Lewis酸脱页岩油中碱性氮的络合工艺及动力学方程

摘要

This paper aimes to remove alkaline nitrogen compounds in shale oil.The research is fo-cused on investigating the denitrification effect of four kind Lewis acids(FeCl3, TiCl4, CuCl2and AlCl3);optimizing CuCl2denitrification process conditions via single factor and orthogonal experiments;and probing into the kinetics of Lewis acid complexing alkaline nitrogen.The optimized process condi-tions of CuCl2denitrification consist of the reaction temperature of 65 ℃; CuCl2dosage of 0.5 mol/kg shale oil;the solvent-to-shale oil volume ratio of 5;and the reaction time of 25 min,all of which contrib-ute to the denitrification rate of up to 87.7%.The analysis using the spectrum of FTIR and gas chroma-tography/mass spectrometry indicates the presence of derivatives of aromatic amines or pyridines,and a-mine nitrogen groups in the removed components by CuCl2.The analysis building on the kinetics of Lewis acid complexing alkaline nitrogen shows the conformity of both the concentrations of CuCl2and basic ni-trogen to the 0.5-order kinetics,with the total reaction rate being expressed in one-order kinetics model. The results show that CuCl2offers the best removal of alkaline nitrogen in shale oil; The research may provide a viable technical scheme and theoretical basis for the complexing denitrification of shale oil.%为脱除页岩油中的碱性含氮化合物,在研究四种Lewis酸的络合脱氮效果的基础上,通过单因素和正交实验,优化CuCl2脱氮工艺条件,并分析络合反应的动力学方程.优化的CuCl2脱氮工艺条件为:反应温度65 ℃,每千克页岩油CuCl2用量0.5 mol,剂油体积比为5,反应时间25 min,在该条件下脱氮率可达87.7%.红外分析和气相色谱/质谱联用分析说明,被脱除组分中含有芳香胺或吡啶等的衍生物及胺氮基团.由脱氮动力学分析可知,络合反应速率与CuCl2浓度和碱性氮浓度均符合0.5级反应规律,总反应级数为1级.结果表明,CuCl2对页岩油中碱性氮的脱除效果最好.该研究为页岩油的络合脱氮工艺提供了技术方案和理论依据.