Citation: LIU Zhao-xian, GUO Ai-jun, CHEN Kun, WANG Zong-xian, CHU Jun, CHEN Jian-tao. Changes in chemical structure and solvation of heavy oil components during thermal upgrading of a vacuum residue[J]. Journal of Fuel Chemistry and Technology, ;2016, 44(3): 366-374. shu

Changes in chemical structure and solvation of heavy oil components during thermal upgrading of a vacuum residue

1.
State Key Laboratory of Heavy Oil, College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China
2.
College of Science, China University of Petroleum (East China), Qingdao 266580, China
3.
Construction and Management Commission Office of Beibu Bay Economic Zone, Beihai 536000, China

Corresponding author: GUO Ai-jun, ajguo@upc.edu.cn
Received Date: 12 October 2015
Revised Date: 8 January 2016

Fund Project: the Application Research of Independent Innovation Foundation of Qingdao 15-9-1-77-jchthe Provincial Natural Science Foundation of Shandong ZR2014BQ030National Natural Science Foundation of China U1362101and the China National Petroleum Corporation (CNPC) Grant on Research and Development for Commercial Application of Novel Technologies in Processing Inferior Heavy Oil PRIKY15002and the China National Petroleum Corporation (CNPC) Grant on Research and Development for Commercial Application of Novel Technologies in Processing Inferior Heavy Oil PRIKY15009and the China National Petroleum Corporation (CNPC) Grant on Research and Development for Commercial Application of Novel Technologies in Processing Inferior Heavy Oil PRIKY15008the Fundamental Research Funds for the Central Universities 14CX02120A

Figures(6)

