煤焦油沥青质与减压渣油沥青质结构组成的对比  

Comparison of Molecular Composition and Structure of Asphaltene From Coal Tar and Vacuum Residue

作　　者：王蕴[1] 汪燮卿[1] 吴治国[1] 王鹏飞[1] 王卫平[1] 邹亮 WANG Yun;WANG Xieqing;WU Zhiguo;WANG Pengfei;WANG Weiping;ZOU Liang(Research Institute of Petroleum Processing,SINOPEC,Beijing 100083,China)

机构地区：[1]中国石化石油化工科学研究院,北京100083

出　　处：《石油学报（石油加工）》2019年第2期303-311,M0006,共10页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：中国石油化工股份有限公司项目(111115)资助

摘　　要：基于核磁共振氢谱(~1H-NMR)、核磁共振碳谱(^(13)C-NMR)和傅里叶变换离子回旋共振质谱(FT-ICR MS),分析了煤焦油和减压渣油中正庚烷沥青质的结构和分子组成的差异。在大气压光致电离源(APPI)和电喷雾电离源(ESI)下,质谱测得的煤焦油沥青质相对分子质量分布范围均小于减压渣油沥青质,但其中含氧类化合物或其他含氧多杂原子相对丰度高于减压渣油沥青质。各类化合物中,煤焦油沥青质均含有更小等效双键数(DBE)的化合物;在相同DBE下,减压渣油沥青质的碳数分布范围更大,意味着减压渣油沥青质的烷基侧链分布范围宽。计算了煤焦油沥青质和减压渣油沥青质结构单元平均分子式分别为C_(30.54)H_(26.57)S_(0.04)N_(0.54)O_(2.80)和C_(42.41)H_(41.54)S_(0.85)N_(0.63)O_(0.48)。煤焦油沥青质结构单元的芳香度较高,而芳环数和芳环缩合度均小于减压渣油沥青质。煤焦油沥青质中的低缩合度化合物能够对沥青质聚集体中芳环的堆积作用产生直接的影响,但影响程度仍需进一步研究。Asphaltene from coal tar and petroleum vacuum residue respectively were characterized with nuclear magnetic resonance spectroscopy ( 1H-NMR and 13 C-NMR) and Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS).The relative molecular mass distribution ranges of coal tar asphaltene obtained by mass spectrometry (MS) with both APPI and ESI ionization sources were narrower than those from petroleum asphaltene.The coal tar asphaltene had high relative abundance of oxygen-containing species and other heteroatoms.Compounds with very low double bond equivalent (DBE) were detected in coal tar asphaltene.Molecules in the petroleum asphaltene had higher carbon number values than those of coal tar asphaltene with the same DBE values.This indicated that the petroleum asphaltene had relative long side chains on the molecules.The average molecular formula of the coal tar and petroleum asphaltene were C 30.54 H 26.57 S 0.04 N 0.54 O 2.80 and C 42.41 H 41.54 S 0.85 N 0.63 O 0.48 , respectively.Compared with petroleum asphaltene,the coal tar asphaltene had higher aromaticity degree and lower condensation degree.The compounds with low DBE values in coal tar asphaltene might have direct impact on aromatic sheets stacking during asphaltene agglomeration process,which needs to be further studied.

关 键 词：沥青质 分子结构 分子组成 核磁 傅里叶变换离子回旋共振质谱 

分 类 号：TE622[石油与天然气工程—油气加工工程]