吴建勋
毕业时间：2020年12月（博士）
毕业去向：中国石油大学（北京）
导师：史权 教授
学科专业：化学工程与技术
研究方向：石油与天然气化学
学位论文题目
原油有机硫化物分子结构分析及其地球化学意义
Molecular structure characterization and geochemical significance of sulfur compounds in crude oils
论文摘要
原油中有机硫化物类型丰富，结构多样，在分子层次上表征石油含硫化合物化学组成，有助于研究石油的地质成因，为石油加工过程中脱硫工艺及催化剂设计提供重要理论指导。本论文围绕原油中的含硫化合物，开发分离新方法；制定原油全馏程含硫化合物分子组成与结构表征的分析方案，鉴定新型含硫化合物，解释硫醚类化合物的成因机理。主要内容包括：基于对含硫化合物在硅胶和氧化铝表面的吸附机理的深入认识，建立了分离和富集石油中硫醚类化合物的新方法。主要步骤包括：利用氧化铝吸附色谱，将硫醚组分和烃类初步富集在一起，除去大部分芳烃类、噻吩类和氮化物；再利用硅胶吸附色谱，实现硫醚组分与烃类的进一步分离。该方法简单、高效，适用于原油、馏分油及石油产品中硫醚类化合物的快速分离。
提出一个原油硫化物分子组成与结构分析的解决方案，适用于不同性质原油及其馏分油的硫化物组成分析。基本程序为：采用甲基化-脱甲基法或氧化铝-硅胶吸附分离法分离出硫醚和噻吩类硫化物，噻吩组分用氧化铝柱进一步分离，得到不同芳环数噻吩类化合物；硫醚组分一部分进行雷尼镍脱硫处理转化为烃类。分离和脱硫组分通过傅里叶变换离子回旋共振质谱和气相色谱质谱分析，获取详细的含硫化合物分子组成与结构信息。
从渤海湾盆地原油中分离和鉴定出各种类型的含硫化合物，对一系列以角鲨烯和类胡萝卜素为生物前体物的新型含硫化合物进行了结构鉴定，这些新型有机硫化物中的硫主要以硫代环己烷或带一个季碳原子的硫代环戊烷结构存在，可能对该原油中噻吩类化合物的形成造成障碍，此外Lexane及其含硫化合物的存在表明成岩早期为还原环境，同时还原环境以及还原性无机硫的存在促进了非生物硫掺入和加氢过程。
通过馏分蒸馏切割结合硫化物选择性分离，完成了对一个中东高硫原油中有机硫化物的定性和定量分析。石脑油馏分实现单体硫化物的定性定量分析；中间馏分油中按照噻吩类和硫醚类分类，C10-C25苯并噻吩和二苯并噻吩，单环二环和三环的环硫醚以及一笼和二笼的硫代金刚烷系列是中间馏分油中主要存在的有机硫化物；渣油中能够分离出的噻吩和硫醚占总硫含量不到一半，硫化物碳数高达C60以上。
分析了塔里木盆地、准格尔盆地和渤海湾盆地不同地质来源代表性原油的硫化物组成与分布，从地球化学角度解释了硫醚类化物的成因机理并阐述其地球化学意义。沉积和成岩早期有机质中的烃烯与硫化氢的结合形成大量硫醚类化合物，这些化合物保留了生物分子的特征碳骨架，可以作为生物标志化合物用来研究石油的成因机理和演化途径。
关键词：石油含硫化合物；硫醚类化合物；分子结构；高分辨质谱
创新点
（1）揭示石油硫化物在不同吸附剂的作用机理，建立一种快速、高效的分离富集石油组分中硫醚类化合物的新方法。（见第2章）
（2）提出面向原油全馏分的含硫化合物分子组成与结构分析的解决方案，实现了代表性原油中含硫化合物的定性、定量分析。（见第3章及第5章）
（3）在原油中鉴定出以角鲨烯和类胡萝卜素等为生物前体物的一系列新型含硫生物标志化合物，提出沉积早期烯烃硫化形成硫醚类化合物的演化机理，并探讨了这些含硫化合物的地球化学意义。（见第4章、第6章）
吴建勋博士在实验室多年研究积累的基础上，进一步完善了石油含硫化合物分析方法，系统研究了原油中有机硫化物的分子结构特征。
他从地球化学角度系统解释了不同类型含硫化合物的形成机理，为认识石油中含硫化合物的成因与演化提供了重要的科学依据，研究结果对石油地球化学和石油加工领域均具有参考价值。
发表学术论文
[1]李素梅; 徐田武; 史权; 张云献; 吴建勋; 柯昌炜. 东濮凹陷盐湖相原油氮/氧化合物分布特征及其应用. 现代地质 2019, 33 (6), 1137–1150
https://doi.org/10.19657/j.geoscience.1000-8527.2019.06.01[2]徐田武; 李素梅; 张洪安; 张云献; 吴建勋; 史权; 陈湘飞; 纪红; 万中华. 东濮凹陷原油含硫化合物的分布特征及其应用. 现代地质 2019, 33 (3), 629–642
https://doi.org/10.19657/j.geoscience.1000-8527.2019.03.15[3]李硕凡; 吴建勋; 李运运; 李玉果; 张亚和; 史权. 石油饱和烃分子组成分析方法综述. 分析试验室 2021, 40 (12), 1472–1479
https://doi.org/10.13595/j.cnki.issn1000-0720.2021.020902[4]李运运; 何晨; 吴建勋; 张亚和; 梁咏梅; 史权; 张传伦. 甘油四醚类化合物的高分辨质谱表征. 质谱学报 2021, 42 (6), 1127–1138.
[5]李二庭; 靳军; 陈亮; 鲁锋; 史权; 吴建勋; 迪丽达尔·肉孜; 张宇. 准噶尔盆地南缘井筒堵塞物中沥青质分子组成研究. 石油实验地质 2022, 44 (2), 306–313.
[6]李二庭; 史权; 马聪; 雷海艳; 吴建勋; 迪丽达尔·肉孜; 高秀伟; 王明. 生物降解稠油极性化合物负离子电喷雾傅立叶变换离子回旋共振质谱分析. 石油实验地质 2022, 44 (3), 515–521.
