石油基中间相沥青形成机理探究  

Research of Generation Mechanism of Petroleum-Based Mesophase Pitch

作　　者：于德志 闫昊辰 查如俊 凌昊[1] YU Dezhi;YAN Haochen;ZHA Rujun;LING Hao(Petroleum Processing Research Center,School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学化工学院石油加工研究所,上海200237

出　　处：《石油学报(石油加工)》2025年第2期573-584,共12页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(22378131)资助。

摘　　要：采用红外光谱、核磁共振氢谱、MALDI-TOF MS、偏光显微镜、XRD和四组分族组成等表征手段对3种石油基原料及其高温热缩聚中间相沥青(MP)的组成和结构进行分析。结果表明:芳烃质量分数75%的芳烃抽出油(AEO)易形成中间相体积分数接近100%、广域流线型织构的MP;脱固油浆(DSO)的胶质、沥青质含量低,芳核上烷基短链较多,形成的MP体积分数只有54%;重脱油(DHO)的重均相对分子质量达到571 Da,胶质质量分数为62.40%,也可制备体积分数接近100%的MP,但呈马赛克型中间相织构。通过分析MP的氢分布和平均分子结构参数以及反应的气体和液体组成分布,可以认为MP的制备过程为多环芳烃(PAH)的低聚和缩聚过程,PAH烷基侧链断裂生成自由基,随后自由基与PAH分子间低聚和缩聚形成MP,提出了PAH低聚反应生成MP的可能机理。The composition and structure of three petroleum-based raw materials and the mesophase pitch(MP)prepared by high-temperature thermal polycondensation were characterized using FTIR,H-NMR,MALDI-TOF MS,polarizing optical microscope,XRD,four-component family composition,and etc.The results indicate that the aromatic extract oil(AEO)with an aromatic mass fraction of about 75%is prone to form MP with the mesophase volume fraction of approximately 100%and wide-area streamlined texture.The de-solidification slurry oil(DSO)has low resin and asphaltene content,and a high number of short-chain alkyl substitutions on the aryl nucleus,contributing to forming MP with a volume fraction of only 54%.The deasphalted heavy oil(DHO)has a weight-average relative molecular mass of 571 Da and a resin mass fraction of 62.40%,which can also form MP with a volume fraction of almost 100%and a mosaic mesophase texture.Through analyzing the hydrogen distribution and average molecular structure parameters of MP,as well as the compositional distribution of reaction gas and liquid,it can be assumed that the preparation of MP is a process of oligomerization and condensation of polycyclic aromatic hydrocarbon(PAH),where the alkyl side chain of PAH is broken to generate free radicals,and the radicals undergo intermolecular oligomerization and polymerization of PAH to form MP.Finally,a possible mechanism of producing MP by PAH oligomerization is proposed.

关 键 词：中间相沥青 石油基 热缩聚 分子结构 广域流线型 

分 类 号：TE626[石油与天然气工程—油气加工工程]