甲醇分子(CH3OH)光谱性质的理论计算

研究了气相甲醇分子(CH3OH)基态和激发态性质。在对不同方法基组所得计算结果和实验结果进行比较之后,选用MP2(full)/6-311++G(2d,2p)理论方法进行计算,得到甲醇分子(CH3OH)基态和三重激发态的几何结构、能量以及频率信息;频率计算显示基态和三重态都为稳定构型。从三重态的结构出发,解释了三重态势能面为排斥型势能面的合理性。计算了甲醇分子单重激发态的垂直激发能,比较不同方法不同基组计算的甲醇分子单重激发态的垂直激发能,发现用TDDFT 中的b3p86方法使用6-311++G**基组的计算值和实验值符合得最好。计算得到的甲醇分子在MP2(full)/6-311++G(2d,2p)的绝热电离能和垂直电离能分别为11.18eV和11.32eV;计算得到的绝热电子亲和势与垂直电子亲和势分别为0.888eV和0.893eV。计算结果对实验研究有指导意义。     

Numerical study of influence of molecular diffusion in the Mild combustion regime

In this paper, the importance of molecular diffusion versus turbulent transport in the moderate or intense low-oxygen dilution (Mild) combustion mode has been numerically studied. The experimental conditions of Dally et al. [Proc. Combust. Inst. 29 (2002) 1147–1154] were used for modelling. The EDC model was used to describe the turbulence–chemistry interaction. The DRM-22 reduced mechanism and the GRI 2.11 full mechanism were used to represent the chemical reactions of an H₂/methane jet flame. The importance of molecular diffusion for various O₂ levels, jet Reynolds numbers and H₂ fuel contents was investigated. Results show that the molecular diffusion in Mild combustion cannot be ignored in comparison with the turbulent transport. Also, the method of inclusion of molecular diffusion in combustion modelling has a considerable effect on the accuracy of numerical modelling of Mild combustion. By decreasing the jet Reynolds number, decreasing the oxygen concentration in the airflow or increasing H₂ in the fuel mixture, the influence of molecular diffusion on Mild combustion increases.     

Microgravity droplet combustion: effect of tethering fiber on burning rate and flame structure

Droplets tethering on fibers has become a well established technique for conducting droplet combustion experiments in microgravity conditions. The effects of these supporting fibers are frequently assumed to be negligible and are not considered in the experimental analysis or in numerical simulations. In this work, the effect of supporting fibers on the characteristics of microgravity droplet combustion has been investigated numerically; a priori predictions have then been compared with published experimental data. The simulations were conducted using a transient one-dimensional spherosymmetric droplet combustion model, where the effect of the supporting fiber was implicitly taken into account. The model applied staggered convective flux finite volume method combined with high-order implicit time integration. Thermal radiation was evaluated using a statistical narrow band radiation model. Chemical kinetics and thermophysical properties were represented in rigorous detail. Tether fiber diameter, droplet diameter, ambient pressure and oxygen concentration were varied over a range for n-decane droplets in the simulations. The results of the simulations were compared to previously published experiments conducted in the Japan Microgravity Center (JAMIC) 10 second drop tower and the NASA Glenn Research Center (GRC) 5.2 second drop tower. The model reproduces closely nearly all aspects of tethered n-decane droplet burning phenomena, which included droplet burning history, transient and average burning rate, and flame standoff ratio. The predictions show that the presence of the tethering fiber significantly influences the observed burning rate, standoff ratio, and extinction.     

Large Eddy Simulations of a piloted lean premix jet flame using finite-rate chemistry

A Large Eddy Simulation (LES) model capable of accurately representing finite-rate chemistry effects in turbulent premixed combustion is presented. The LES computations use finite-rate chemistry and implicit LES combustion modelling to simulate an experimentally well-documented lean-premixed jet flame stabilized by a stoichiometric pilot. The validity of the implicit LES assumption is discussed and criteria are expressed in terms of subgrid scale Damköhler and Karlovitz numbers. Simulation results are compared to experimental data for velocity, temperature and species mass fractions of CH₄, CO and OH. The simulation results highlight the validity and capability of the present approach for the flame and in general the combustion regime examined. A sensitivity analysis to the choice of the finite-rate chemistry mechanism is reported, this analysis indicates that the one and two-step global reaction mechanisms evaluated fail to capture the reaction layer with sufficient accuracy, while a 20-species skeletal mechanism reproduces the experimental observations accurately including the key finite-rate chemistry indicators CO and OH. The LES results are shown to be grid insensitive and that the grid resolution within the bounds examined is far less important compared to the sensitivity of the finite-rate chemistry representation. The results are analyzed in terms of the flame dynamics and it is shown that intense small scale mixing (high Karlovitz number) between the pilot and the jet is an important mechanism for the stabilization of the flame.     

