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The Promotional Effect of Initiators in Hydro-thermal Cracking of Resids

ע⣺ՓڡACS Prepr. Div. Fuel Chem., New Orleans, USA, 44 (4), pp.801.l
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Jie Chang, Li Fan  and Kaoru Fujimoto
Department of Applied Chemistry, School of Engineering, The University of Tokyo

Introduction
With growing worldwide demand for transport fuels and other middle distillates, much attention has been paid to the upgrading of heavy oil feedstock. It was forecasted that up to early 2000, the petroleum product slate will continue to shift from fuel oil to transportation fuels, distillate and jet will be the products with the strongest growth, and the conversion will be increased worldwide to meet this trend (Sonnemans, 1995). Based on cracking mechanism, there are three main industrial processes to produce middle distillate from resid, thermal cracking, catalytic cracking and hydrocracking. Hydro-thermal cracking, the combination of thermal cracking and catalytic hydrogenating, is a novel method developed by Fujimoto laboratory to upgrade resids aiming at maximum middle distillate (Fujimoto et al., 1988; Aimoto et al., 1991; Yang et al., 1998). The following elementary steps are important during hydro-thermal cracking reactions: (1) Initiation free radical (homolytic cleavage of a hydrocarbon molecule into two free radicals). (2) Free radical dissociation (scission). (3) Hydrogen transfer (between H2, radical and hydrocarbon). H transfer from H2 to radical may suppress the secondary cracking of hydrocarbon. It was supposed that some effective initiators could probably enhance the conversion of resids by increasing the concentration of free radicals. Much research has been carried out on catalyst development, reaction mechanism, process design and optimization in the above refinery processes in the last half century. But the issue of adding initiators in the cracking of resids was very rarely addressed. The present work showed the promotional effect of initiators in hydro-thermal cracking of resids and its model compound.

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