毕业时间：2024年6月

毕业去向：中国石油大学（华东）

学位论文：稠油分子组成表征及其在火驱过程中分子转化

火驱（in-situ combustion, ISC）是一种最大限度提高稠油采收率的终端开发技术，但其涉及复杂的反应过程，相关的现场研究十分匮乏。从分子层次去认识稠油的化学组成及其在ISC过程中的转化是实现ISC效益最大化的有效手段。本论文首先取得了新疆ISC稠油的全分子组成认识，围绕ISC过程中稠油经历的热反应展开研究，主要是高温裂解和低温氧化反应，并揭示稠油分子在反应前后的组成变化，最后对ISC现场采出液进行综合分析，确定了采出油界面活性组分和采出水DOM的分子组成变化，主要内容如下：

使用气相色谱质谱联用技术（GC-MS）和傅里叶变换离子回旋共振质谱（FT-ICR MS）结合各种化学衍生化技术，对新疆ISC稠油进行了详细的分子组成表征。结果表明，ISC生成了丰富的包括吡啶类氮杂芳烃在内的小分子芳香烃，是造成稠油黏度大幅降低的主要原因。ISC稠油的饱和分和芳香分含量较高，且饱和烃分子组成以长侧链低环环烷烃为主，这表明ISC稠油具有生产高品质润滑油基础油的潜力。

使用黄金管生烃热模拟装置对稠油进行高温裂解反应，基于超高分辨率质谱和气相色谱质谱技术分析了裂解产物分子组成随温度的变化规律。结果表明，新疆稠油于450 ºC前通过裂解形成丰富的小分子芳烃和链烷烃，收率高达27%，在ISC开发过程中起到很好的原位稀释作用。于裂解产物中检测到丰富的多环芳烃（PAHs）生成，包括迫位缩合形成的线性PAHs、渺位缩合形成的非线性PAHs以及通过芳基-碳键连接形成的联苯型多环芳烃。随着温度升高，苯基萘、联萘等联苯型多环芳烃因其具有更高的结构热稳定性在裂解产物中富集，可作为指示ISC现场高温裂解程度的分子标记物。

利用反应釜对新疆稠油进行低温氧化反应，基于超高分辨率质谱和气相色谱质谱技术分析稠油氧化前后的分子组成分布。根据分子极性和溶解度的差异，通过梯度索式抽提法结合微固相萃取技术对氧化残渣进行处理，首次从分子层面揭示了氧化焦的化学组成特征。与裂解焦相比，氧化焦在化学组成上并不是真正的“焦炭”，而是由高度氧化的含氧化合物经氧化偶联反应生成。

在取得了稠油在热解和低温氧化反应中的分子转化认识后，对三组ISC现场采出液进行详细表征。结果表明，随着ISC稠油黏度降低，采出油乳化性能显著降低。通过70%含水硅胶直接从原油中分离富集出相应的界面活性组分（IM）并进行模型乳化实验评价。结果表明，相同浓度下各采出油中活性组分的乳化能力相似，高温裂解为主导的ISC开发过程对界面活性组分的组成基本无影响，ISC将形成并促进低缩合度的多元有机酸溶于水，这将导致采出水具有更高的环境污染风险并增大后续水处理工艺的负担。

研究生期间发表论文

1. 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

2. Xiao S, Chen J, Shen Y, Chen Q, Wang Y, Li Y, He C, Cai R, Shi Q, Jiao N, Zheng Q (2023) Molecular characterization of organic matter transformation mediated by microorganisms under anoxic/hypoxic conditions. Sci China Earth Sci 66 (4):894-909. doi:10.1007/s11430-022-1080-8

3. Su R, Li Y, Ma S, Xiang H, Wang Z, Hu Z, Zhao Q, Chen L, Pan J, Xu C, Liao G, Shi Q (2023) Evolution of Hydrocarbons and Carboxylic Acids in Heavy Oil during In Situ Combustion in Xinjiang Oilfield. Energy Fuels 37 (18):13751-13758. doi:10.1021/acs.energyfuels.3c02475

4. Ma S, Li YY, Su RG, Wang XS, Pan JJ, Shi Q, Liao GZ, Xu CM (2023) Molecular composition of low-temperature oxidation products of the heavy oil. Petrol Sci 20 (5):3264-3271. doi:10.1016/j.petsci.2023.09.008

