Computational singular perturbation analysis of two-stage ignition of large hydrocarbons

Computational singular perturbation (CSP) analysis has been used to gain understanding of the complex kinetic behavior associated with two-stage ignition of large hydrocarbon molecules. To this end, available detailed and reduced chemical kinetics models commonly used in numerical simulations of n-heptane oxidation phenomena are directly analyzed to interpret the underlying fundamental steps leading to two-stage ignition. Unlike previous implementations of the CSP methodology, temperature is included as one of the state variables so that factors controlling ignition can be unambiguously determined. The analyzed models show differences in the factors contributing to the initial development and shutdown of the first ignition stage. However, during the second stage, both models show the importance of the degenerate branching decomposition of hydrogen peroxide, which contradicts some previous interpretations of this phenomenon.     

甲基肼/四氧化二氮反应化学动力学模型构建及分析

甲基肼(MMH)和四氧化二氮(NTO)是常用的液体火箭发动机推进剂,但目前对其反应机理的研究还十分有限.本文首先构建了一个包含23种组分和20个基元反应的MMH/NTO反应动力学模型;对MMH/NTO自燃着火过程进行的验证计算表明,该机理能够合理地描述MMH/NTO的自燃温升过程,准确预测反应物系统的着火延迟时间及平衡温度,并能合理地反映MMH/NTO反应物系统着火延迟时间对反应初始压力以及氧燃比的依赖关系;通过灵敏度分析方法指出了影响MMH/NTO着火过程的关键反应.模拟分析了在不同压力和氧燃比条件下MMH/NTO系统的自燃温升过程,结果表明,随着压力的升高,系统着火延迟时间变短,平衡温度升高;在一定范围内增大氧燃比,着火延迟时间变长,平衡温度先升高后减小.     

不同液化条件下生物质残渣的燃烧特性研究

对锯屑在不同液化条件（溶剂、气氛、温度、催化剂）下所得液化残渣在热天平上进行了燃烧特性研究,通过比较液化残渣燃烧的三个特征温度,着火点ti、燃烧峰温tp和燃烬温度tb,分析了液化条件对残渣燃烧特性的影响。同时通过热重曲线所得数据探讨了液化残渣燃烧过程的动力学,并计算了活化能和频率因子 。结果表明,不同溶剂下所得液化残渣的燃烧特性显著不同,以四氢萘为溶剂所得液化残渣具有较好的燃烧特性;不同气氛下所得残渣的燃烧特性没有明显的不同;350℃下所得液化残渣的燃烧特性要好于300℃下所得液化残渣的燃烧特性;由于催化剂的影响,加入1%Mo后降低了所得液化残渣的燃烧特性;液化残渣的燃烧反应符合两段一级反应动力学。     

Comprehensive H2/O2 kinetic model for high‐pressure combustion

An updated H₂/O₂ kinetic model based on that of Li et al. (Int J Chem Kinet 36, 2004, 566–575) is presented and tested against a wide range of combustion targets. The primary motivations of the model revision are to incorporate recent improvements in rate constant treatment and resolve discrepancies between experimental data and predictions using recently published kinetic models in dilute, high‐pressure flames. Attempts are made to identify major remaining sources of uncertainties, in both the reaction rate parameters and the assumptions of the kinetic model, affecting predictions of relevant combustion behavior. With regard to model parameters, present uncertainties in the temperature and pressure dependence of rate constants for HO₂ formation and consumption reactions are demonstrated to substantially affect predictive capabilities at high‐pressure, low‐temperature conditions. With regard to model assumptions, calculations are performed to investigate several reactions/processes that have not received much attention previously. Results from ab initio calculations and modeling studies imply that inclusion of H + HO₂ = H₂O + O in the kinetic model might be warranted, though further studies are necessary to ascertain its role in combustion modeling. In addition, it appears that characterization of nonlinear bath‐gas mixture rule behavior for H + O₂(+ M) = HO₂(+ M) in multicomponent bath gases might be necessary to predict high‐pressure flame speeds within ～15%. The updated model is tested against all of the previous validation targets considered by Li et al. as well as new targets from a number of recent studies. Special attention is devoted to establishing a context for evaluating model performance against experimental data by careful consideration of uncertainties in measurements, initial conditions, and physical model assumptions. For example, ignition delay times in shock tubes are shown to be sensitive to potential impurity effects, which have been suggested to accelerate early radical pool growth in shock tube speciation studies. In addition, speciation predictions in burner‐stabilized flames are found to be more sensitive to uncertainties in experimental boundary conditions than to uncertainties in kinetics and transport. Predictions using the present model adequately reproduce previous validation targets and show substantially improved agreement against recent high‐pressure flame speed and shock tube speciation measurements. Comparisons of predictions of several other kinetic models with the experimental data for nearly the entire validation set used here are also provided in the Supporting Information. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 44: 444–474, 2012     

