焦化柴油氮化物组成分布及其在加氢转化过程中的分子选择性  

Composition Distribution of Nitrogen Compounds in Coking Diesel and Their Molecular Selectivity in the Hydrogenation Process

作　　者：孙进[1] 张亚和[2] 郭蓉[1] 李硕凡 李扬[1] 李晗 史权[2] SUN Jin;ZHANG Yahe;GUO Rong;LI Shuofan;LI Yang;LI Han;SHI Quan(Dalian Research Institute of Petroleum and Petrochemicals,SINOPEC,Dalian 116045,China;State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing 102249,China)

机构地区：[1]中国石化大连石油化工研究院,辽宁大连116045 [2]中国石油大学(北京)重质油国家重点实验室,北京102249

出　　处：《石油学报（石油加工）》2022年第3期702-709,共8页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点研发计划项目(2021YFA1501200)基金资助。

摘　　要：采用气相色谱和电喷雾高分辨质谱深入分析焦化柴油及其窄馏分中氮化物分子组成,研究不同加氢脱氮条件下反应规律,揭示氮化物分布及加氢过程分子选择性,讨论脱氮反应机理。焦化柴油氮化物以吲哚类、咔唑类中性氮化物为主,其次为苯胺类、吡啶类、喹啉类碱性氮化物。随着馏分变重,总氮和碱性氮含量增加。在选定的基准加氢反应条件下,总氮、中性氮、碱性氮和总硫的脱除率均达到99%以上。通过升温、增压、降低体积空速等优化操作,可以达到更高的加氢脱氮和脱硫率。在加氢过程中,长烷基取代氮化物转化为短烷基取代氮化物,部分中性氮加氢转化为碱性氮。加氢产物中残余的氮化物主要为C_(2)~C_(5)烷基取代咔唑类;在加氢产物中检测到环烷胺类碱性氮化物中间体,证实了柴油加氢脱氮反应路径。Using gas chromatography and electrospray ionization high-resolution mass spectrometry,the authors deeply investigate nitrogen compounds in the coking diesel and its narrow distillate,study the reaction rules under different hydrodenitrification conditions,reveal the distribution of nitrogen compounds and molecular selectivity in the hydrogenation process and discuss the mechanism of denitrification reaction.Coking diesel is dominated by neutral nitrogen compounds such as indoles and carbazoles,followed by basic nitrogen compounds such as anilines,pyridines and quinolines.As distillate become heavier,the total and basic nitrogen content increases.Under the selected fiducial hydrogenation conditions,the removal rates of total nitrogen,neutral nitrogen,basic nitrogen and total sulfur are all above 99%,and higher rate of hydrodenitrification and desulfuration can be achieved by optimized operations such as heating,pressurizing and reducing the liquid hourly space velocity.In the hydrogenation process,long alkyls substituted nitrogen compounds,which were converted into short alkyls and then substituted nitrogen compounds,and some neutral nitrogen compounds were converted into basic nitrogen compounds.In addition,the residual nitrogen compounds in the hydrogenated products are mainly C_(2)—C_(5)alkyl substituted carbazoles;the intermediate of basic nitrogen compounds such as naphthenic amines in the hydrogenated products has verified the hydrodenitrification reaction path of diesel.

关 键 词：焦化柴油 加氢脱氮 氮化物 分子组成 分子选择性 

分 类 号：TE622[石油与天然气工程—油气加工工程]