5. 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

6. 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

7. Xu J, Chen Q, Lønborg C, Li Y, Cai R, He C, Shi Q, Hu Y, Wang Y, Jiao N, Zheng Q (2022) You Exude What You Eat: How Carbon-, Nitrogen-, and Sulfur-Rich Organic Substrates Shape Microbial Community Composition and the Dissolved Organic Matter Pool. Appl Environ Microbiol 88 (23). doi:10.1128/aem.01558-22

8. She Z, Wang J, He C, Pan X, Shi Q, Shao R, Li Y, Yue Z (2022) New Insights into Microbial Interactions with Dissolved Organic Matter in Acid Mine Drainage with the Integration of Microbial Community and Chemical Composition Analysis. ACS Environ Sci Technol W 2 (2):278-287. doi:10.1021/acsestwater.1c00273

9. Li Y, Liao G, Wang Z, Su R, Ma S, Zhang H, Wang L, Wang X, Pan J, Shi Q (2022) Molecular composition of low-temperature oxidation products in a simulated crude oil In-situ combustion. Fuel 316. doi:10.1016/j.fuel.2022.123297

10. Li L, Li Y, Fang Z, He C (2022) Study on molecular structure characteristics of natural dissolved organic nitrogen by use of negative and positive ion mode electrospray ionization Orbitrap mass spectrometry and collision-induced dissociation. Sci Total Environ 810. doi:10.1016/j.scitotenv.2021.152116

11. Chen Q, Lønborg C, Chen F, Gonsior M, Li Y, Cai R, He C, Chen J, Wang Y, Shi Q, Jiao N, Zheng Q (2022) Increased microbial and substrate complexity result in higher molecular diversity of the dissolved organic matter pool. Limnol Oceanogr 67 (11):2360-2373. doi:10.1002/lno.12206

12. Zheng Q, Lin W, Wang Y, Li Y, He C, Shen Y, Guo W, Shi Q, Jiao N (2021) Highly enriched N-containing organic molecules of Synechococcus lysates and their rapid transformation by heterotrophic bacteria. Limnol Oceanogr 66 (2):335-348. doi:10.1002/lno.11608

13. Wang K, Pang Y, Li Y, He C, Shi Q, Wang Y, He D (2021) Characterizing Dissolved Organic Matter across a Riparian Soil-Water Interface: Preliminary Insights from a Molecular Level Perspective. ACS Earth Space Chem 5 (5):1102-1113. doi:10.1021/acsearthspacechem.1c00029

14. Wang J, Yue Z, She Z, He C, Pan X, Li Y, Zhang S, Shi Q (2021) The stratified distribution of dissolved organic matter in an AMD lake revealed by multi-sample evaluation procedure. Environ Sci Technol 55 (12):8401-8409. doi:10.1021/acs.est.0c05319

15. Pang Y, Wang K, Sun Y, Zhou Y, Yang S, Li Y, He C, Shi Q, He D (2021) Linking the unique molecular complexity of dissolved organic matter to flood period in the Yangtze River mainstream. Sci Total Environ 764. doi:10.1016/j.scitotenv.2020.142803

16. 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

17. Chen Q, Chen F, Gonsior M, Li Y, Wang Y, He C, Cai R, Xu J, Wang Y, Xu D, Sun J, Zhang T, Shi Q, Jiao N, Zheng Q (2021) Correspondence between DOM molecules and microbial community in a subtropical coastal estuary on a spatiotemporal scale. Environ Int 154. doi:10.1016/j.envint.2021.106558

18. Zhang SY, Yue ZB, She ZX, Pan X, Shao R, Shi Q, He C, Li YY, Wang J (2020) Characteristics analysis of dissolved organic matter in the acid mine drainage. Zhongguo Huanjing Kexue 40 (8):3401-3407

19. Wang J, Zhang S, He C, She Z, Pan X, Li Y, Shao R, Shi Q, Yue Z (2020) Source identification and component characterization of dissolved organic matter in an acid mine drainage reservoir. Sci Total Environ 739. doi:10.1016/j.scitotenv.2020.139732

20. He D, Wang K, Pang Y, He C, Li P, Li Y, Xiao S, Shi Q, Sun Y (2020) Hydrological management constraints on the chemistry of dissolved organic matter in the Three Gorges Reservoir. Water Res 187. doi:10.1016/j.watres.2020.116413