典型燃料点火延迟时间的一阶和二阶局部和全局敏感度分析

Sensitivity analysis is an important tool in model validation and evaluation that has been employed extensively in the analysis of chemical kinetic models of combustion processes. The input parameters of a chemical kinetic model are always associated with some uncertainties, and the effects of these uncertainties on the predicted combustion properties can be determined through sensitivity analysis. In this work, first- and second-order global and local sensitivity coefficients of ignition delay time with respect to the scaling factor for reaction rate constants in chemical kinetic mechanisms for combustion of H₂, methane, n-butane, and n-heptane are examined. In the sensitivity analysis performed here, the output of the model is taken to be natural logarithm of ignition delay time and the input parameters are the natural logarithms of the factors that scale the reaction rate constants. The output of the model is expressed as a polynomial function of the input parameters, with up to coupling between two input parameters in the present sensitivity analysis. This polynomial function is determined by varying one or two input parameters, and allows the determination of both local and global sensitivity coefficients. The order of the polynomial function in the present work is four, and the factor that scales the reaction rate constant is in the range from 1/e to e, where e is the base of the natural logarithm. A relatively small number of sample runs are required in this approach compared to the global sensitivity analysis based on the highly dimensional model representation method, which utilizes random sampling of input (RS-HDMR). In RS-HDMR, sensitivity coefficients are determined only for the rate constants of a limited number of reactions; the present approach, by contrast, affords sensitivity coefficients for a larger number of reactions. Reactions and reaction pairs with the largest sensitivity coefficients are listed for ignition delay times of four typical fuels. Global sensitivity coefficients are always positive, while local sensitivity coefficients can be either positive or negative. A negative local sensitivity coefficient indicates that the reaction promotes ignition, while a positive local sensitivity coefficient suggests that the reaction actually suppresses ignition. Our results show that important reactions or reaction pairs identified by global sensitivity analysis are usually rather similar to those based on local sensitivity analysis. This finding can probably be attributed to the fact that the values of input parameters are within a rather small range in the sensitivity analysis, and nonlinear effects for such a small range of parameters are negligible. It is possible to determine global sensitivity coefficients by varying the input parameters over a larger range using the present approach. Such analysis shows that correlation effects between an important reaction and a minor reaction can have relatively sizable second-order sensitivity coefficient in some cases. On the other hand, first-order global sensitivity coefficients in the present approach will be affected by coupling between two reactions, and some results of the first-order global sensitivity analysis will be different from those determined by local sensitivity analysis or global sensitivity analysis under conditions where the correlation effects of two reactions are neglected. The present sensitivity analysis approach provides valuable information on important reactions as well as correlated effects of two reactions on the combustion characteristics of a chemical kinetic mechanism. In addition, the analysis can also be employed to aid global sensitivity analysis using RS-HDMR, where global sensitivity coefficients are determined more reliably.     

正十二烷高温机理简化及验证

由于详细化学反应机理在模拟燃烧室燃烧时,计算量极大,很难被广泛运用。为了满足工程设计要求,采用替代燃料的简化机理进行计算不失为一种行之有效的方法。本文基于误差传播的直接关系图法和敏感性分析法对正十二烷180组分1962步高温机理(温度大于1100 K)进行简化,获得40组分234步化学反应机理。在温度为1100–1650 K,压力为0.1–4 MPa条件下,采用简化机理及详细机理对不同当量比、压力下着火延迟时间进行模拟,模拟结果与实验数据吻合得较好。通过对不同压力及温度下火焰传播速度进行模拟,验证了简化机理能够正确地反映正十二烷的燃烧特性。利用C_(12)H_(26)/OH/H_2O/CO_2等重要组分随时间变化的数据,验证了简化机理能够准确描述燃烧过程反应物消耗、基团变化、生成物产生的过程,并表明该机理具有较高的模拟精度。利用该简化机理对本生灯进行数值分析,结果表明该机理能够准确地反映火焰区温度和组分浓度的变化。紧凑的正十二烷高温简化机理不仅能够正确体现其物理化学特性,而且能够用于三维数值模拟,具有较高的工程运用价值和应用前景。     

