毕业时间：2020年12月

毕业去向：中国石油大学（北京）优秀学科博士后（2023年留校）

简历：见 工作人员

学位论文：原油有机硫化物分子结构分析及其地球化学意义

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

学术论文（含博士后期间工作）：

1. Zhao QH, Wu JX, Zhou TH, Zhao SQ, Shi Q (2024) Impact of molecular composition on viscosity of heavy oil: Machine learning based on semi-quantitative analysis results from high-resolution mass spectrometry. Petrol Sci. doi:10.1016/j.petsci.2024.03.026

2. Zhang W, Wu J, Li S, Zhang Y, Zhao S, Shi Q (2024) Classification Method of Heavy Oil Based on Chemical Composition and Bulk Properties. Energies 17 (15). doi:10.3390/en17153733

3. Zhang B, Xu C, Shi Q, Li Y, Liu Z, Wu J (2024) Wettability of Different Mineral Surfaces in Supercritical CO2 Extraction: Interpretations from the Molecular Composition of Crude Oil. Energy Fuels 38 (10):8589-8597. doi:10.1021/acs.energyfuels.4c00808

4. Wu JX, Li SF, Li QF, Yan F, Zhou QL, Ma S, Zhang YH, Zhao SQ, Shi Q (2024) Characterization of chemical composition of high viscosity heavy oils: Macroscopic properties, and semi-quantitative analysis of molecular composition using high-resolution mass spectrometry. Petrol Sci 21 (5):3612-3620. doi:10.1016/j.petsci.2024.02.019

5. Wu J, Hamid AA, Zhang W, Li S, Zhang Y, Liao Y, Shi Q (2024) The occurrence and geochemical origin of 9-alkyl HDBTs substituted by long isoprenoid alkyl chains in crude oil. Org Geochem 188. doi:10.1016/j.orggeochem.2023.104721

6. Wang Y, Chen J, Wu J, Zhang W, Su Y, Zhang Y, Shi Q (2024) PetroSulfur: A Gas Chromatography and Mass Spectrometry Database of Organic Sulfur Compounds in Petroleum. Energy Fuels 38 (19):18431-18440. doi:10.1021/acs.energyfuels.4c02760

7. Li S, Wu J, Wang Y, Zhang X, Zhang W, Zhang Y, Shi Q (2024) Isolation and characterization of thiols in petroleum using Ag+-silica solid phase extraction followed by gas chromatography-mass spectrometry and high-resolution mass spectrometry. Fuel 363. doi:10.1016/j.fuel.2024.130946

8. Li S, Wu J, Chen J, Li Y, Hu M, Huang S, Ren X, Zhang W, Zhang Y, Xu C, Shi Q (2024) Semiquantitative Molecular Characterization of Crude Oil. Energy Fuels 38 (5):3769-3783. doi:10.1021/acs.energyfuels.3c05086

9. Li S, Hu H, Wu J, Kong F, Wang J, Shi Q (2024) Rapid On-Column Esterification and Separation of Carboxylic Acids in Petroleum Fractions. Energy Fuels 38 (12):10737-10743. doi:10.1021/acs.energyfuels.4c01119

10. Hu H, Li S, Wang Y, Yang R, Wu J, Zhang W, He C, Li H, Zhang Y, Zhu D, Shi Q (2024) Molecular characterization of petroleum acids from diverse geological origins via n-Butylsilane reduction. Fuel 374. doi:10.1016/j.fuel.2024.132429

11. Zhao QH, Ma S, Wu JX, Chang WF, Zhang SF, Sun XG, Zhou B, Lun ZM, Chung KH, Shi Q (2023) Molecular composition of naphthenic acids in a Chinese heavy crude oil and their impacts on oil viscosity. Petrol Sci 20 (2):1225-1230. doi:10.1016/j.petsci.2022.09.016

12. Wu J, Zhang W, Wang Y, Zhang Y, Shi Q (2023) Identification of sulfur-containing isoprenoids with non-adamantane cage structures in crude oil. Fuel 339. doi:10.1016/j.fuel.2023.127390

