3D simulation of mixture formation and combustion of biodiesel fuel spray...     

反应NH~4ClO~4+Mg+K~2Cr~2O~7的非线性化学动力学2: 固相 振荡燃烧的化学模 型

建立了NH~4ClO~4+Mg+K~2Cr~2O~7固相振荡燃烧体系的非吸热三变量立方自催化化学模型,应用非线性数学分析方法,研究了固相振荡燃烧的非线性化学动力学机理,并对此进行了数值模拟,结果反映了这一振荡燃烧体系所具有的非线性化学动力学特性。