正丁烷/空气在微反应器内的气相与催化反应

本文通过实验研究了富燃的正丁烷/空气混合物在有、无Pt催化剂蜂窝陶瓷反应器内的气相与表面反应过程。实验结果表明,根据反应温度的不同,正丁烷/空气混合物的催化氧化过程分为三个区域:低温的表面催化反应控制区、高温的气相反应控制区和中温的催化/气相反应共同控制区。在表面催化反应控制区,即使是富燃料混合物,其反应产物也只有完全氧化产物,而不存在CO等不完全氧化产物。在达到气相着火后的气相反应控制区,混合物主要发生部分氧化和热裂解反应过程,表面催化反应的影响很小,反应产物主要是部分氧化产物和裂解产物CO,H_2、CH_4、C_2H_4、C_3H_6等。     

正丙醚低温氧化特性的反应机理研究

醚类被认为是优质的直接燃料或燃料添加剂。为进一步揭示醚类的低温氧化反应机制,本文构建了包含详细机理的正丙醚燃烧反应动力学模型,并利用前人的高压氧化实验数据对模型进行了验证。相比于前人的模型,本文模型可以准确预测不同当量比条件下正丙醚的氧化特性。基于模型分析,本文揭示了不同温度下OH自由基的来源以及不同温度下正丙醚的氧化路径差异,为正丙醚的进一步研究提供了方向。     

柴油/甲烷和柴油/甲醇二元燃料着火反应机理比较研究

本文在定容燃烧弹中利用高速摄像技术研究了柴油在甲烷/空气和甲醇/空气氛围中低温着火特性,并基于正庚烷/甲烷简化机理和正庚烷/甲醇骨架机理,对比分析了两种二元燃料的低温氧化路径。试验和模拟结果均表明甲烷和甲醇都能使柴油着火时刻推迟,且甲醇推迟作用更明显,柴油推迟着火现象随甲烷和甲醇当量比增大而更明显,随环境温度升高而减弱。反应路径分析表明,甲烷和甲醇的脱氢反应消耗了大量OH抑制了正庚烷着火,甲醇抑制作用强于甲烷原因在于甲醇消耗OH速率快,且只通过低温下很稳定的H_2O_2分解向自由基池中提供OH,而甲烷消耗的OH少,还能通过链传递反应(CH_3+HO_2=CH_3O+OH)贡献相当数量的OH。     

基于解耦法构建柴油表征燃料的骨架机理

本文构建了一个包含正癸烷、异辛烷、甲苯和甲基环己烷的柴油表征燃料模型。基于解耦法构建了一个包含70种组分和193个反应的柴油表征燃料的骨架机理。在解耦法中,骨架机理被分为两部分:一部分是极其简化的C_2-C_n机理,用于预测燃料的滞燃期和消耗;另一部分为详细的H_2/CO/C_1机理,用于预测火焰速度和熄火极限,以及碳氢和一氧化碳的排放。通过与激波管中的滞燃期、搅拌反应器(JSR)中的组分浓度、层流火焰速度以及预混压燃(PCCI)发动机中的燃烧和排放的实验数据对比,发现机理较好地预测了柴油的着火、燃烧和排放特性。     

正庚烷化学动力学简化模型的构建及优化

提出了一个新的适用于HCCI发动机燃烧模拟的正庚烷化学反应动力学简化模型(40种组分和62个反应)。由三个子模型组成:低温反应子模型是在Li等人模型的基础上,定义具体的醛类(RCHO)产物和小分子碳氢产物(Rs)而构建;增加了用于链接低温反应向高温反应过渡的大分子直接裂解成小分子反应子模型;高温反应子模型是在Griffiths等人模型的基础上,去除了无关的基元反应,增加两个关于CO和CH3O的氧化反应而构建。另外,采用遗传优化技术对模型动力学参数进行调整。计算表明,新模型能够在当量比0．2-1．2,温度从300-3000 K的范围内精确模拟正庚烷HCCI燃烧时冷焰和热焰反应过程,与详细模型(544种组分和2446个反应)计算结果吻合较好。     

适用于HCCI燃烧的PRF化学动力学骨架机理

本文构建了一个适用于HCCI燃烧的PRF化学反应动力学骨架机理。该机理包含40种组分和65个反应。通过与激波管、喷射搅拌反应器、流动反应器和HCCI发动机的实验数据对比表明,新机理适用于多种反应器,可以较准确地计算着火点及关键组分的演变规律,并且在不同的温度、压力和当量比下具有较好的性能。在HCCI发动机的单区模型计算中,对于燃料PRF 91.8和PRF 70,骨架机理计算结果与Curran等人的详细机理计算结果基本相同。     