13. Wu J, Ma C, Zhang W, Chang W, Zhang Y, Shi Q (2023) Molecular characterization of non-polar sulfur compounds in the full boiling range crude oil fractions. Fuel 338. doi:10.1016/j.fuel.2022.127323

14. Wang Y, Zhu G, Wang M, Wu J, Fu D, Xie Q, Shi Q, Xu C, Han Y (2023) Discovery of novel cage compounds of diamondoids using multi-dimensional mass spectrometry. Chem Eng Sci 273. doi:10.1016/j.ces.2023.118677

15. Wang Y, Wu J, Xie L, Yuan M, Jing Z, Pan S, Zhang W, Zhang Y, Shi Q (2023) Identification and Geochemical Implication of Sulfur Compounds in an Immature Lacustrine Shale Oil. Energy Fuels 37 (17):12946-12952. doi:10.1021/acs.energyfuels.3c01860

16. Wang Y, Wu J, Li S, Zhang W, Wang P, Wang M, Zhu G, Shi Q (2023) Identification and Geological Implication of Thiols in the Condensate Oils. Energy Fuels 37 (16):11675-11682. doi:10.1021/acs.energyfuels.3c01330

17. 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 (2023) Molecular transformation of heavy oil during slurry phase hydrocracking process: A comparison between thermal cracking and hydrocracking. Fuel 351. doi:10.1016/j.fuel.2023.128981

18. Ma S, Li Y, Su R, Wu J, Xie L, Tang J, Wang X, Pan J, Wang Y, Shi Q, Liao G, Xu C (2023) Ketones in Low-Temperature Oxidation Products of Crude Oil. Process 11 (6). doi:10.3390/pr11061664

19. Ma C, Wu JX, Ni HX, Fang Z, Wang W, Gao Y, Shi Q (2023) Molecular Characterization of Dissolved Organic Matter in Coal Coking Wastewater by FT-ICR MS. J Chin Mass Spectrom Soc 44 (3):387-396. doi:10.7538/zpxb.2022.0082

20. Li S, Wu J, Zhang W, Jiang Y, Hu M, Chung KH, Shi Q (2023) Speciation and molecular characterization of thiophenic and sulfide compounds in petroleum by sulfonation and methylation followed by electrospray mass spectrometry. Anal Bioanal Chem 415 (10):1889-1896. doi:10.1007/s00216-023-04593-y

21. Li S, Wu J, Wang Y, Li Y, Zhang W, Zhang Y, He K, Cai C, Bian G, Wang H, Ji Y, Shi Q (2023) Semi-quantitative analysis of molecular composition for petroleum fractions using electrospray ionization high-resolution mass spectrometry. Fuel 335. doi:10.1016/j.fuel.2022.127049

22. Wu J, Li H, Zhao Q, Zhou B, Lun Z, Zhang Y, Chung KH, Shi Q (2022) Characterization of crude oil interfacial material by high-resolution mass spectrometry. J Pet Sci Eng 214. doi:10.1016/j.petrol.2022.110509

23. Li S, Liu Y, Zhang Y, Wu J, Zhang W, Shi Q (2022) Molecular Characterization of Olefins in Petroleum Fractions by Iodine Monochloride Addition and Atmospheric Pressure Chemical Ionization Mass Spectrometry. Energy Fuels 36 (23):14187-14193. doi:10.1021/acs.energyfuels.2c03128

24. Li H, Li S, Wu J, Xie L, Liang Y, Zhang Y, Zhao S, Xu C, Shi Q (2022) Molecular characterization of aromatics in petroleum fractions by combining silica sulfuric acid sulfonation with electrospray ionization high-resolution mass spectrometry. Fuel 317. doi:10.1016/j.fuel.2022.123463

25. Li H, Li S, Wu J, Huo D, Zhang Y, Shi Q (2022) Molecular Characterization of Naphthenic Acids and Naphthenates in the Oil Sludge: A Case Study in Bohai Basin, China. Energy Fuels 36 (24):14907-14912. doi:10.1021/acs.energyfuels.2c03329

26. Li E, Shi Q, Ma C, Lei H, Wu J, Rouzi D, Gao X, Wang M (2022) Analysis of polar compounds in biodegraded heavy oil by negative ion electrospray Fourier transform ion cyclotron resonance mass spectrometry. Petrol Geo Exp 44 (3):515-521. doi:10.11781/sysydz202203515