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https://doi.org/10.1021/acs.energyfuels.8b02756[8]Ren, L.; Wu, J.; Qian, Q.; Liu, X.; Meng, X.; Zhang, Y.; Shi, Q. Separation and Characterization of Sulfoxides in Crude Oils. Energy and Fuels 2019, 33 (2), 796–804
https://doi.org/10.1021/acs.energyfuels.8b03494[9]Wu, J.; Zhang, W.; Ma, C.; Wang, F.; Zhou, X.; Chung, K. H.; Hou, D.; Zhang, Y.; Shi, Q. Isolation and characterization of sulfur compounds in a lacustrine crude oil. Fuel 2019, 253, 1482–1489
https://doi.org/10.1016/j.fuel.2019.05.044[10]Ge, Y.; Wu, J.; Zhang, Y.; Liang, Y.; Shi, Q. Characterization of Sulfur-Containing Compounds in Petroleum Using AgSbF6as a Methylation Reagent. Energy and Fuels 2020, 34 (9), 10842–10848
https://doi.org/10.1021/acs.energyfuels.0c01987[11]Wu, J.; Zhang, W.; Chang, W.; Wu, H.; Zhang, Y.; Shi, Q. Isolation of Sulfides from Petroleum for Molecular Characterization by Alumina and Silica Gel Adsorption. Energy and Fuels 2020, 34 (9), 10837–10841
https://doi.org/10.1021/acs.energyfuels.0c01985[12]Wu, J.; Zhang, W.; Ma, C.; Ren, L.; Li, S.; Zhang, Y.; Shi, Q. Separation and characterization of squalene and carotenoids derived sulfides in a low mature crude oil. Fuel 2020, 270
https://doi.org/10.1016/j.fuel.2020.117536[13]Shi, Q.; Wu, J. Review on Sulfur Compounds in Petroleum and Its Products: State-of-the-Art and Perspectives. Energy and Fuels 2021, 35 (18), 14445–14461
https://doi.org/10.1021/acs.energyfuels.1c02229[14]Zhang, S.; Huo, J.; Sun, X.; Yang, F.; Wang, P.; Wu, J.; Zhang, Y.; Shi, Q. Molecular Composition Reveals Unique Rheological Property of Karamay Heavy Crude Oil. Energy and Fuels 2021, 35 (1), 473–478
https://doi.org/10.1021/acs.energyfuels.0c03639[15]Zhang, Y.; Han, Y.; Wu, J.; Wang, Y.; Li, J.; Shi, Q.; Xu, C.; Hsu, C. S. Comprehensive Composition, Structure, and Size Characterization for Thiophene Compounds in Petroleum Using Ultrahigh-Resolution Mass Spectrometry and Trapped Ion Mobility Spectrometry. Analytical Chemistry 2021, 93 (12), 5089–5097
https://doi.org/10.1021/acs.analchem.0c04667[16]Chen, H.; Kong, W.; Shi, Q.; Wang, F.; He, C.; Wu, J.; Lin, Q.; Zhang, X.; Zhu, Y. G.; Liang, C.; Luo, Y. Patterns and drivers of the degradability of dissolved organic matter in dryland soils on the Tibetan Plateau. Journal of Applied Ecology 2022, 59 (3), 884–894