烷烃/正庚烷和醇/正庚烷二元燃料低温着火特性的模拟研究

二元燃料燃烧技术作为一种应用替代能源的技术已经被广泛应用,为了深入地理解天然气、液化石油气和醇类等被引燃燃料对柴油低温着火的推迟影响,本文对二元燃料低温着火过程进行了模拟研究。结果表明,在初始温度小于1000 K时,被引燃燃料推迟正庚烷着火的能力由高到低的顺序为:乙烷丙烷正丁烷正戊烷正己烷,从正戊烷开始,被引燃燃料对正庚烷着火的抑制作用开始消失。甲醇和乙醇几乎没有低温反应活性,它们将活泼的OH转化为了稳定的H_2O_2;醛类和烯醇的生成反应是醇类燃料推迟正庚烷着火能力强于对应烷烃燃料的原因。     

正庚烷低温燃烧机理构建

基于课题组自主研发的高碳烃燃烧机理自动生成程序ReaxGen,构建了正庚烷低温燃烧详细机理(642个物种,2220步反应)。分别采用物质产率分析和反应路径流量分析方法简化该详细机理,得到半详细机理(510个物种,1472步反应)和骨架机理(20g个物种,770步反应)。对正庚烷的点火延时,层流火焰速度以及主要物种浓度曲线的模拟结果表明这些机理的模拟精度较高。在工程计算流体力学仿真设计中具有良好的应用前景。分析了正庚烷点火延时敏感度,考查了机理中关键反应。     

二甲醚低温氧化及甲醛生成特性实验研究

在常压环境下对二甲醚的低温氧化特性做了实验研究,并在不同当量比下研究了预混气中甲醛的生成特性.实验结果表明,二甲醚在200℃左右开始缓慢发生氧化反应,在250~379℃时氧化反应最为剧烈,750℃时被完全氧化为CO2和水;在二甲醚低温氧化产物中,甲醛是其重要的组分,二甲醚在200~400℃温度环境下最容易氧化而产生甲醛...     

均三甲苯低温氧化的实验和模拟研究

利用射流搅拌反应器研究了常压贫燃条件下均三甲苯在700~1100 K温区内的低温氧化动力学。实验检测了27种产物和中间体,并采用Dievart等人提出的机理进行了模拟。结果表明主要产物和中间体的实验和模拟结果符合较好,少数微量中间体模拟还有待于进一步提高。反应路径分析及敏感性分析指出均三甲苯与OH发生脱氢反应以及氢取代生成间二甲苯是重要的反应。本文研究了均三甲苯在常压条件下的低温氧化特性,为其应用于航空替代燃料提供了理论基础。     

Experimental counterflow ignition temperatures and reaction mechanisms of 1,3-butadiene

The ignition temperatures of nitrogen-diluted 1,3-butadiene by heated air in counterflow were experimentally determined for pressures up to 5 atmospheres and pressure-weighted strain rates from 100 to 250 s⁻¹. The experimental data were compared with computational results using the mechanism of Laskin et al. [A. Laskin, H. Wang and C.K. Law, Int. J. Chem. Kinet. 32 (10) (2000) 589-614], showing that while the overall prediction is approximately within the experimental uncertainty, the mechanism over-predicts ignition temperature by about 25-40 K, with the differences becoming larger at high pressure/low temperature region. Sensitivity analyses for the near-ignition states were performed for both reactions and diffusion, which identified the importance of H₂/CO chain reactions, three 1,3-butadiene reaction pathways, and the binary diffusion between 1,3-butadiene and N₂ on ignition. The detailed mechanism, consisting of 94 species and 614 reactions, was then simplified to a skeletal mechanism consisting of 46 species and 297 reactions by using a new reduction algorithm combining directed relation graph and sensitivity analysis. The skeletal mechanism was further simplified to a 30-step reduced mechanism by using computational singular perturbation and quasi-steady-state assumptions. Both the skeletal and reduced mechanisms mimic the performance of the detailed mechanism with good accuracy in both homogeneous and heterogeneous systems.     

