吸热型碳氢燃料的自氧化反应研究  

STUDY ON THE AUTOXIDATION REACTIONS OF ENDOTHERMIC HYDROCARBON FUELS

作　　者：李丹[1] 方文军[1] 邢燕[1] 郭永胜[1] 林瑞森[1] 

机构地区：[1]浙江大学化学系,浙江杭州310027

出　　处：《石油学报（石油加工）》2007年第6期36-43,共8页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金(20573096);浙江省自然科学基金(Y404329)资助

摘　　要：采用加速热氧化的方法，于100～180℃，测定了2种吸热型碳氢燃料（ZH-100和JP-10）自氧化过程中生成氢过氧化物的浓度，考察了氢过氧化物的浓度随温度、氧化时间的变化。并考察了在100、120和140℃下，cu对吸热型碳氢燃料自氧化反应的影响。结果表明，温度对自氧化反应和氢过氧化物的生成影响很大，温度越高，自氧化反应速率越快，燃料中氢过氧化物的浓度极大值出现越早，但相对数值越小。Cu具有催化自由基链引发反应和催化氧化沉积生成的作用。在氧化后的燃料试样及其胶状沉积物的FT-IR谱图中，明显地观察到了-OH、C-O和C-O等含氧官能团的特征吸收峰，羰基化合物是吸热型碳氢燃料自氧化反应的主要产物。依据烃类燃料自氧化的自由基反应机理，探讨了实验现象和规律，为吸热型碳氢燃料的热氧化安定性研究及燃料开发提供重要理论基础。The hydroperoxide contents in two kinds of endothermic hydrocarbon fuels, ZH-100 and JP-10, during the auto-oxidation at different temperatures from 100 to 180℃ were determined by an accelerated oxidation test. The changes of hydroperoxide content with the autoxidation temperature and time were investigated, and the effects of copper on the autoxidation of the fuels at 100, 120 and 140 ℃ were also studied. The hydroperoxide measurements indicated that the temperature showed strong effects upon the autoxidation of the fuels and the formation of hydroperoxides. The higher the temperature, the faster the reaction rate of autoxidation, the earlier the maximum value of hydroperoxide content occurred, and the less the value of hydroperoxide content. It is found that the copper played catalytic roles in the autoxidation and deposit formation in the fuels. From FT-IR spectra of oxidized fuels and their deposits, the characteristic peaks of the functional groups of -OH, C-O, and C - O were obviously observed. It can be confirmed that carbonyl compounds were the main components in the deposits. The experimental phenomena can be successfully explained by the radical chain mechanism for the auto-oxidation of endothermic hydrocarbon fuels, which presented the important fundamentals for investigating thermal-oxidation stability, and developing endothermic hydrocarbon fuels.

关 键 词：吸热型碳氢燃料 自氧化 氢过氧化物 催化氧化 

分 类 号：TE624.4[石油与天然气工程—油气加工工程]