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张亚和

日期：2026-10-02 | 访问量：


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毕业时间：2014年6月（博士）

毕业去向：中国石油大学（北京）

导师：徐春明 教授、史权 副教授

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

FT-ICR MS方法基础及其在重质油分子组成分析中的应用

Foundation and Applications of FT-ICR MS Methodology for Molecular Characterization of Heavy Petroleum Fractions

 

论文摘要

从分子水平研究重质油化学组成是石油化学研究的难题，关键问题是传统质谱技术无法满足石油样品对分辨率的要求。近年来，新型电离技术的开发和傅立叶变换离子回旋共振质谱（FT-ICR MS）在质量分辨率方面的快速提升，在技术上为重质油分子组成分析提供了条件，亟待解决很多方法学上的基础性问题，为FT-ICR MS应用于重质油分子组成分析提供理论依据。本论文围绕重质油分子组成分析这一主要目标，利用多种离子化技术，在系统考察质谱操作条件基础上，建立重质油分子组成的定性、定量分析方法，并将相关方法应用于多种重质油样品的分子组成分析。主要内容包括：研究了石油样品在不同电离源中的电离特性，提出了适用于不同重质油组分的成套离子化方案。包括钌离子催化氧化结合电喷雾（ESI）电离源分析饱和烃；大气压光致电离（APPI）分析芳烃、硫化物和卟啉化合物；甲基化结合电喷雾（MeESI）分析硫化物；E SI电离分析酸性化合物、中性氮化物、碱性氮化物和卟啉化合物等。考察了ESI中石油分子的电离抑制效应，发现电离抑制主要影响不同类型化合物间的相对丰度，而对同系物间的相对丰度影响不大，证明了ESI定量分析石油分子组成的可行性。发现FT-ICR MS离子转输过程存在比较严重的质量歧视效应，对产生质量歧视的原因及其影响进行深入研究，阐明了不同操作条件对离子传输效率和产生质量歧视的影响机制，基于分段优化操作，提出FT-ICR MS宽程谱图合成方法和定量分析理论。

综合运用多种方法，对委内瑞拉减压渣油进行分子组成表征，分别针对饱和烃、芳烃、硫化物、酸性化合物、中性氮化物、碱性氮化物和卟啉化合物进行了详细的组成分析。从分子层面揭示了渣油在烷烃超临界流体萃取分离过程中不同组分的走向与分布。

对比不同电离源分析重质油高分辨质谱结果的一致性，回答了关于不同电离源条件下高分辨质谱分析结果的可信度问题。

基于FT-ICR MS对石油分子组成的精细分析，建立了石油酸和中性氮化物的高效分离方法，分离和鉴定出包括类异戊二烯苯酚、生育酚及大分子四元羧酸等具有特殊地质意义的生物标志化合物。研究成果为石油化学相关研究奠定理论和方法基础，对重质油的勘探、开发和加工利用具有重大的应用价值。

关键词：重质油；分子组成；傅立叶变换离子回旋共振质谱；电离源；高分辨质谱

 

创新点

（1）系统研究了石油组分在不同电离源中的电离特性，探索出一套重质油分子适用的电离方法。

（2）考察了电喷雾离子源中石油组分的电离抑制和响应因子效应，证实阐明了同时定量分析石油组分中不同类型化合物的可行性。

（3）开发了一种石油组分FT-ICR MS分析的全谱谱图合并的方法，可以在宽质量范围内校正FT-ICR MS存在的质量歧视。

（4）系统地分析了委内瑞拉减压渣油分子组成，包括饱和烃、芳烃、硫化物、酸性化合物、中性氮化物、碱性氮化物和卟啉化合物。从分子组成层面阐明了烷烃超临界流体萃取分离对渣油中不同化合物的选择性。

（5）基于FT-ICR MS分析对石油分子组成的深入认识，建立了石油酸和中性氮化物分离的新型分离方法，并为重质油其它类型化合物的分离分析提供了方法论和理论指导。

 

科研成果评价

张亚和博士是课题组核心骨干成员，自2004年起在实验室工作，在完成博士论文期间始终坚守工作岗位，体现了高度的责任感与奉献精神。

他在实验室日常运行中发挥了重要作用，尤其是在傅立叶变换离子回旋共振质谱（FT-ICR MS）的建设、管理与维护方面做出了卓越贡献，为实验室高质量分子组成数据平台的建设和科研工作的顺利开展提供了坚实保障。

 

发表学术论文

  1. [1]陆小泉; 史权; 赵锁奇; 高金森; 张亚和; 何俊辉. 碱液萃取前后原油中酸性化合物组成的高分辨质谱分析. 分析化学 2008, (5), 614–618.

