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水热提质条件下褐煤脱氧过程的量子化学研究

DOI: 10.13334/j.0258-8013.pcsee.2014.32.009, PP. 5757-5762

Keywords: 褐煤,水热提质,苯甲酸,苯甲醛,量子化学,密度泛函数

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Abstract:

水热脱水提质能够有效地脱除褐煤等低阶煤内部水分与含氧官能团,提高褐煤的煤阶及应用价值。选用褐煤的简化含氧模型化合物苯甲酸和苯甲醛,在分子水平上对褐煤的脱氧反应机制进行研究。采用量子化学B3LYP/6-31G(d)密度泛函数方法,得到水热提质条件下反应过程中各反应物、中间体、过渡态和产物的几何构型和能量变化,进而得到反应过程的热力学和动力学参数。计算结果表明:在水热提质的压力条件下,苯甲酸脱羧基的反应能自发进行,而苯甲醛脱羰基的反应在较低温度时是热力学禁阻的,需要约500K以上时才是热力学可行的。同时,脱羧反应的活化能小于脱羰反应的活化能,说明羧基的反应活性强于羰基,脱除难度较低,所以CO2的生成温度低于CO。

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