The Venezuelan vacuum residue was used as a feedstock for thermal upgrading experiments to investigate the changes in chemical structure and composition and the solvation interaction of heavy oil components in a micro-batch reactor at 410℃ with an initial pressure of nitrogen 2.0MPa. The ¹H-nuclear magnetic resonance measurement was applied to analyze the reaction pathway of hydrogen atoms with different chemical shift of the heavy oil components. The average molecular structural parameters of asphaltenes and heavy resins in the oil produced by thermal upgrading of the feedstock were calculated and analyzed by the modified Brown-Lander methods. The vapor pressure osmometry was used to determine the average molecular weights of supramolecular structures formed by asphaltenes and heavy resins in toluene. The results show that both H/C atomic ratio and hydrogen donating ability of asphaltenes and heavy resins decrease with reaction time, and the conjugate degree of aromatic ring system and f_A become greater clearly after 45min. The aggregation of asphaltenes rises slowly and increases sharply after 15 min, while there is a slight change of aggregation for the heavy resins during the whole reaction time, and the differences in aggregation correlation values between asphaltenes and heavy resins are increased by 1.5% at 15min, 50.8% at 25min, and 142.3% at 45min, respectively. The solvation interaction of heavy resins with asphaltenes weakens with time, and the solvation parameters decrease from 32.9% at the beginning to 29.5% at 15min, 14.1% at 25min, and 9.6% at 45min, respectively. The changes may contribute to the dropping of thermal colloidal stability of resins and the increasing of spot ratings.
- thermal upgrading,
- asphaltenes,
- heavy resins,
- chemical structure and composition,
- solvation
1. [1]
  YAO Guo-xin. Current status and development prospects for processing of Venezuelan extra-heavy crude and Canadian oil sand bitumen[J]. Sino-Global Energy, 2012,17(1):3-22.
2. [2]
  LI S H, LIU C G, QUE G H, LIANG W J, ZHU Y J. Colloidal structures of three Chinese petroleum vacuum residues[J]. Fuel, 1996,75(8):1025-1029. doi: 10.1016/0016-2361(95)00315-0
3. [3]
  ZHAO B, SHAW J M. Composition and size distribution of coherent nanostructures in Athabasca bitumen and Maya crude oil[J]. Energy Fuels, 2007,21(5):2795-2804. doi: 10.1021/ef070119u
4. [4]
  INDO K, RATULOWSKI J, DINDORUK B, GAO J L, ZUO J L, MULLINS O C. Asphaltene nanoaggregates measured in a live crude oil by centrifugation[J]. Energy Fuels, 2009,23(9):4460-4469. doi: 10.1021/ef900369r
5. [5]
  CHANG C L, FOGLER H S. Stabilization of asphaltenes in aliphatic solvents using alkylbenzene-derived amphiphiles. 2. Study of the asphaltene-amphiphile interactions and structures using fourier transform infrared spectroscopy and small-angle x-ray scattering techniques[J]. Langmuir, 1994,10(6):1758-1766. doi: 10.1021/la00018a023
6. [6]
  GONZÁLEZ G, NEVES G B M, SARAIVA S M, LUCAS E F, SOUSA M D A D. Electrokinetic characterization of asphaltenes and the asphaltenes-resins interaction[J]. Energy Fuels, 2003,17(4):879-886. doi: 10.1021/ef020249x
7. [7]
  LEÓN O, CONTRERAS E, ROGEL E, DAMBAKLI G, ESPIDEL J, ACEVEDO S. The influence of the adsorption of amphiphiles and resins in controlling asphaltene flocculation[J]. Energy Fuels, 2001,15(5):1028-1032. doi: 10.1021/ef010032n
8. [8]
  LEÓN O, CONTRERAS E, ROGEL E, DAMBAKLI G, ACEVEDO S, CARBOGNANI L, ESPIDEL J. Adsorption of native resins on asphaltene particles: A correlation between adsorption and activity[J]. Langmuir, 2002,18(13):5106-5112. doi: 10.1021/la011394q
9. [9]
  DANIEL M G, ANDERSEN S I. Thermodynamic characterization of asphaltene-resin interaction by microcalorimetry[J]. Langmuir, 2004,20(11):4559-4565. doi: 10.1021/la0499315
10. [10]
  SOORGHALI F, ZOLGHADR A, AYATOLLAHI S. Effects of native and non-native resins on asphaltene deposition and the change of surface topography at different pressures: An experimental investigation[J]. Energy Fuels, 2015,29(9):5487-5494. doi: 10.1021/acs.energyfuels.5b00366
11. [11]
  WANG Qi, GUO Lei, WANG Zong-xian, MU Bao-quan, GUO Ai-jun, LIU He. Hydrogen donor visbreaking of Venezuelan vacuum residue[J]. J Fuel Chem Technol, 2012,40(11):1317-1322. doi: 10.1016/S1872-5813(13)60001-8
12. [12]
  GOULD K A, WIEHE I A. Natural hydrogen donors in petroleum resids[J]. Energy Fuels, 2006,21(3):1199-1204.
13. [13]
  WANG Z X, JI S F, LIU H, CHEN K, GUO A J. Hydrogen transfer of petroleum residue subfractions during thermal processing under hydrogen[J]. Energy Technol, 2015,3(3):259-264. doi: 10.1002/ente.201402190
14. [14]
  GUO A J, WANG Z Q, ZHANG H J, ZHANG X J, WANG Z X. Hydrogen transfer and coking propensity of petroleum residues under thermal processing[J]. Energy Fuels, 2010,24(5):3093-3100. doi: 10.1021/ef100172r
15. [15]
  BROWN J K, LADNER W R. A study of the hydrogen distribution in coal-like materials by high-resolution nuclear magnetic resonance spectroscopy Ⅱ. A comparison with infra-red measurement and the conversion to carbon structure[J]. Fuel, 1960,39:87-96.
16. [16]
  LIU He, CHEN Kun, WANG Zong-xian, GUO Ai-jun. Evaluation of relative hydrogen-donating abilities of different heavy oils during mild thermal conversion by ¹H-NMR[J]. J Fuel Chem Technol, 2013,41(10):1191-1198.
17. [17]
  DICKIE J P, YEN T F. Macrostructures of asphaltic fractions by various instrumental methods[J]. Anal Chem, 1967,39(14):1847-1852. doi: 10.1021/ac50157a057
18. [18]
  LI Chuan, WANG Ji-qian, SUI Li-tao, CUI Min, DENG Wen-an. Study on XPS of Venezuela heavy oil asphaltene[J]. Acta Pet Sin (Pet Proc Sect), 2013,29(3):459-463.