Effect of radiation absorption modes on ignition time of translucent polymers subjected to time-dependent heat flux

Majority of previous solid ignition models, including numerical and analytical ones, considered only surface absorption of incident heat flux for simplification. However, the influence of in-depth absorption on pyrolysis and subsequent ignition cannot be ignored for infrared translucent polymers. This work addresses this problem and focuses on time-dependent heat flux to establish an analytical model for ignition behaviors prediction by means of theoretical analysis. Ignition temperature was utilized as the ignition criterion, and both surface and in-depth absorption scenarios were considered. Thermally thick polymethyl methacrylate and polyamide 6 were selected as reference materials to verify the reliability and applicability of the proposed model by comparing the analysis results with experimental data as well as numerical simulations. A method for determining the approximation parameters of the theoretical analysis was presented to derive the relationship between ignition time and the coefficients in heat flux expressions. The results show that the higher surface temperature owing to surface absorption accelerates the pyrolysis rate and results in a shorter ignition time, while in-depth absorption affects the ignition time inversely. The effect of surface heat loss was also evaluated quantitatively through both analytical and numerical models. The uncertainty of the proposed model is mainly caused by the selection of the approximation parameters. Nevertheless, it provides an alternative approach to estimate the ignition time of translucent polymers besides numerical simulation.

     

Experimental and modeling study of the oxidation of cyclohexene

Ignition delays of cyclohexene–oxygen–argon mixtures were measured behind shock. Mixtures contained 1 or 2% of hydrocarbons for equivalence ratios ranging from 0.5 to 2. Reflected shock waves permitted to obtain temperatures from 1050 to 1520 K and pressures from 7.7 to 9.1 atm. The experimental results exhibit an Arrhenius variation vs. temperature. A detailed mechanism of the combustion of cyclohexene has been written in the line of the mechanism developed previously for the reaction of C₃? C₄ unsaturated hydrocarbons (propyne, allene, 1,3‐butadiene, butynes); it is based on recent kinetic data values published in the literature and is consistent with thermochemistry. This mechanism has been validated by comparing the results of the simulations to the experimental results obtained for ignition delays. The main reaction pathways have been derived from flow rate and sensitivity analyses for the different temperature areas studied. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 273–285, 2003     

增压O_2/CO_2气氛下煤燃烧特性实验研究

增压O2/CO2燃烧是一种可高效分离回收CO2的新兴燃烧技术,其燃烧机理与常压空气、常压O2/CO2燃烧存在较大差异。在加压热重分析仪上研究了增压条件下总压、氧浓度、气氛及粒径等反应参数对美国烟煤和淮北无烟煤燃烧特性的影响,确定了煤的着火温度,并对其进行燃烧动力学分析。结果表明,增压O2/CO2气氛下,随着压力或氧浓度的增加,DTG曲线向低温区移动,煤样整体燃烧速率加快。压力提升、氧浓度增加及煤粉细化均可改善O2/CO2气氛下煤样的着火特性。常压O2/CO2气氛下煤粉燃烧基本属于一级反应;增压O2/CO2气氛下,低温区属于0.5级反应,而高温区属于1.5级反应。     