An improved path flux analysis with multi generations method for mechanism reduction

An improved path flux analysis with a multi generations (IMPFA) method is proposed to eliminate unimportant species and reactions, and to generate skeletal mechanisms. The production and consumption path fluxes of each species at multiple reaction paths are calculated and analysed to identify the importance of the species and of the elementary reactions. On the basis of the indexes of each reaction path of the first, second, and third generations, the improved path flux analysis with two generations (IMPFA2) and improved path flux analysis with three generations (IMPFA3) are used to generate skeletal mechanisms that contain different numbers of species. The skeletal mechanisms are validated in the case of homogeneous autoignition and perfectly stirred reactor of methane and n-decane/air mixtures. Simulation results of the skeletal mechanisms generated by IMPFA2 and IMPFA3 are compared with those obtained by path flux analysis (PFA) with two and three generations, respectively. The comparisons of ignition delay times, final temperatures, and temperature dependence on flow residence time show that the skeletal mechanisms generated by the present IMPFA method are more accurate than those obtained by the PFA method, with almost the same number of species under a range of initial conditions. By considering the accuracy and computational efficiency, when using the IMPFA (or PFA) method, three generations may be the best choice for the reduction of large-scale detailed chemistry.     

A reduced mechanism for biodiesel surrogates with low temperature chemistry for compression ignition engine applications

Biodiesel is a promising alternative fuel for compression ignition (CI) engines. It is a renewable energy source that can be used in these engines without significant alteration in design. The detailed chemical kinetics of biodiesel is however highly complex. In the present study, a skeletal mechanism with 123 species and 394 reactions for a tri-component biodiesel surrogate, which consists of methyl decanoate, methyl 9-decanoate and n-heptane was developed for simulations of 3-D turbulent spray combustion under engine-like conditions. The reduction was based on an improved directed relation graph (DRG) method that is particularly suitable for mechanisms with many isomers, followed by isomer lumping and DRG-aided sensitivity analysis (DRGASA). The reduction was performed for pressures from 1 to 100 atm and equivalence ratios from 0.5 to 2 for both extinction and ignition applications. The initial temperatures for ignition were from 700 to 1800 K. The wide parameter range ensures the applicability of the skeletal mechanism under engine-like conditions. As such the skeletal mechanism is applicable for ignition at both low and high temperatures. Compared with the detailed mechanism that consists of 3299 species and 10806 reactions, the skeletal mechanism features a significant reduction in size while still retaining good accuracy and comprehensiveness. The validations of ignition delay time, flame lift-off length and important species profiles were also performed in 3-D engine simulations and compared with the experimental data from Sandia National Laboratories under CI engine conditions.     

Systematic analysis and reduction of combustion mechanisms for ignition of multi-component kerosene surrogate

Currently, most detailed chemical kinetic mechanisms for combustion are still not comprehensive enough and update of key reaction rate is still required to improve the combustion mechanisms. The development of systematic mechanism reduction methods have made significant progress, and have greatly facilitated analysis of the reaction mechanisms and identification of important species and key reactions. In the present work, time-integrated element flux analysis is employed to analyze a skeletal combustion mechanism of a tri-component kerosene surrogate mixture, consisting of n-decane, n-propylcyclohexane, and n-propylbenzene. The results of element flux analysis indicate that major reaction pathways for each component in the surrogate model are captured by the skeletal mechanism compared with the detailed mechanism. After that, sensitivity analysis (SA) and chemical explosive mode analysis (CEMA) are conducted to identify the dominant ignition chemistry. The SA and CEMA results demonstrate that the ignition of n-decane and n-propylcyclohexane is sensitive only to the oxidation chemistry of H₂/CO and C1–C4 small hydrocarbons, while the ignition of n-propylbenzene is very sensitive to the initial reactions of n-propylbenzene and related aromatic intermediates. This demonstrates that the hierarchic structure should be maintained in the reduction of detailed mechanism of substituted aromatic fuels. The skeletal mechanism is further reduced by combining the computational singular perturbation (CSP) method and quasi steady state approximation (QSSA). A 34-species global reduced mechanism is obtained and validated over a wide range of parameters for ignition.     

Generalized entropy production analysis for mechanism reduction

The paper introduces a generalized formulation for the computation of the relative contribution of each elementary reaction to the total entropy production, which has been proposed as a measure of the importance of elementary reactions and used for the reduction of detailed chemical reaction mechanisms. The reduction method is extended for the cases where the principle of detailed balance does not hold or apply, namely in the case of irreversible reactions or when the reverse rate constants are not computed via the thermodynamic equilibrium constants. Using a mechanism for n-butane consisting exclusively of reversible reactions, the new formulation is compared to the original one, and then applied for the construction of a skeletal mechanism for n-dodecane starting from a detailed mechanism which includes predominantly irreversible reactions. The skeletal scheme is found to accurately capture the ignition delay times over an extended range of pressure, initial temperature and equivalence ratio, the steady-state temperature as function of the residence time in a non-isothermal adiabatic perfectly stirred reactor, and the laminar flame speed of atmospheric flames at different unburned mixture temperatures and equivalence ratios.     