27. Li E, Jin J, Chen L, Lu F, Shi Q, Wu J, Rouzi D, Zhang Y (2022) Molecular composition of asphaltene in wellbore blockageon the southern margin of Junggar Basin. Petrol Geo Exp 44 (2):306-313. doi:10.11781/sysydz202202306

28. Huo D, Wu J, Li H, Huang H, Chung KH, Shi Q (2022) Calcium in crude oil: a review. Petrol Sci Technol 40 (23):2861-2876. doi:10.1080/10916466.2022.2050387

29. Chen Z, Wang Y, Wu J, Wang B, Jiang T, Yu J, Yang H, Zhao S, Shi Q, Xu C (2022) Composition of sulfur species in deasphalted oils and their molecular-level transformation during the hydrotreating process. Fuel 328. doi:10.1016/j.fuel.2022.125335

30. Zhang Y, Han Y, Wu J, Wang Y, Li J, Shi Q, Xu C, Hsu CS (2021) Comprehensive Composition, Structure, and Size Characterization for Thiophene Compounds in Petroleum Using Ultrahigh-Resolution Mass Spectrometry and Trapped Ion Mobility Spectrometry. Anal Chem 93 (12):5089-5097. doi:10.1021/acs.analchem.0c04667

31. Zhang S, Huo J, Sun X, Yang F, Wang P, Wu J, Zhang Y, Shi Q (2021) Molecular Composition Reveals Unique Rheological Property of Karamay Heavy Crude Oil. Energy Fuels 35 (1):473-478. doi:10.1021/acs.energyfuels.0c03639

32. Shi Q, Wu J (2021) Review on Sulfur Compounds in Petroleum and Its Products: State-of-the-Art and Perspectives. Energy Fuels 35 (18):14445-14461. doi:10.1021/acs.energyfuels.1c02229

33. Li YY, He C, Wu JX, Zhang YH, Liang YM, Shi Q, Zhang CL (2021) Molecular Characterization of Glycerol Dialkyl Glycerol Tetraethers by High Resolution Orbitrap Mass Spectrometry. J Chin Mass Spectrom Soc 42 (6):1127-1138. doi:10.7538/zpxb.2020.0089

34. Wu J, Zhang W, Ma C, Ren L, Li S, Zhang Y, Shi Q (2020) Separation and characterization of squalene and carotenoids derived sulfides in a low mature crude oil. Fuel 270. doi:10.1016/j.fuel.2020.117536

35. Wu J, Zhang W, Chang W, Wu H, Zhang Y, Shi Q (2020) Isolation of Sulfides from Petroleum for Molecular Characterization by Alumina and Silica Gel Adsorption. Energy Fuels 34 (9):10837-10841. doi:10.1021/acs.energyfuels.0c01985

36. Ge Y, Wu J, Zhang Y, Liang Y, Shi Q (2020) Characterization of Sulfur-Containing Compounds in Petroleum Using AgSbF6as a Methylation Reagent. Energy Fuels 34 (9):10842-10848. doi:10.1021/acs.energyfuels.0c01987

37. Wu J, Zhang W, Ma C, Wang F, Zhou X, Chung KH, Hou D, Zhang Y, Shi Q (2019) Isolation and characterization of sulfur compounds in a lacustrine crude oil. Fuel 253:1482-1489. doi:10.1016/j.fuel.2019.05.044

38. Ren L, Wu J, Qian Q, Liu X, Meng X, Zhang Y, Shi Q (2019) Separation and Characterization of Sulfoxides in Crude Oils. Energy Fuels 33 (2):796-804. doi:10.1021/acs.energyfuels.8b03494

39. Li H, Chen X, Wu J, Zhang Y, Liu X, Shi Q, Zhao S, Xu C, Hsu CS (2019) Selective Methylation of Sulfides in Petroleum for Electrospray Ionization Mass Spectrometry Analysis. Energy Fuels 33 (3):1797-1802. doi:10.1021/acs.energyfuels.8b02756