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OALib Journal期刊
ISSN: 2333-9721
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吸热型碳氢燃料正癸烷热裂解机理、热沉及产物分布的理论研究
, PP. 1136-1145
Keywords: 正癸烷,热裂解机理,速率常数,动力学模拟,热沉,产物分布
Abstract:
？采用密度泛函理论(dft)的b3lyp方法在6-311g(d,p)基组水平上对正癸烷裂解过程中涉及的反应物、产物及过渡态进行了几何构型优化和振动频率计算,运用b3lyp/aug-cc-pvtz方法计算单点能并构建势能剖面图。利用therate程序包及eckart校正模型计算了各反应速率常数k。采用统计热力学原理求得不同温度下的热容cp,mθ及熵s298kθ,并通过设计等键反应获得了各物种的标准生成焓△fh298kθ。用chemkinii程序模拟预测了产物分布,理论计算了热沉值,并讨论了温度、压力对产物分布和热沉的影响。结果表明,c-c键断裂过程是反应的初始步骤,且抽氢反应较β键断裂反应更易进行。裂解起始温度为500℃,反应主要发生在600~700℃,其主要产物为氢气、甲烷、乙烯、乙烷、丙烯和1,3-丁二烯,且产物分布随温度不同而变化。模拟计算获得正癸烷在温度600℃、压力2.5mpa条件下的总热沉值为2.334mj/kg,对应的热裂解转化率为25.9%,该热沉值可以满足速率为5~6马赫数的飞行器的冷却要求。
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