不同基属重油加氢改质与沥青质超分子缔合体解构  

Hydrogenation of Different Base Heavy Oils and Deconstruction ofAsphaltene Supramolecular Aggregates

作　　者：张宸玮 方东 金翔 许顺年 张亚红[1] 王刚[1] ZHANG Chenwei;FANG Dong;JIN Xiang;XU Shunnian;ZHANG Yahong;WANG Gang(State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing 102249,China;PetroChina North China Petrochemical Company,Renqiu 062552,China)

机构地区：[1]中国石油大学(北京)重质油全国重点实验室,北京102249 [2]中国石油华北石化分公司,河北任丘062552

出　　处：《石油学报（石油加工）》2024年第5期1364-1372,共9页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金面上项目(22178385);中国石油天然气股份有限公司科技开发项目(2022DJ6003,2022ZS_(2)7,F-785022K6)资助。

摘　　要：沥青质缔合体是重油中的超分子结构,对其进行加氢解构是重质油改质的关键。将石蜡基华北重油和中间基巴士拉重油进行加氢改质反应,采用正庚烷对加氢改质前后的重油样品分离沥青质,考察沥青质似晶缔合体的加氢解构程度以及沥青质平均分子结构的变化规律。研究表明:受沥青质超分子结构转化性能的影响,华北重油中金属(Ni和V)、残炭、氮、硫等杂质脱除率分别比巴士拉重油低14.6、18.7、8.8和1.1百分点;受单元片层烷基侧链所形成的空间位阻的影响,华北重油沥青质似晶缔合体的转化率比巴士拉重油低8.34百分点;受单元片层中多环芳烃饱和与杂原子脱除效率的影响,加氢过程中华北重油沥青质缩合度的增幅比巴士拉重油高5.4百分点,因此华北重油次生沥青质中的杂质浓集程度更高。Asphaltene aggregate is a supramolecular structure in heavy oil,and its hydro-deconstruction is crucial for heavy oil upgrading.The degree of deconstruction of asphaltene nanoaggregates and the change law of average molecular structure of asphaltenes were investigated by using n-heptane to separate the asphaltenes of heavy oils before and after hydro-upgrading of the paraffin-based Huabei heavy oil and intermediate-based Basrah heavy oil.Results show that due to the influence of asphaltene supramolecular structures conversion performance,the removal rates of metals(Ni and V),carbon residue,nitrogen and sulfur in Huabei heavy oil are 14.6,18.7,8.8 and 1.1 percentage points lower than those in Basrah heavy oil,respectively;the conversion rate of asphaltene nanoaggregates in Huabei heavy oil is 8.34 percentage points lower than that in Basrah heavy oil,which is attributed to the spatial hindrance caused by alkyl side chains in the unit layers;the increment amplitude of asphaltene condensation degree in Huabei heavy oil is 5.4 percentage points higher than that in Basrah heavy oil during hydrogenation,which is attributed to the efficiency of saturating polycyclic aromatic hydrocarbons and removing heteroatoms in the unit layers.Therefore,the concentration degree of impurities in the secondary asphaltene of Huabei heavy oil is higher.

关 键 词：重油 加氢 沥青质 解构 平均分子结构 超分子缔合体 杂质脱除率 

分 类 号：TE622[石油与天然气工程—油气加工工程]