https://doi.org/10.1111/1365-2664.14105[17]Chen, Z.; Wang, Y.; Wu, J.; Wang, B.; Jiang, T.; Yu, J.; Yang, H.; Zhao, S.; Shi, Q.; Xu, C. Composition of sulfur species in deasphalted oils and their molecular-level transformation during the hydrotreating process. Fuel 2022, 328
https://doi.org/10.1016/j.fuel.2022.125335[18]Huo, D.; Wu, J.; Li, H.; Huang, H.; Chung, K. H.; Shi, Q. Calcium in crude oil: a review. Petroleum Science and Technology 2022, 40 (23), 2861–2876
https://doi.org/10.1080/10916466.2022.2050387[19]Li, H.; Li, S.; Wu, J.; Huo, D.; Zhang, Y.; Shi, Q. Molecular Characterization of Naphthenic Acids and Naphthenates in the Oil Sludge: A Case Study in Bohai Basin, China. Energy and Fuels 2022, 36 (24), 14907–14912
https://doi.org/10.1021/acs.energyfuels.2c03329[20]Li, H.; Li, S.; Wu, J.; Xie, L.; Liang, Y.; Zhang, Y.; Zhao, S.; Xu, C.; Shi, Q. Molecular characterization of aromatics in petroleum fractions by combining silica sulfuric acid sulfonation with electrospray ionization high-resolution mass spectrometry. Fuel 2022, 317
https://doi.org/10.1016/j.fuel.2022.123463[21]Li, S.; Liu, Y.; Zhang, Y.; Wu, J.; Zhang, W.; Shi, Q. Molecular Characterization of Olefins in Petroleum Fractions by Iodine Monochloride Addition and Atmospheric Pressure Chemical Ionization Mass Spectrometry. Energy and Fuels 2022, 36 (23), 14187–14193
https://doi.org/10.1021/acs.energyfuels.2c03128[22]Wu, J.; Li, H.; Zhao, Q.; Zhou, B.; Lun, Z.; Zhang, Y.; Chung, K. H.; Shi, Q. Characterization of crude oil interfacial material by high-resolution mass spectrometry. Journal of Petroleum Science and Engineering 2022, 214
https://doi.org/10.1016/j.petrol.2022.110509[23]Li, S.; Wu, J.; Wang, Y.; Li, Y.; Zhang, W.; Zhang, Y.; He, K.; Cai, C.; Bian, G.; Wang, H.; Ji, Y.; Shi, Q. Semi-quantitative analysis of molecular composition for petroleum fractions using electrospray ionization high-resolution mass spectrometry. Fuel 2023, 335
https://doi.org/10.1016/j.fuel.2022.127049[24]Li, S.; Wu, J.; Zhang, W.; Jiang, Y.; Hu, M.; Chung, K. H.; Shi, Q. Speciation and molecular characterization of thiophenic and sulfide compounds in petroleum by sulfonation and methylation followed by electrospray mass spectrometry. Analytical and Bioanalytical Chemistry 2023, 415 (10), 1889–1896