19. [19]
  WANG Zhi-qing. Research on the colloidal stability and hydrogen-transfer of vacuum residue during thermal conversion[D]. Qingdao: China University of Petroleum, 2006.
20. [20]
  SEDGHI M, GOUAL L, WELCH W, KUBELKA J. Effect of asphaltene structure on association and aggregation using molecular dynamics[J]. J Phys Chem B, 2013,117(18):5765-5776. doi: 10.1021/jp401584u
1. [1]
  Tao Jiang , Yuting Wang , Lüjin Gao , Yi Zou , Bowen Zhu , Li Chen , Xianzeng Li . Experimental Design for the Preparation of Composite Solid Electrolytes for Application in All-Solid-State Batteries: Exploration of Comprehensive Chemistry Laboratory Teaching. University Chemistry, 2024, 39(2): 371-378. doi: 10.3866/PKU.DXHX202308057
2. [2]
  Jiandong Liu , Zhijia Zhang , Mikhail Kamenskii , Filipp Volkov , Svetlana Eliseeva , Jianmin Ma . Research Progress on Cathode Electrolyte Interphase in High-Voltage Lithium Batteries. Acta Physico-Chimica Sinica, 2025, 41(2): 100011-. doi: 10.3866/PKU.WHXB202308048
3. [3]
  Zhaoxuan ZHU , Lixin WANG , Xiaoning TANG , Long LI , Yan SHI , Jiaojing SHAO . Application of poly(vinyl alcohol) conductive hydrogel electrolytes in zinc ion batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 893-902. doi: 10.11862/CJIC.20240368
4. [4]
  Yanxin Wang , Hongjuan Wang , Yuren Shi , Yunxia Yang . Application of Python for Visualizing in Structural Chemistry Teaching. University Chemistry, 2024, 39(3): 108-117. doi: 10.3866/PKU.DXHX202306005
5. [5]
  Yecang Tang , Shan Ling , Zhen Fang . Exploration of a Hierarchical and Integration-Oriented Talent Training Model in the Demonstration Center for Experimental Chemistry Education. University Chemistry, 2024, 39(7): 188-192. doi: 10.12461/PKU.DXHX202405107
6. [6]
  Chengshan Yuan , Xiaolong Li , Xiuping Yang , Xiangfeng Shao , Zitong Liu , Xiaolei Wang , Yongwen Shen . Standardized Operational Guidelines for Mixed-Solvent Recrystallization in Organic Chemistry Experiment. University Chemistry, 2025, 40(5): 122-127. doi: 10.12461/PKU.DXHX202504073
7. [7]
  Zunxiang Zeng , Yuling Hu , Yufei Hu , Hua Xiao . Analysis of Plant Essential Oils by Supercritical CO₂Extraction with Gas Chromatography-Mass Spectrometry: An Instrumental Analysis Comprehensive Experiment Teaching Reform. University Chemistry, 2024, 39(3): 274-282. doi: 10.3866/PKU.DXHX202309069
8. [8]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . 液相法制备硫化物固体电解质及其在全固态锂电池中的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2309019-. doi: 10.3866/PKU.WHXB202309019
9. [9]
  Yu Peng , Jiawei Chen , Yue Yin , Yongjie Cao , Mochou Liao , Congxiao Wang , Xiaoli Dong , Yongyao Xia . 无碳酸乙烯酯电解液定向构筑正极电解质界面相实现高电压钴酸锂的宽温域稳定运行. Acta Physico-Chimica Sinica, 2025, 41(8): 100087-. doi: 10.1016/j.actphy.2025.100087
10. [10]
  Yinyin Qian , Rui Xu . Utilizing VESTA Software in the Context of Material Chemistry: Analyzing Twin Crystal Nanostructures in Indium Antimonide. University Chemistry, 2024, 39(3): 103-107. doi: 10.3866/PKU.DXHX202307051
11. [11]
  Qiying Xia , Guokui Liu , Yunzhi Li , Yaoyao Wei , Xia Leng , Guangli Zhou , Aixiang Wang , Congcong Mi , Dengxue Ma . Construction and Practice of “Teaching-Learning-Assessment Integration” Model Based on Outcome Orientation: Taking “Structural Chemistry” as an Example. University Chemistry, 2024, 39(10): 361-368. doi: 10.3866/PKU.DXHX202311007
12. [12]
  Zian Lin , Yingxue Jin . Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI-MS) for Disease Marker Screening and Identification: A Comprehensive Experiment Teaching Reform in Instrumental Analysis. University Chemistry, 2024, 39(11): 327-334. doi: 10.12461/PKU.DXHX202403066
13. [13]
  Yang Lv , Yingping Jia , Yanhua Li , Hexiang Zhong , Xinping Wang . Integrating the Ideological Elements with the “Chemical Reaction Heat” Teaching. University Chemistry, 2024, 39(11): 44-51. doi: 10.12461/PKU.DXHX202402059
14. [14]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
15. [15]
  Lijun Dong , Pengcheng Du , Guangnong Lu , Wei Wang . Exploration and Practice of Independent Design Experiments in Inorganic and Analytical Chemistry: A Case Study of “Preparation and Composition Analysis of Tetraammine Copper(II) Sulfate”. University Chemistry, 2024, 39(4): 361-366. doi: 10.3866/PKU.DXHX202310041
16. [16]
  Yuqiao Zhou , Weidi Cao , Shunxi Dong , Lili Lin , Xiaohua Liu . Study on the Teaching Reformation of Practical X-ray Crystallography. University Chemistry, 2024, 39(3): 23-28. doi: 10.3866/PKU.DXHX202303003
17. [17]
  Yahui HAN , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Synthesis, crystal structure, thermal decomposition mechanism, and fluorescence properties of benzoic acid and 4-hydroxy-2, 2′: 6′, 2″-terpyridine lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 969-982. doi: 10.11862/CJIC.20240395
18. [18]
  Yingxian Wang , Tianye Su , Limiao Shen , Jinping Gao , Qinghe Wu . Introduction of Chinese Lacquer from the Perspective of Chemistry: Popularizing Chemistry in Lacquer and Inherit Lacquer Art. University Chemistry, 2024, 39(5): 371-379. doi: 10.3866/PKU.DXHX202312015
19. [19]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
20. [20]
  Xu Liu , Chengfang Liu , Jie Huang , Xiangchun Li , Wenyong Lai . Research on the Application of Diversified Teaching Models in the Teaching of Physical Chemistry. University Chemistry, 2024, 39(8): 112-118. doi: 10.3866/PKU.DXHX202402021

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(989)
HTML views(47)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142