摘要
水冲压发动机是一种新型的水下推进装置,其只携带水反应金属燃料,并以外界环境中的海水为主要氧化剂。通过金属燃料与水反应产生发动机所需推力,因此具有较高的质量能量密度和体积能量密度。综合比较各种金属与水反应的能量密度及反应活性,认为金属镁是水反应金属燃料的首选。研究镁/水反应机理是掌握水反应金属燃料与水的反应机理的基础,对于提高该类发动机燃烧效率和能量转换效率有重要意义。本文主要进行了四个方面的研究,包括镁在水蒸气中着火和燃烧的机理及模型研究,镁/水高温均相化学反应机理研究,镁铝合金在水蒸气中燃烧特性研究。
本文首先研究了镁在水蒸气中的着火机理及模型,在高温管式炉中考察了加热速率、水蒸气浓度和粒径等因素,对镁颗粒着火温度和着火延迟时间的影响规律。在此基础上建立了镁颗粒在水蒸气中着火的能量方程,对能量方程中各控制变量进行分析简化,根据实验结果计算得到了不同粒径镁颗粒在水蒸气中着火的动力学参数,并对不同粒径的镁颗粒在水蒸气中的着火温度和着火时间进行了预测。
然后研究了镁在水蒸气中的燃烧机理和模型,在可视化氙灯加热燃烧试验台上利用高速照相机拍摄了镁颗粒燃烧过程中表面形态的变化,检测了燃烧火焰的发射光谱,通过燃烧火焰中镁、氧化镁等物质的特征谱线确定了颗粒的燃烧时间,对不同粒径镁颗粒的燃烧时间进行测量。在实验的基础上,建立了镁颗粒在水蒸气中准稳态燃烧的物理数学模型,认为该过程为受扩散控制蒸发燃烧过程,同时考虑了氧化镁冷凝沉积等因素对燃烧过程的影响。根据模型计算得到的镁颗粒的燃烧时间,常压下与直径的2.5次幂近似成正比,高压下与直径的1.5次幂近似成正比,并与水蒸气浓度的0.9幂成反比关系,与实验结果基本吻合。同时对100μm镁颗粒在不同环境温度中的氧化、着火和燃烧过程进行了数值模拟。
利用量子化学方法研究了镁/水高温均相化学反应机理,在B3LYP/6-311++G(3df,2p)水平上优化了镁/水反应的反应物、生成物、过渡态和中间体的结构,并用G2M(CC2)方法计算了反应通道上各驻点的能量。结果显示高温下镁/水的均相化学反应,先生成一个非平面结构的镁/水加合物Mg·OH2,其可以通过氢原子解离途径生成最终产物,反应中间体为MgOH和H；也可以通过氢原子转移途径生成最终产物,反应中间体为HMgOH,通过量子化学估算两个过程的活化能分别为48.28kcal/mol和32.51kcal/mol.根据计算得到反应途径及势能面数据,采用变分过渡态理论计算了高温下镁/水均相化学反应速率,并应用零曲率隧道法对反应速率进行了修正,计算得到在1000K～5000K温度范围内,镁/水均相总反应速率为k=3.85×10-10×T0.39×exp(-17852/T)。在此基础上,建立了高温下镁/水详细的反应机理和相应的燃烧数学模型,并利用CHEMKIN程序中的OPPDIF模块对镁/水燃烧火焰进行模拟分析。
最后研究了镁铝合金在水蒸气中的燃烧特性,分别对金属镁、铝以及铝含量分别为40%、50%和60%的三种镁铝合金粉末的理化特性和物质组成进行了分析。并通过高温氢氧焰试验台研究了镁铝合金的燃烧特性,发现燃烧过程可分为两个阶段：第一阶段镁燃烧的时间基本不变,而第二阶段铝燃烧的时间随着铝含量的增加逐渐变长。对收集的燃烧产物进行了XRD检测,在此基础上分析了镁铝合金与水蒸气的反应途径,认为在合金中镁含量较多时,燃烧产物主要为MgO和MgAl2O4,只有当铝含量较多时,燃烧产物中才会出现Al2O3。
Water ramjet as a new type of underwater propulsion device, using hydro-reactive metal fuel and seawater in the external environment as the main oxidant. The propulsion of the engine is generated by the metal fuels reacting with water, which has very high mass and volumetric energy densities. Comprehensive comparison of the energy density and the reactivity of various metal reacting with water, magnesium is the first choice for hydro-reactive metal fuel. Studying the Mg/H2O reaction mechanism is the basis to grasp the reaction mechanism of the metal fuel reacting with water, which is important for enhancing the combustion efficiency and energy conversion efficiency of the water ramjet. This paper mainly performance four areas of research, including the ignition and combustion mechanism and model of magnesium in steam, high temperature homogeneous chemical reaction mechanism between magnesium and water, and the combustion characteristics of magnesium-aluminum alloy in steam.