Plasma Assisted Low Temperature Combustion

This paper presents recent kinetic and flame studies in plasma assisted low temperature combustion. First, the kinetic pathways of plasma chemistry to enhance low temperature fuel oxidation are discussed. The impacts of plasma chemistry on fuel oxidation pathways at low temperature conditions, substantially enhancing ignition and flame stabilization, are analyzed base on the ignition and extinction S-curve. Secondly, plasma assisted low temperature ignition, direct ignition to flame transition, diffusion cool flames, and premixed cool flames are demonstrated experimentally by using dimethyl ether and n-heptane as fuels. The results show that non-equilibrium plasma is an effective way to accelerate low temperature ignition and fuel oxidation, thus enabling the establishment of stable cool flames at atmospheric pressure. Finally, the experiments from both a non-equilibrium plasma reactor and a photolysis reactor are discussed, in which the direct measurements of intermediate species during the low temperature oxidations of methane/methanol and ethylene are performed, allowing the investigation of modified kinetic pathways by plasma-combustion chemistry interactions. Finally, the validity of kinetic mechanisms for plasma assisted low temperature combustion is investigated. Technical challenges for future research in plasma assisted low temperature combustion are then summarized.     

The Importance of Relative Reaction Rates in the Optimization of Detailed Kinetic Models

Numerous mathematical tools intended to adjust rate constants employed in complex detailed kinetic models to make them consistent with multiple sets of experimental data have been reported in the literature. Application of such model optimization methods typically begins with the assignment of uncertainties in the absolute rate constants in a starting model, followed by variation of the rate constants within these uncertainty bounds to tune rate parameters to match model outputs to experimental observations. The present work examines the impact of including information on relative reaction rates in the optimization strategy, which is not typically done in current implementations. It is shown that where such rate constant data are available, the available parameter space changes dramatically due to the correlations inherent in such measurements. Relative rate constants are typically measured with greater relative accuracy than corresponding absolute rate constant measurements. This greater accuracy further reduces the available parameter space, which significantly affects the uncertainty in the model outcomes as a result of kinetic parameter uncertainties. We demonstrate this effect by considering a simple example case emulating an ignition event and show that use of relative rate measurements leads to a significantly smaller uncertainty in the output ignition delay time in comparison with results based on absolute measurements. This is true even though the same range of absolute rate constants is sampled in each case. Implications of the results with respect to the maintenance of physically realistic kinetics in optimized models are discussed, and suggestions are made for the path forward in the refinement of detailed kinetic models.     

Chemical‐kinetic modeling of ignition delay: Considerations in interpreting shock tube data

High‐pressure shock tube ignition delays have been and continue to be one of the key sources of data that are important to characterizing the combustion properties of real fuels. At pressures and temperatures of importance to practical applications, concerns have recently been raised as to the large differences observed between experimental data and chemical‐kinetic predictions using the common assumption that the shock tube behaves as a constant volume (V) system with constant internal energy (U). Here, a concise review is presented of phenomena that can considerably affect shock tube data at the extended test times (several milliseconds or longer) needed for the measurement of fuel/air ignition at practical conditions (i.e., high pressures and relatively low temperatures). These effects include fluid dynamic nonidealities as well as deflagrative processes typical of mild ignition events. Proposed modeling approaches that attempt to take into account these effects, by employing isentropic assumptions and pressure‐ and temperature‐varying systems, are evaluated and shown to significantly improve modeling results. Finally, it is argued that at the conditions of interest ignition delay data do not represent pure chemical‐kinetic observations but are affected by phenomena that are in some measure facility specific. This hampers direct cross comparison of the experimental ignition data collected in different venues. In such cases, pressure/temperature histories should be provided in order to properly interpret shock tube ignition data. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 143–150, 2010     

NOFBX新型绿色推进剂燃烧化学反应动力学模型

本文以具有绿色无毒、高性能、低成本等诸多优势的N_2O-C_2烃类燃料单元复合推进剂(即NOFBX)为对象,首先发展了包含52组分、325反应的燃烧化学反应机理模型。该机理不仅能够准确计算N_2O热解过程中重要组分的分布,而且能够在较宽的温度、压力、化学计量比范围内准确预测N_2O-C_2烃类燃料体系的着火延迟时间和层流火焰传播速度。鉴于本文提出的N_2O-C_2烃类燃料反应机理具有机理规模小、实验验证充分的特点,有望在NOFBX发动机的多维燃烧数值模拟中得到广泛应用。     