  2. [2]史权; 董智勇; 张亚和; 赵锁奇; 徐春明. 石油组分高分辨质谱的数据处理. 分析测试学报 2008, (S1), 246–248.

  3. [3]史权; 王铁冠; 钟宁宁; 张枝焕; 张亚和. 苯并苊类化合物在气溶胶中的检出及其环境地球化学意义. 科学通报 2008, (4), 433–436.

  4. [4]张亚和; 史权; 何俊辉; 胡伟峰; 朱雷. 固相萃取法对原油中咔唑类含氮化合物的分离. 分析测试学报 2008, (S1), 252–255.

  5. [5]潘娜; 史权; 徐春明; 刘鹏; 张亚和; 何俊辉; 赵锁奇. 直馏柴油中硫化物甲基锍盐合成及电喷雾-高分辨质谱分析. 分析化学 2010, 38 (3), 413–416.

  6. [6]史权; 张亚和; 徐春明; 赵锁奇; H, C. K. 石油组分高分辨质谱分析进展与展望. 中国科学:化学 2014, 44 (5), 694–700.

  7. [7]Liu, P.; Shi, Q.; Chung, K. H.; Zhang, Y.; Pan, N.; Zhao, S.; Xu, C. Molecular characterization of sulfur compounds in venezuela crude oil and its SARA fractions by electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. In Energy and Fuels, 2010; Vol. 24, pp 5089–5096
    https://doi.org/10.1021/ef100904k

  8. [8]Liu, P.; Xu, C.; Shi, Q.; Pan, N.; Zhang, Y.; Zhao, S.; Chung, K. H. Characterization of sulfide compounds in petroleum: Selective oxidation followed by positive-ion electrospray fourier transform ion cyclotron resonance mass spectrometry. In Analytical Chemistry, 2010; Vol. 82, pp 6601–6606
    https://doi.org/10.1021/ac1010553

  9. [9]Shi, Q.; Hou, D.; Chung, K. H.; Xu, C.; Zhao, S.; Zhang, Y. Characterization of heteroatom compounds in a crude oil and its saturates, aromatics, resins, and asphaltenes (SARA) and non-basic nitrogen fractions analyzed by negative-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. In Energy and Fuels, 2010; Vol. 24, pp 2545–2553
    https://doi.org/10.1021/ef901564e

  10. [10]Shi, Q.; Pan, N.; Liu, P.; Chung, K. H.; Zhao, S.; Zhang, Y.; Xu, C. Characterization of sulfur compounds in oilsands bitumen by methylation followed by positive-ion electrospray ionization and fourier transform ion cyclotron resonance mass spectrometry. Energy and Fuels 2010, 24 (5), 3014–3019
    https://doi.org/10.1021/ef9016174

  11. [11]Shi, Q.; Xu, C.; Zhao, S.; Chung, K. H.; Zhang, Y.; Gao, W. Characterization of basic nitrogen species in coker gas oils by positive-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. In Energy and Fuels, 2010; Vol. 24, pp 563–569
    https://doi.org/10.1021/ef9008983

  12. [12]Shi, Q.; Zhao, S.; Xu, Z.; Chung, K. H.; Zhang, Y.; Xu, C. Distribution of acids and neutral nitrogen compounds in a Chinese crude oil and its fractions: Characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Energy and Fuels 2010, 24 (7), 4005–4011
    https://doi.org/10.1021/ef1004557

  13. [13]Zhang, Y.; Xu, C.; Shi, Q.; Zhao, S.; Chung, K. H.; Hou, D. Tracking neutral nitrogen compounds in subfractions of crude oil obtained by liquid chromatography separation using negative-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. Energy and Fuels 2010, 24 (12), 6321–6326
    https://doi.org/10.1021/ef1011512

