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
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