Numerical study of the effect of turbulence on rate of reactions in the MILD combustion regime

In this paper, the importance of fluctuations in flow field parameters is studied under MILD combustion conditions. In this way, a turbulent non-premixed CH₄+H₂ jet flame issuing into a hot and deficient co-flow air is modeled using the RANS Axisymmetric equations. The modeling is carried out using the EDC model to describe the turbulence-chemistry interaction. The DRM-22 reduced mechanism and the GRI2.11 full mechanism are used to represent the chemical reactions of H₂/methane jet flame. Results illustrate that although the fluctuations in temperature field are small and the reaction zone volume are large in the MILD regime, the fluctuations in temperature and species concentrations are still effective on the flow field. Also, inappropriate dealing with the turbulence effect on chemistry leads to errors in prediction of temperature up to 15% in the present flame. By decreasing of O₂ concentration of hot co-flow air, the effect of fluctuations in flow field parameters on flame characteristics are still significant and its effect on species reaction rates does not decrease. On the other hand, although decreasing of jet inlet Reynolds number at constant inlet turbulence intensity addresses to smaller fluctuations in flow filed, it does not lead to lower the effect of turbulence on species distribution and temperature field under MILD combustion conditions.     

The role of cool-flame chemistry in quasi-steady combustion and extinction of n-heptane droplets

Experiments on the combustion of large n-heptane droplets, performed by the National Aeronautics and Space Administration in the International Space Station, revealed a second stage of continued quasi-steady burning, supported by low-temperature chemistry, that follows radiative extinction of the first stage of burning, which is supported by normal hot-flame chemistry. The second stage of combustion experienced diffusive extinction, after which a large vapour cloud was observed to form around the droplet. In the present work, a 770-step reduced chemical-kinetic mechanism and a new 62-step skeletal chemical-kinetic mechanism, developed as an extension of an earlier 56-step mechanism, are employed to calculate the droplet burning rates, flame structures, and extinction diameters for this cool-flame regime. The calculations are performed for quasi-steady burning with the mixture fraction as the independent variable, which is then related to the physical variables of droplet combustion. The predictions with the new mechanism, which agree well with measured autoignition times, reveal that, in decreasing order of abundance, H₂O, CO, H₂O₂, CH₂O, and C₂H₄ are the principal reaction products during the low-temperature stage and that, during this stage, there is substantial leakage of n-heptane and O₂ through the flame, and very little production of CO₂ with no soot in the mechanism. The fuel leakage has been suggested to be the source of the observed vapour cloud that forms after flame extinction. While the new skeletal chemical-kinetic mechanism facilitates understanding of the chemical kinetics and predicts ignition times well, its predicted droplet diameters at extinction are appreciably larger than observed experimentally, but predictions with the 770-step reduced chemical-kinetic mechanism are in reasonably good agreement with experiment. The computations show how the key ketohydroperoxide compounds control the diffusion-flame structure and its extinction.     

基于激光诱导偏振光谱与激光诱导荧光技术的CH4/AIR火焰参数测量

建立了激光诱导偏振光谱（LIPS）和激光诱导荧光（LIF）联合的燃烧流场诊断系统,测量了CH4/AIR预混火焰中心不同高度处的OH荧光光谱和激光诱导偏振光谱,计算了OH的浓度及燃烧场温度分布。分析了燃烧炉表面对荧光收集效率的影响,并对两种技术的测量数据进行了分析比对,获得了火焰中心OH密度的分布规律。实验结果表明,联合LIPS和LIF两种技术测量CH4/AIR预混火焰参数是可行的,两种技术测量结果的一致性较好,OH浓度的相对偏差小于5%,温度的相对偏差小于8%。     