  14. [14]Liu, P.; Shi, Q.; Pan, N.; Zhang, Y.; Chung, K. H.; Zhao, S.; Xu, C. Distribution of sulfides and thiophenic compounds in VGO subfractions: Characterized by positive-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry. In Energy and Fuels, 2011; Vol. 25, pp 3014–3020
    https://doi.org/10.1021/ef200496k

  15. [15]Zhang, Y.; Shi, Q.; Li, A.; Chung, K. H.; Zhao, S.; Xu, C. Partitioning of crude oil acidic compounds into subfractions by extrography and identification of isoprenoidyl phenols and tocopherols. Energy and Fuels 2011, 25 (11), 5083–5089
    https://doi.org/10.1021/ef2011854

  16. [16]Zhang, Y.; Zhao, H.; Shi, Q.; Chung, K. H.; Zhao, S.; Xu, C. Molecular investigation of crude oil sludge from an electric dehydrator. In Energy and Fuels, 2011; Vol. 25, pp 3116–3124
    https://doi.org/10.1021/ef200512c

  17. [17]Zhu, X.; Shi, Q.; Zhang, Y.; Pan, N.; Xu, C.; Chung, K. H.; Zhao, S. Characterization of nitrogen compounds in coker heavy gas oil and its subfractions by liquid chromatographic separation followed by fourier transform ion cyclotron resonance mass spectrometry. Energy and Fuels 2011, 25 (1), 281–287
    https://doi.org/10.1021/ef101328n

  18. [18]Liao, Y.; Shi, Q.; Hsu, C. S.; Pan, Y.; Zhang, Y. Distribution of acids and nitrogen-containing compounds in biodegraded oils of the Liaohe Basin by negative ion ESI FT-ICR MS. Organic Geochemistry 2012, 47, 51–65
    https://doi.org/10.1016/j.orggeochem.2012.03.006

  19. [19]Liu, Y.; Shi, Q.; Zhang, Y.; He, Y.; Chung, K. H.; Zhao, S.; Xu, C. Characterization of red pine pyrolysis bio-oil by gas chromatography-mass spectrometry and negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. In Energy and Fuels, 2012; Vol. 26, pp 4532–4539
    https://doi.org/10.1021/ef300501t

  20. [20]Long, H.; Shi, Q.; Pan, N.; Zhang, Y.; Cui, D.; Chung, K. H.; Zhao, S.; Xu, C. Characterization of middle-temperature gasification coal tar. Part 2: Neutral fraction by extrography followed by gas chromatography-mass spectrometry and electrospray ionization coupled with fourier transform ion cyclotron resonance mass spectrometry. In Energy and Fuels, 2012; Vol. 26, pp 3424–3431
    https://doi.org/10.1021/ef2020167

  21. [21]Pan, N.; Cui, D.; Li, R.; Shi, Q.; Chung, K. H.; Long, H.; Li, Y.; Zhang, Y.; Zhao, S.; Xu, C. Characterization of middle-temperature gasification coal tar. Part 1: Bulk properties and molecular compositions of distillates and basic fractions. Energy and Fuels 2012, 26 (9), 5719–5728
    https://doi.org/10.1021/ef3007323

  22. [22]Zhang, H.; Zhang, Y.; Shi, Q.; Hu, J.; Chu, M.; Yu, J.; Yang, M. Study on transformation of natural organic matter in source water during chlorination and its chlorinated products using ultrahigh resolution mass spectrometry. Environmental Science and Technology 2012, 46 (8), 4396–4402
    https://doi.org/10.1021/es203587q

  23. [23]Zhang, H.; Zhang, Y.; Shi, Q.; Ren, S.; Yu, J.; Ji, F.; Luo, W.; Yang, M. Characterization of low molecular weight dissolved natural organic matter along the treatment trait of a waterworks using Fourier transform ion cyclotron resonance mass spectrometry. Water Research 2012, 46 (16), 5197–5204
    https://doi.org/10.1016/j.watres.2012.07.004

