【作者】 陈颖；

【导师】 张秋民； 宋福玉；

【作者基本信息】 大连理工大学 ， 化学工程（专业学位）， 2014， 硕士

【摘要】 在全球化石能源趋紧、世界原油价格不断上涨的情况下,发展油页岩等非常规能源代替部分石油,具有特别重要的战略意义。但是传统热解工艺的页岩油产率较低,本文采用固定床热解装置,在乙醇气氛下,对柳树河油页岩进行热解实验研究,总结乙醇气氛下产物生成的规律,分析了乙醇在油页岩热解过程中的作用。实验考察了在氮气及乙醇气氛下,热解温度(480～580℃)、恒温时间(0～30min)、体系压力(0.2--1.OMPa)、氮气流量(50～200ml/min)、乙醇流量(0.04-0.12ml/min)、恒温段乙醇通入时间等反应条件对产物产率的影响。氮气气氛下柳树河油页岩最佳的热解条件为：热解温度520℃,恒温反应10min,压力0.4MPa,氮气流量50ml/min。该条件下页岩油产率(干基油页岩为基准)为16.8%。乙醇气氛下柳树河油页岩热解的最佳条件为：热解温度520℃,乙醇流量0.1ml/min,恒温反应10min,压力0.4MPa,恒温段内连续通乙醇。该条件下页岩油产率为17.26%,与氮气气氛相比页岩油产率大约上升了2.7%。热解温度越高,热解页岩气产率越大。气相色谱分析结果表明,乙醇引入体系后,页岩气中CH4、CO、C2H4和H2S的产率明显增加。对柳树河油页岩热解页岩油进行酸碱洗-柱层析处理,得到酸性分、碱性分等五个族组分,并通过气质联用分析各族组分的组成。在最佳的实验条件下,对比乙醇加入前后,各族组分的产率变化,分析乙醇在热解中的作用。本文作者通过对比分析认为乙醇参与了热解反应,乙醇为油页岩热解供给了氢自由基,稳定了热解过程中的自由基碎片,抑制了自由基碎片彼此缩合为半焦,从而提升页岩油产率和品质。更多还原

【Abstract】 In the case of global fossil energy increasingly tense and crude oil prices rising, Developing oil shale and other unconventional energy instead of part of the oil, is more and more important. While the shale oil yields of the traditional pyrolysis processed were low, in this paper, under ethanol atmosphere.The pyrolysis of Liushuhe oil shale was investigated on a fixed-bed reactor. The regularity of yields and compositions of the pyrolysis products was summarized under ethanol atmosphere. The ethanol was studied about reaction function during pyrolysis of oil shale.The effect of reaction conditions such as temperature (480癈-580癈), holding time (0min-30min), pressure (0.2MPa-1.0MPa),flow rate of nitrogen (50ml/min-200mI/min), ethanol flow rate (0.04ml/min-0.12ml/min) on the products yields was studied in experiments under nitrogen and ethanol atmosphere. Under nitrogen atmosphere, the most suitable conditions for Liushuhe oil shale pyrolysis were:temperature520癈, holding time lOmin, pressure0.4MPa and nitrogen flow rate50ml/min. The yield of shale oil was16.8%under this condition. While under ethanol atmosphere, the most suitable conditions for Liushuhe oil shale pyrolysis were:temperature520癈, ethanol flow rate O.lml/min, holding time lOmin, pressure0.4MPa and continuously added ethanol in system during holding time. The yield of shale oil was17.26%under this condition, and the yield of shale oil was about2.7%higher than that under nitrogen atmosphere.The higher of the pyrolysis temperature, the yield of pyrolysis shale gas was greater. Analysis of pyrolysis shale gas by GC showed that, the yields of CH^CCK C2H4and H2S were significantly increased:Shale oil of Liushuhe oil shale pyrolysis was treated with acidity, alkaline washing and column chromatography, then it was detached into acidic and alkaline etc., five group components together. Which’s composition was analyzed by GC-MS. Under the most suitable conditions, we analysed the yield of all nationalities’component and studied the reaction function of ethanol during pyrolysis of oil shale.The auther insisted that the ethanol attended in the reactions during shale pyrolysis by comparison and analysis. Ethanol supplied hydro radicals to the reaction system of shale pyrolysis, they stabilized fragment radicals and inhibited condensation reactions among fragments, so that the yield and quality of shale oil were improved.更多还原