This paper firstly studied the ignition mechanism and model of the magnesium in steam. The effects of heating rate, steam concentration and particle diameter on ignition temperature and ignition delay time of magnesium in steam were studied by tube reactor. Based on experimental study, the ignition energy equation of magnesium particles in steam was established, and control variables in the energy equation were analysed and simplified. According to the experimental results, the kinetic parameters of magnesium particles with different diameters were calculated, and the ignition temperature and time of magnesium particles in steam were predicted.
Then the combustion mechanism and model of the magnesium in steam were studied. The surface morphology of the magnesium particle in combustion process was shot by high-speed camera in visualization xenon lamp heating burner, the emission spectrum of the combustion flame was detected. The burning time of magnesium particle was determined by characteristic lines of combustion flame, and the burning time of magnesium particles with different diameters was measured. Based on experimental study, the quasi-steady physical and mathematical model of the combustion of magnesium particles in steam was established, mainly affected by the diffusion-controlled evaporation combustion process, and the magnesium oxide condensation and deposition was also considered. The burning time was calculated by the combustion model. The results shows that it is approximate proportion to the2.5power of the diameter in atmospheric pressure and1.5power of the diameter in high pressure, and inversely proportion to the0.9power of steam concentration, which are consistent with the experimental results. The oxidation, ignition and combustion process of100μm magnesium particles at different ambient temperature was also simulated.
Reaction mechanism of Mg with water was investigated by ab initio quantum chemical methods. The geometries and frequencies of all reactants, products, intermediates and transition states were calculated at the B3LYP/6-311G++(3df.2p) level. Higher-level energies were obtained at G2M (CC2) level using the B3LYP-optimized geometries. The Mg and water firstly formed an atom-molecule adduct Mg·OH2, and then either formed MgOH+H by a H-dissociation process or formed HMgOH by a H-migration process. The barrier heights of two processes are48.28kcal/mol and32.51kcal/mol. The rate constants were calculated by using the variational transition-state theory with the zero-curvature tunneling correction in a temperature range of1000-5000K, and the total rate constant of Mg/water is3.85×10-10×T0.39×exp(-17852/T). Then a detailed reaction mechanism of magnesium/water under high temperature and combustion mathematical model was established, and OPPDIF simulator in CHEMKIN program was used to analysis the structure of the combustion flame.
Finally, the combustion characteristics of magnesium aluminum alloy in steam were studied. The physical and chemical properties and composition of magnesium, aluminum, and magnesium-aluminum alloy with aluminum content of40%，50%and 60%were analyzed. The combustion characteristics of magnesium-aluminum alloy was studied in high-temperature hydrogen-oxygen flame, and found that the combustion process is divided into two phases:the first stage is the combustion of magnesium with nearly the same burning time, and the second stage is combustion of aluminum with longer burning time when the aluminum content in alloy increased. The combustion products were collected and analyzed by XRD. The reaction pathway of magnesium-aluminum alloy with steam is also analyzed, found that the combustion products are mainly the MgO, and MgAl2O4when the magnesium content in the alloy is more than aluminum, and the combustion products Al2O3only appears when the aluminum content is higher.
引文
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