  24. [24]Zhang, L.; Xu, Z.; Shi, Q.; Sun, X.; Zhang, N.; Zhang, Y.; Chung, K. H.; Xu, C.; Zhao, S. Molecular characterization of polar heteroatom species in Venezuela Orinoco petroleum vacuum residue and its supercritical fluid extraction subfractions. Energy and Fuels 2012, 26 (9), 5795–5803
    https://doi.org/10.1021/ef3009663

  25. [25]Zhou, X.; Shi, Q.; Zhang, Y.; Zhao, S.; Zhang, R.; Chung, K. H.; Xu, C. Analysis of saturated hydrocarbons by redox reaction with negative-ion electrospray fourier transform ion cyclotron resonance mass spectrometry. Analytical Chemistry 2012, 84 (7), 3192–3199
    https://doi.org/10.1021/ac203035k

  26. [26]Wang, L.; He, C.; Liu, Y.; Zhao, S.; Zhang, Y.; Xu, C.; Chung, K. H.; Shi, Q. Effects of experimental conditions on the molecular composition of maltenes and asphaltenes derived from oilsands bitumen: Characterized by negative-ion ESI FT-ICR MS. In Science China Chemistry, 2013; Vol. 56, pp 863–873
    https://doi.org/10.1007/s11426-013-4902-0

  27. [27]Wang, L.; He, C.; Zhang, Y.; Zhao, S.; Chung, K. H.; Xu, C.; Hsu, C. S.; Shi, Q. Characterization of acidic compounds in heavy petroleum resid by fractionation and negative-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrometry analysis. In Energy and Fuels, 2013; Vol. 27, pp 4555–4563
    https://doi.org/10.1021/ef400459m

  28. [28]Zhang, L.; Zhang, Y.; Zhao, S.; Xu, C.; Chung, K. H.; Shi, Q. Characterization of heavy petroleum fraction by positive-ion electrospray ionization FT-ICR mass spectrometry and collision induced dissociation: Bond dissociation behavior and aromatic ring architecture of basic nitrogen compounds. In Science China Chemistry, 2013; Vol. 56, pp 874–882
    https://doi.org/10.1007/s11426-013-4899-4

  29. [29]Zhao, X.; Liu, Y.; Xu, C.; Yan, Y.; Zhang, Y.; Zhang, Q.; Zhao, S.; Chung, K.; Gray, M. R.; Shi, Q. Separation and characterization of vanadyl porphyrins in Venezuela Orinoco heavy crude oil. Energy and Fuels 2013, 27 (6), 2874–2882
    https://doi.org/10.1021/ef400161p

  30. [30]Zhou, X.; Zhang, Y.; Zhao, S.; Hsu, C. S.; Shi, Q. Observation of CO2 and solvent adduct ions during negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric analysis of monohydric alcohols. Rapid Communications in Mass Spectrometry 2013, 27 (23), 2581–2587
    https://doi.org/10.1002/rcm.6721

  31. [31]Zhang, H.; Zhang, Y.; Shi, Q.; Zheng, H.; Yang, M. Characterization of unknown brominated disinfection byproducts during chlorination using ultrahigh resolution mass spectrometry. Environmental Science and Technology 2014, 48 (6), 3112–3119
    https://doi.org/10.1021/es4057399

  32. [32]Zhang, L.; Zhang, Y.; Zhao, S.; Chung, K. H.; Xu, C.; Shi, Q. Effect of apodization on FT-ICR mass spectrometry analysis of petroleum. International Journal of Mass Spectrometry 2014, 373, 27–33
    https://doi.org/10.1016/j.ijms.2014.08.030

  33. [33]Zhang, Y.; Zhang, L.; Xu, Z.; Zhang, N.; Chung, K. H.; Zhao, S.; Xu, C.; Shi, Q. Molecular characterization of vacuum resid and its fractions by Fourier transform ion cyclotron resonance mass spectrometry with various ionization techniques. Energy and Fuels 2014, 28 (12), 7448–7456
    https://doi.org/10.1021/ef502162b

  34. [34]Zhou, X.; Zhang, Y.; Zhao, S.; Chung, K. H.; Xu, C.; Shi, Q. Characterization of saturated hydrocarbons in vacuum petroleum residua: Redox derivatization followed by negative-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. In Energy and Fuels, 2014; Vol. 28, pp 417–422
    https://doi.org/10.1021/ef4016284