A normalised residence time transport equation for the numerical simulation of combustion with high-temperature air

This study concerns the numerical simulation of turbulent non-premixed combustion in highly preheated air streams. One of the objectives is to settle an efficient computational procedure to proceed with the numerical simulation of large-scale industrial devices. It is also expected that the availability of such a computational framework may facilitate comprehensive sensitivity analyses as well as the development of mathematical models able to represent turbulence-chemistry interactions (TCI) in such conditions. Based on the salient physical ingredients that characterise scalar mixing, propagation, and self-ignition processes, a turbulent combustion modelling framework is thus introduced and applied to the numerical simulation of well-documented laboratory flames. In the corresponding geometries, the bulk flow velocities of the reactants streams can reach rather large values, which lead the flame to lift from the burner rim. Partially premixed flame edges thus stabilise the whole flame structure and the temperature of the oxidising stream can be increased by vitiation with burned gases so as to promote the corresponding flame-stabilisation processes. For sufficiently large values of the vitiated airstream temperature, self-ignition mechanisms may be triggered thus leading to a competition between mixing, propagation, and ignition processes. In this context, the ratio of the residence time to the self-ignition delay is thought to be a relevant variable to delineate the possible influence of ignition phenomena. Therefore, a modelled transport equation for this normalised residence time is considered. The performance of the corresponding modelling proposal is analysed with special emphasis placed on its ability to reproduce ‘memory’ or ‘lagrangian’ effects related to thermal aging processes. In this respect, it is noteworthy that the present set of computations makes use of tabulated quantities associated to (i) steady laminar one-dimensional diffusion flamelets, so as to describe the composition of combustion products, (ii) steady laminar one-dimensional premixed flamelets, to describe the flame brush propagation, and (iii) temporal evolution of zero-dimensional homogeneous mixtures to account for the possible occurrence of self-ignition phenomena. In particular, the tabulated self-ignition time value is used to evaluate the increase in the normalised residence time. Finally, two modelling parameters are put into evidence and studied through a detailed sensitivity analysis.     

Multiple speeds of flame edge propagation for Lewis numbers above one

Edges of diffusion flames in a counterflow burner are examined numerically for Lewis greater than unity. When the speed of propagation is plotted against Damköhler for a range of Lewis a fold bifurcation is observed. It is shown that there exist stable positively and negatively propagating edges for some Damköhler and Lewis number pairs. It is further shown that changed local conditions can lead to a transition from positive (advancing into the unburnt gasses) to negative (receding) propagation.     

Multi-environment probability density function method for modelling turbulent combustion using realistic chemical kinetics

A computational fluid dynamics (CFD) tool for performing turbulent combustion simulations that require finite-rate chemistry is developed and tested by modelling a series of bluff-body stabilized flames that exhibit different levels of finite-rate chemistry effects ranging from near equilibrium to near global extinction. The new modelling tool is based on the multi-environment probability density function (MEPDF) methodology and combines the following: the direct quadrature method of moments (DQMOM); the interaction-by-exchange-with-the-mean (IEM) mixing model; and realistic combustion chemistry. Using DQMOM, the MEPDF model can be derived from the transport PDF equation by depicting the joint composition PDF as a weighted summation of a finite number of multi-dimensional Dirac delta functions in the composition space. The MEPDF method with multiple reactive scalars retains the unique property of the joint PDF method of treating chemical reactions exactly. However, unlike the joint PDF methods that typically must resort to particle-based Monte-Carlo solution schemes, the MEPDF equations (i.e. the transport equations of the weighted delta-peaks) can be solved by traditional Eulerian grid-based techniques. In the current study, a pseudo time-splitting scheme is adopted to solve the MEPDF equations; the reaction source terms are computed with a highly efficient and accurate in-situ adaptive tabulation (ISAT) algorithm. A 19-species reduced mechanism based on quasi-steady state assumptions is used in the simulations of the bluff-body flames. The modelling results are compared with the experimental data, including mixing, temperature, major species and important minor species such as CO and NO. Compared with simulations using a Monte-Carlo joint PDF method, the new approach shows comparable accuracy.