空气污染组分H_2O和CO_2对乙烯燃烧性能的影响(Ⅱ)——反应机理和动力学模拟

超燃冲压发动机在高空工作时,以高温高速纯净空气作氧化剂使燃料燃烧.但在地面实验中,高温空气往往通过燃烧加热方式获得,会使空气中含有H2O和CO2等污染组分.本文用活塞流反应器进行动力学模拟,研究在不同初温、压强和燃气比的条件下,H2O和CO2污染组分对乙烯燃烧的温度、压强和点火延迟时间等特性的影响.模拟结果表明:乙烯在含有H2O/CO2污染物的空气中燃烧,相比纯净的空气而言,H2O对乙烯的点火有一定的促进作用,而CO2有一定的抑制作用;空气中含H2O和CO2污染物使乙烯燃烧的平衡温度和压强降低,在污染物浓度相同时,CO2引起的下降幅度比H2O的大.模拟结果能较好地解释现有的实验现象.     

低温燃料化学特性对湍流预混火焰传播的影响

大分子碳氢燃料的低温化学反应及两阶段点火特性会显著影响火焰的分区及燃烧情况。本文采用数值模拟的方法探究了正庚烷/空气预混混合气在RATS燃具上的湍流火焰传播,与试验结果具有一致性。模拟使用的是44种物质,112步的正庚烷简化动力学机理。使用Open FOAM的reacting Foam求解器建立了简化模拟流道及出口的三维模型,模拟了在大气环境下,初始反应温度450–700 K、入口速度6 m·s~(-1)与10 m·s~(-1)、焰前流动滞留时间100 ms及60 ms、当量比φ=0.6的正庚烷/空气混合气湍流火焰燃烧情况。结果发现,标准化湍流燃烧速度与混合气初始温度以及流动滞留时间有关。在低温点火阶段,正庚烷氧化程度受到初始温度与速度的影响,燃料分解并在预热区中产生大量中间物质如CH_2O,继而会影响湍流火焰燃烧速度。随着初始反应温度的升高,湍流燃烧火焰逐渐由化学反应冻结区过渡到低温点火区;温度超过一定数值后,燃料不再发生低温反应,此时燃烧位于高温点火区域。     

Reduced combustion time model for methane in gas turbine flow fields

Computational fluid dynamics (CFD) modeling of the complex processes that occur within the burner of a gas turbine engine has become a critical step in the design process. However, due to computer limitations, it is very difficult to completely couple the fluid mechanics solver with the full combustion chemistry. Therefore, simplified chemistry models are required, and the topic of this research was to provide reduced chemistry models for CH4/O2 gas turbine flow fields to be integrated into CFD codes for the simulation of flow fields of natural gas-fueled burners. The reduction procedure for the CH4/O2 model utilized a response modeling technique wherein the full mechanism was solved over a range of temperatures, pressures, and mixture ratios to establish the response of a particular variable, namely the chemical reaction time. The conditions covered were between 1000 and 2500 K for temperature, 0.1 and 2 for equivalence ratio in air, and 0.1 and 50 atm for pressure. The kinetic time models in the form of ignition time correlations are given in Arrhenius-type formulas as functions of equivaience ratio, temperature, and pressure; or fuel-to-air ratio, temperature, and pressure. A single ignition time model was obtained for the entire range of conditions, and separate models for the low-temperature and high-temperature regions as well as for fuel-lean and rich cases were also derived. Predictions using the reduced model were verified using results from the full mechanism and empirical correlations from experiments. The models are intended for (but not limited to) use in CFD codes for flow field simulations of gas turbine combustors in which initial conditions and degree of mixedness of the fuel and air are key factors in achieving stable and robust combustion processes and acceptable emission levels. The chemical time model was utilized successfully in CFD simulations of a generic gas turbine combustor with four different cases with various levels of fuel-air premixing.     

Uncertainty analysis of correlated parameters in automated reaction mechanism generation