https://doi.org/10.1007/s00216-023-04593-y[25]Ma, C.; Wu, J. X.; Ni, H. X.; Fang, Z.; Wang, W.; Gao, Y.; Shi, Q. Molecular Characterization of Dissolved Organic Matter in Coal Coking Wastewater by FT-ICR MS. Journal of Chinese Mass Spectrometry Society 2023, 44 (3), 387–396
https://doi.org/10.7538/zpxb.2022.0082[26]Ma, S.; Li, Y.; Su, R.; Wu, J.; Xie, L.; Tang, J.; Wang, X.; Pan, J.; Wang, Y.; Shi, Q.; Liao, G.; Xu, C. Ketones in Low-Temperature Oxidation Products of Crude Oil. Processes 2023, 11 (6)
https://doi.org/10.3390/pr11061664[27]Wang, Y.; Lu, J.; Zhang, X.; Zhang, X.; Zhang, B.; Wu, J.; Guan, D.; Zhang, Y.; Chen, J.; Feng, X.; Zhang, Y.; Zhou, Z.; Zhang, L.; Shi, Q. Molecular transformation of heavy oil during slurry phase hydrocracking process: A comparison between thermal cracking and hydrocracking. Fuel 2023, 351
https://doi.org/10.1016/j.fuel.2023.128981[28]Wang, Y.; Wu, J.; Li, S.; Zhang, W.; Wang, P.; Wang, M.; Zhu, G.; Shi, Q. Identification and Geological Implication of Thiols in the Condensate Oils. Energy and Fuels 2023, 37 (16), 11675–11682
https://doi.org/10.1021/acs.energyfuels.3c01330[29]Wang, Y.; Wu, J.; Xie, L.; Yuan, M.; Jing, Z.; Pan, S.; Zhang, W.; Zhang, Y.; Shi, Q. Identification and Geochemical Implication of Sulfur Compounds in an Immature Lacustrine Shale Oil. Energy and Fuels 2023, 37 (17), 12946–12952
https://doi.org/10.1021/acs.energyfuels.3c01860[30]Wang, Y.; Zhu, G.; Wang, M.; Wu, J.; Fu, D.; Xie, Q.; Shi, Q.; Xu, C.; Han, Y. Discovery of novel cage compounds of diamondoids using multi-dimensional mass spectrometry. Chemical Engineering Science 2023, 273
https://doi.org/10.1016/j.ces.2023.118677[31]Wu, J.; Ma, C.; Zhang, W.; Chang, W.; Zhang, Y.; Shi, Q. Molecular characterization of non-polar sulfur compounds in the full boiling range crude oil fractions. Fuel 2023, 338
https://doi.org/10.1016/j.fuel.2022.127323[32]Wu, J.; Zhang, W.; Wang, Y.; Zhang, Y.; Shi, Q. Identification of sulfur-containing isoprenoids with non-adamantane cage structures in crude oil. Fuel 2023, 339
https://doi.org/10.1016/j.fuel.2023.127390[33]Zhao, Q. H.; Ma, S.; Wu, J. X.; Chang, W. F.; Zhang, S. F.; Sun, X. G.; Zhou, B.; Lun, Z. M.; Chung, K. H.; Shi, Q. Molecular composition of naphthenic acids in a Chinese heavy crude oil and their impacts on oil viscosity. Petroleum Science 2023, 20 (2), 1225–1230
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