Low temperature oxidized coke of the ultra-heavy oil during in-situ combustion process: Structural characterization and evolution elucidation

Abstract

Fundamental knowledge on the evolution of low temperature oxidized coke was a prerequisite towards a deep understanding of coke deposition and subsequent combustion of ultra-heavy oils during in-situ combustion (ISC) process. This study investigated the structural characterization (oxidation behavior, elemental composition, functional groups, and morphology) and elucidated evolution mechanism of cokes generated from the low temperature oxidation/pyrolysis of the ultra-heavy oil during ISC process. The results shown that, compared with pyrolytic coke, the intermediate groups of C-O/C-OH (1260–1060 cm−1) were further oxidized into C = O (1850–1650 cm−1) groups and finally converted into C = C groups (“coke peak”, 1590 cm−1) in highly conjugated aromatic structures for oxidized cokes. Besides, the oxidized coking condition would result in a higher degree of substitution (γCHAr1, γCHAr4) of aromatic rings (900–700 cm−1) and promote the evolution of N- and S- functional groups. Although >78 % of C 1 s belonged to the graphitic carbon for four cokes, morphologies of oxidized cokes were relatively coarse with much looser distribution. In addition, the corresponding enthalpies were in the order cokeLTO3 (25.51 kJ·g−1) > cokeLTP (24.22 kJ·g−1) > cokeLTO2 (23.23 kJ·g−1) > cokeLTO1 (17.45 kJ·g−1), indicating a considerable contribution of low temperature oxidation reactions on derived coke morphology, oxidizability and exothermicity, which contained complicated and crucial dehydrogenation, crosslinking and polymerization reactions to accelerate coke evolution.