煤基和石油基C7-沥青质的结构特征及缔合行为  

Structure characteristics and association behavior of coal and petroleum C7-asphaltenes

作　　者：杜俊涛 张大奎 张敏鑫 郏慧娜 聂毅 孙一凯 邓文安[3] 李传[3] DU Jun-tao;ZHANG Da-kui;ZHANG Min-xin;JIA Hui-na;NIE Yi;SUN Yi-kai;DENG Wen-an;LI Chuan(Department of Green Technology Research,Zhengzhou Institute of Emerging Industrial Technology(Institute of Process Engineering,Chinese Academy of Sciences,Zhengzhou),Zhengzhou 450000,China;Ansteel Chemical Technology Co.,Ltd.,Anshan 114000,China;State Key Laboratory of Heavy Oil,China University of Petroleum(East China),Qingdao 266580,China)

机构地区：[1]郑州中科新兴产业技术研究院(中科院过程所郑州分所)绿色技术研究部,河南郑州450000 [2]鞍钢化学科技有限公司,辽宁鞍山114000 [3]中国石油大学(华东)重质油国家重点实验室,山东青岛266580

出　　处：《燃料化学学报》2020年第6期674-682,I0003,共10页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金项目(21908206)资助。

摘　　要：采用核磁(NMR)、小角散射分析(SAXS)、X射线光电子能谱(XPS)、改进的B-L法等手段,研究了煤基C7-沥青质(CT-asp)和石油基C7-沥青质(M-asp)两类沥青质的化学组成、官能团和分子结构等组成结构特征以及差异性,进而通过极性溶剂中沥青质稳定参数研究两类沥青质的缔合行为和聚集体尺寸以及两者之间的氢键和酸碱作用。结果表明,CT-asp分子芳香环数较少且有较多短烷基侧链,且芳香度较高,较高含量氧杂原子以芳香醚和酚羟基赋存形态为主;而M-asp的芳香核尺寸和平均相对分子质量明显高于CT-asp,芳香环数虽较多且有较多长烷基支链,且芳香度较小;两类沥青质缔合聚集程度关联物质的量比(nCT-asp/nM-asp)及其分子结构特征,源于杂原子官能团的氢键和酸碱作用是两类沥青质缔合的主要作用力。The structural characteristics and differences of coal tar and petroleum C7-asphaltenes were studied,such as chemical composition,functional groups and molecular structure,using nuclear magnetic resonance(NMR),small angle X-ray scattering(SAXS),X-ray photoelectron spectroscopy(XPS),improved B-L method and other methods.Furthermore,the association behavior and aggregation size of two different types of asphaltenes as well as the hydrogen bonds and acidic-basic interaction were analyzed by asphaltenes solubility parameters in polar solvents.The experiment results showed that the coal tar asphaltenes(CT-asp)was mainly composed of less aromatic rings with more short alkyl branched chains and possessed a high aromaticity degree.The higher content oxygen heteroatoms of CT-asp were mostly presented as aromatic ether bonds and phenolic hydroxyl groups.The aromatic nucleus size and the average relative molecular weight of petroleum asphaltenes(M-asp)were larger than that of CT-asp.The M-asp consisted primarily of more aromatic rings with more long alkyl branched chains and possessed a low aromaticity degree.The association and aggregation degree between CT-asp and M-asp was associated with the amount of substance ratio(ncr-asp/nM-asp)and their molecular structure characteristics.The association force of two types mainly was the hydrogen bonds and the acidic-basic interaction from heteroatomic functional groups.

关 键 词：煤焦油 石油 C7-沥青质 分子结构 缔合行为 

分 类 号：TQ524[化学工程—煤化学工程]