The potential applications of shale oil as a substitute energy source are adversely influenced due to its high nitrogen content.In this work,four imidazolium ionic liquids(ILs),i.e.,1-butyl-3-methylimidazolium chlorid...The potential applications of shale oil as a substitute energy source are adversely influenced due to its high nitrogen content.In this work,four imidazolium ionic liquids(ILs),i.e.,1-butyl-3-methylimidazolium chloride([Bmim]Cl),1-butyl-3-methylimidazolium acetate([Bmim]Ac),1-butyl-3-methylimidazolium acetate/ZnAc2([Bmim]Ac/ZnAc2)and 1-butyl-3-methylimidazolium chloride/ZnAc2([Bmim]Cl/ZnAc2),were used to extract the basic nitrides and neutral nitrides from shale oil.The influence of extraction time,temperature,properties of N-compounds,ILs structure,mass ratio of IL/oil,multiple cycles of denitrogenation,physical mixing of ILs and ILs recyclability on extractive denitrogenation was systematically investigated.The denitrogenation performance of all ILs was determined and investigated from micro-level view withσ-profile.It was observed that,ILs composed of anions with weaker HB acceptor capacity,have the higher N-extraction efficiency to the neutral nitrogen compounds with weaker HB acceptor capacity.More than 96%N-extraction efficiency was achieved at the end of a single extraction cycle for time<10 min under 40℃C and 1:1 of IL:oil(w/w),especially 100%N-extraction efficiency was realized for carbazole and indole.The N-extraction efficiency up to 60.1%and 53.7%for real shale oil was realized by[Bmim]Ac and[Bmim]Ac/ZnAc2,respectively,which are about 10%better than other non-hydrodenitrogenation technologies.Moreover,[Bmim]Ac and[Bmim]Ac/ZnAc2 exhibited almost the same extractive denitrogenation performance after regeneration.This work has developed a new approach to lessen the nitrogen content of shale oil effectively and economically.展开更多
研究了Hβ型分子筛对直馏柴油中碱性氮化物静态吸附的热力学和动力学特征。热力学研究结果表明,使用Freundlich方程拟合静态吸附等温线效果较好;由于焓变大于零,所以吸附是吸热过程;由于吸附过程的焓变大于零且绝对值小于60 k J/mol,所...研究了Hβ型分子筛对直馏柴油中碱性氮化物静态吸附的热力学和动力学特征。热力学研究结果表明,使用Freundlich方程拟合静态吸附等温线效果较好;由于焓变大于零,所以吸附是吸热过程;由于吸附过程的焓变大于零且绝对值小于60 k J/mol,所以吸附过程以物理吸附为主;由于吉布斯自由能变小于零,所以吸附是自发过程。动力学研究结果表明,二级反应方程与实验数据间具有良好的相关性,吸附速率随操作温度的升高而增大,表观活化能为2.34 k J/mol。展开更多
基金This work was financially supported by the Natural Science Foundation of China(21176021,21276020)the China postdoctoral science foundation(2018M641164)+1 种基金We extend our appreciation to the Natural Science Foundation of China(21176021,21276020)China postdoctoral science foundation(2018M641164)for funding the work.
文摘The potential applications of shale oil as a substitute energy source are adversely influenced due to its high nitrogen content.In this work,four imidazolium ionic liquids(ILs),i.e.,1-butyl-3-methylimidazolium chloride([Bmim]Cl),1-butyl-3-methylimidazolium acetate([Bmim]Ac),1-butyl-3-methylimidazolium acetate/ZnAc2([Bmim]Ac/ZnAc2)and 1-butyl-3-methylimidazolium chloride/ZnAc2([Bmim]Cl/ZnAc2),were used to extract the basic nitrides and neutral nitrides from shale oil.The influence of extraction time,temperature,properties of N-compounds,ILs structure,mass ratio of IL/oil,multiple cycles of denitrogenation,physical mixing of ILs and ILs recyclability on extractive denitrogenation was systematically investigated.The denitrogenation performance of all ILs was determined and investigated from micro-level view withσ-profile.It was observed that,ILs composed of anions with weaker HB acceptor capacity,have the higher N-extraction efficiency to the neutral nitrogen compounds with weaker HB acceptor capacity.More than 96%N-extraction efficiency was achieved at the end of a single extraction cycle for time<10 min under 40℃C and 1:1 of IL:oil(w/w),especially 100%N-extraction efficiency was realized for carbazole and indole.The N-extraction efficiency up to 60.1%and 53.7%for real shale oil was realized by[Bmim]Ac and[Bmim]Ac/ZnAc2,respectively,which are about 10%better than other non-hydrodenitrogenation technologies.Moreover,[Bmim]Ac and[Bmim]Ac/ZnAc2 exhibited almost the same extractive denitrogenation performance after regeneration.This work has developed a new approach to lessen the nitrogen content of shale oil effectively and economically.
文摘研究了Hβ型分子筛对直馏柴油中碱性氮化物静态吸附的热力学和动力学特征。热力学研究结果表明,使用Freundlich方程拟合静态吸附等温线效果较好;由于焓变大于零,所以吸附是吸热过程;由于吸附过程的焓变大于零且绝对值小于60 k J/mol,所以吸附过程以物理吸附为主;由于吉布斯自由能变小于零,所以吸附是自发过程。动力学研究结果表明,二级反应方程与实验数据间具有良好的相关性,吸附速率随操作温度的升高而增大,表观活化能为2.34 k J/mol。
