Pyrolyse du n-butylcyclohexane à haute pression (100 bar) : application à la stabilité thermique des naphtènes dans les fluides pétroliers HP/HT

Abstract : This thesis aims at better understanding the thermal cracking reactions of naphthenes (saturated cyclic hydrocarbons), occurring in petroleum reservoirs. Naphthenes represent a significant fraction of “High Pressure/High Temperature” oils in deeply buried reservoirs; however, studies in these conditions are very limited in literature. The pyrolysis of n-butylcyclohexane is studied in a gold sealed tube reactor between 300 and 425°C, at 100 bar. n-Butylcylohexane mainly leads to n-alkanes (C1-C4), other naphthenes and aromatic compounds. A detailed model is developed (833 reactions, mainly free-radical reactions); a good agreement with our experimental results is reached up to a conversion of 60%. According to simulation results obtained by extrapolating to lower temperature, this compound starts to undergo thermal cracking at 180°C and its time of half-life corresponds to a temperature around 200-210°C, while considering the following burial scenario of an oil reservoir: initial temperature of 160°C and a heating rate of 2°C/MY (Million Years). Other chemical systems including naphthenes, are also studied at 400°C and 100 bar. The study of 1-n-butyldecaline shows, that this bicyclic compound and n-butylcyclohexane have a similar reactivity at 400°C. The study of the binary mixture n-butylcyclohexane/n-octane at 400°C does not provide any significant evidence of a kinetic effect of n-butylcyclohexane on the thermal decomposition of n-octane, but the extrapolation of our model at geological conditions shows that naphthenes are inhibitors of the decomposition of n-alkanes at low temperature (200°C) and at high pressure (100 bar)
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Andrianjafy Darwin Rakotoalimanana. Pyrolyse du n-butylcyclohexane à haute pression (100 bar) : application à la stabilité thermique des naphtènes dans les fluides pétroliers HP/HT. Alimentation et Nutrition. Université de Lorraine, 2016. Français. ⟨NNT : 2016LORR0029⟩. ⟨tel-01752230⟩

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