Uncertainty analysis is a useful tool for inspecting and improving detailed kinetic mechanisms because it can identify the greatest sources of model output error. Owing to the very nonlinear relationship between kinetic and thermodynamic parameters and computed concentrations, model predictions can be extremely sensitive to uncertainties in some parameters while uncertainties in other parameters can be irrelevant. Error propagation becomes even more convoluted in automatically generated kinetic models, where input uncertainties are correlated through kinetic rate rules and thermodynamic group values. Local and global uncertainty analyses were implemented and used to analyze error propagation in Reaction Mechanism Generator (RMG), an open-source software for generating kinetic models. A framework for automatically assigning parameter uncertainties to estimated thermodynamics and kinetics was created, enabling tracking of correlated uncertainties. Local first-order uncertainty propagation was implemented using sensitivities computed natively within RMG. Global uncertainty analysis was implemented using adaptive Smolyak pseudospectral approximations as implemented in the MIT Uncertainty Quantification Library to efficiently compute and construct polynomial chaos expansions to approximate the dependence of outputs on a subset of uncertain inputs. Cantera was used as a backend for simulating the reactor system in the global analysis. Analyses were performed for a phenyldodecane pyrolysis model. Local and global methods demonstrated similar trends; however, many uncertainties were significantly overestimated by the local analysis. Both local and global analyses show that correlated uncertainties based on kinetic rate rules and thermochemical groups drastically reduce a model's degrees of freedom and have a large impact on the determination of the most influential input parameters. These results highlight the necessity of incorporating uncertainty analysis in the mechanism generation workflow.     

Development and application of a ReaxFF reactive force field for hydrogen combustion

To investigate the reaction kinetics of hydrogen combustion at high-pressure and high-temperature conditions, we constructed a ReaxFF training set to include reaction energies and transition states relevant to hydrogen combustion and optimized the ReaxFF force field parameters against training data obtained from quantum mechanical calculations and experimental values. The optimized ReaxFF potential functions were used to run NVT MD (i.e., molecular dynamics simulation with fixed number of atoms, volume, and temperature) simulations for various H(2)/O(2) mixtures. We observed that the hydroperoxyl (HO(2)) radical plays a key role in the reaction kinetics at our input conditions (T ≥ 3000 K, P > 400 atm). The reaction mechanism observed is in good agreement with predictions of existing continuum-scale kinetic models for hydrogen combustion, and a transition of reaction mechanism is observed as we move from high pressure, low temperature to low pressure, high temperature. Since ReaxFF derives its parameters from quantum mechanical data and can simulate reaction pathways without any preconditioning, we believe that atomistic simulations through ReaxFF could be a useful tool in enhancing existing continuum-scale kinetic models for prediction of hydrogen combustion kinetics at high-pressure and high-temperature conditions, which otherwise is difficult to attain through experiments.     

Study of the combustion mechanism of oil shale semicoke in a thermogravimetric analyzer

Oil shale semicoke, formed in retort furnaces, is a source of severe environmental pollution and is classified as a dangerous solid waste. For the industrial application of oil shale semicoke in combustion, this present work focused on the thermal analysis of its combustion characteristics. The pyrolysis and combustion experiments of semicoke were conducted in a Pyris thermogravimetric analyzer. From the comparison of pyrolysis curves with combustion curves, the ignition mechanism of semicoke samples prepared at different carbonization temperatures was deduced, and was found to be homogeneous for semicoke samples obtained at lower carbonization temperature, shifting to heterogeneous with an increase in the carbonization temperature. The effect of carbonization temperatures and heating rates on the combustion process was studied as well. At last, combustion kinetic parameters of semicoke were calculated with the binary linear regression method, showing that activation energy will increase with increasing the heating rate.     

Investigation on 1-Heptene/Air Laminar Flame Propagation under Elevated Pressures

The laminar flame propagation of 1-heptene/air mixtures covering equivalence ratios from 0.7 to 1.5 is investigated in a constant-volume cylindrical combustion vessel at 373 K and elevated pressures (1, 2, 5, and 10 atm). Laminar flame speed and Markstein length are derived from the recorded schlieren images. A kinetic model of 1-heptene combustion is developed based on our previous kinetic model of 1-hexene. The model is validated against the laminar flame speed data measured in this work and the ignition delay time data in literature. Modeling analyses, such as sensitivity analysis and rate of production analysis, are performed to help understand the high temperature chemistry of 1-heptene under various pressures and its influence on the laminar flame propagation. Furthermore, the laminar flame propagation of 1-heptene/air mixtures is compared with that of n-heptane/air mixtures reported in our previous work. The laminar flame speed values of 1-heptene/air mixtures are observed to be faster than those of n-heptane/air mixtures under most conditions due to the enhanced exothermicity and reactivity.