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在生物柴油和菲舍-托普施燃料中的关键分支反应的初步研究
Alexander C Davis1, Joseph S Francisco
1Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393, USA.
燃料中的甲基基基对于燃烧化学至关重要. 这项研究显示,它们的气迁移反应比以前想象的要快,影响了燃料模型.
科学领域:
- 化学动力学 化学动力学
- 燃烧化学 燃烧化学是什么
- 计算化学计算化学
背景情况:
- 分支基在生物燃料和合成燃料中普遍存在.
- 在氧化过程中形成的甲基基是关键的中间体.
- 关于甲基基基反应的数据有限,特别是对于较大的分子,是有限的.
研究的目的:
- 研究甲基基基 (n=2-6) 中的迁移反应.
- 确定甲基对单分子,链分支反应的影响.
- 为燃烧建模提供准确的热力学和动力学参数.
主要方法:
- 采用了CBS-Q,G2和G4复合计算方法.
- 在广泛的温度范围内分析了气迁移反应.
- 对甲基基基的计算激活能量和速率参数.
主要成果:
- 涉及甲基组的气迁移反应显示了较低的激活能 (0.8-1.6 kcal mol(-1)).
- 目前的模型大大低于预测这些连锁分支反应的重要性.
- 特定的分支基,如2,2,4,4,6,8,8-heptamethylnonane,可能不能准确地代表柴油燃料替代品.
- 与理论相反,在某些甲基基基中,二次迁移可能比三次迁移更快.
结论:
- 甲基组显著影响迁移反应的动力学.
- 现有的燃烧模型需要修订,以准确地纳入甲基基基的化学成分.
- 这些发现对理解和建模分支碳化合物的燃烧具有重要意义.
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