大港减压渣油超临界萃取残渣极性组分的化学结构特征  

CHEMICAL STRUCTURE FEATURES OF POLAR FRACTIONS OF SFEF TAILING FROM DAGANG VACUUM RESIDUE

作　　者：张占纲[1] 郭绍辉[1] 赵锁奇[1] 闫光绪[1] 

机构地区：[1]中国石油大学重质油国家重点实验室

出　　处：《石油学报（石油加工）》2007年第4期82-88,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点基础研究发展计划"973"项目(2004CB217801)资助

摘　　要：将大港减压渣油超临界萃取(SFEF)的残渣利用中性Al2O3色谱柱进行四组分(SARA)分离,得到饱和分、芳香分、胶质和沥青质。然后对其中的芳香分、胶质和沥青质3个极性组分进行钌离子催化氧化反应(RICO)选择性降解,生成的混合物分离处理后,非挥发性羧酸用CH2N2-乙醚溶液酯化,挥发性羧酸用苯甲酰甲基溴酯化。采用GC-MS、GC、FT-IR等手段对这些酯化产物进行定性和定量分析,检测到各组分的降解产物含有一系列的一元正构脂肪酸、α,ω-二元正构脂肪酸和多种芳羧酸,以此可了解各组分的结构特征。结果表明,3个组分的RICO产物中,芳环上的正构烷基侧链含量和连接2个不同芳碳的聚亚甲基桥含量均随着碳链增长呈递减趋势。沥青质组分的芳核中迫位缩合结构比芳香分要多,而芳香分中的联苯和渺位缩合结构比沥青质中的比例要大,胶质中各种结构的分布介于两者之间。The SFEF tailing from Dagang vacuum residue was separated into four groups （saturates,aromatics, resins, and asphaltenes, known as SARA） on a neutral Al2O3 column in a specific condition. The three polar fractions, including aromatics, resins and asphaltenes, were then degraded by Ru ion catalytic oxidation （RICO）. After being separated, involatile acids in the products were methylated with diazomethane-ether solution, while volatile acids were esterified with phenacyl bromide. Based on GC-MS and GC analysis of these esters, homologous series of n-alkanoic acids, α, ω-di-n-alkanoic acids and benzenepolycarboxylic acids were quantitatively determined respectively, which could give a sight on the major mode of aromatic condensations and the concentration of specific aromatic nuclear in the three polar fractions of the SFEF tailing. It is indicated from those analysis results that the molar concentration of n-alkyl groups （C4-C30） and polymethylene （C3- C20） connecting two different aromatic carbons were monotonously declined with the increase of chain length. There was more peri-condensation structure units in the aromatic nucleuses in asphaltene fraction than in aromatics, while more cata-condensation and bibenzyl structure units in aromatics fraction, and for these structure distribution, resin fraction was between asphaltene and aromatics fractions.

关 键 词：超临界萃取残渣 极性组分 钌离子催化氧化(RICO) 化学结构 

分 类 号：TE624[石油与天然气工程—油气加工工程]