Development and validation of an n-dodecane skeletal mechanism for spray combustion applications

n-Dodecane is a promising surrogate fuel for diesel engine study because its physicochemical properties are similar to those of the practical diesel fuels. In the present study, a skeletal mechanism for n-dodecane with 105 species and 420 reactions was developed for spray combustion simulations. The reduction starts from the most recent detailed mechanism for n-alkanes consisting of 2755 species and 11,173 reactions developed by the Lawrence Livermore National Laboratory. An algorithm combining direct relation graph with expert knowledge (DRGX) and sensitivity analysis was employed for the present skeletal reduction. The skeletal mechanism was first extensively validated in 0-D and 1-D combustion systems, including auto-ignition, jet stirred reactor (JSR), laminar premixed flame and counter flow diffusion flame. Then it was coupled with well-established spray models and further validated in 3-D turbulent spray combustion simulations under engine-like conditions. These simulations were compared with the recent experiments with n-dodecane as a surrogate for diesel fuels. It can be seen that combustion characteristics such as ignition delay and flame lift-off length were well captured by the skeletal mechanism, particularly under conditions with high ambient temperatures. Simulations also captured the transient flame development phenomenon fairly well. The results further show that ignition delay may not be the only factor controlling the stabilisation of the present flames since a good match in ignition delay does not necessarily result in improved flame lift-off length prediction.     

DME/LPG混合燃料HCCI燃烧模拟

根据碳氢燃料化学反应系统具有层次结构的特性,本文通过分析二甲醚(DME)与液化石油气(LPG)的详细化学反应机理,构建了反映DME／LPG混合燃料均质压燃(HCCI)燃烧的详细化学反应机理．采用该机理应用单区燃烧模型对DME／LPG混合燃料HCCI燃烧的化学反应动力学过程进行了数值计算．计算结果与试验结果对比表明,所构建的DME／LPG混合燃料氧化的详细化学反应机理能够准确预测DME／LPG混合燃料的两阶段放热特性,对低温和高温着火始点的预测很好;但高温反应过程预测欠佳,高温反应机理需要改进．     

Skeletal mechanism generation and analysis for n-heptane with CSP

We use a procedure based on the decomposition into fast and slow dynamical components offered by the Computational Singular Perturbation (CSP) method to generate automatically skeletal kinetic mechanisms for the simplification of the kinetics of n-heptane oxidation. The detailed mechanism of the n-heptane oxidation here considered has been proposed by Curran et al. and involves 561 species and 2538 reactions. After carrying out a critical assessment of important aspects of this procedure, we show that the comprehensive skeletal kinetic mechanisms so generated are able to reproduce the main features of n-heptane ignition at various initial pressures and temperatures and equivalence ratios. A by-product of the algorithm that generates the skeletal mechanisms is the identification of the network of important species and reactions at a given state of the kinetic system. The analysis of this network is carried out by resorting to a visual representation of the pathways at selected time instants of the ignition process. Visual inspection of the pathways enables the identification and comparison of the relevant kinetic processes as obtained at different ignition regimes. The graphs are generated by interfacing the model reduction procedure with the open-source package graphviz.     

二甲醚HCCI燃烧高温反应动力学分析

应用单区燃烧模型对二甲醚均质压燃燃烧的化学反应动力学过程进行了数值模拟研究。通过分析在内燃机压燃燃烧边界条件下二甲醚高温氧化反应过程中的关键基元反应速度、关键中间产物以及自由基的浓度随曲轴转角的变化,得到了二甲醚燃烧氧化的高温反应途经。结果表明,二甲醚均质压燃燃烧具有明显的两阶段放热特性,即低温反应放热和高温反应放热。高温反应阶段又可分为蓝焰反应阶段和热焰反应阶段,其中蓝焰反应阶段是甲醛氧化成CO的过程,热焰反应主要是CO氧化成CO2的过程。二甲醚氧化产物之一甲酸(HOCHO)在蓝焰反应阶段分解生成CO2。