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Enhancing Effect of Local Heating by an Inside Filament on Hydrothermal Cracking of Hydrocarbon Catalyzed by Ni/Al2O3

ע⣺ՓڡSekiyu Gakkaishi (J. Japan Petrol. Inst.) 43 (6), pp. 414.l
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Jie CHANG†1), Noritatsu TSUBAKI†1)*, Kaoru FUJIMOTO†1) and Masao YOSHIMOTO†2)
†1) Dept. of Applied Chemistry, School of Engineering, The University of Tokyo,
Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-8656, JAPAN
†2) Petroleum Energy Center of Japan, KSP R&D Build. D-12-1237, 3-2-1, Sakado,
Takatsu-ku, Kawasaki, Kanagawa, 213-0012, JAPAN

    During the hydrothermal cracking of hydrocarbon and heavy oil catalyzed by Ni/Al2O3, the conversions of hydrocarbon and heavy oil were remarkably enhanced by heating with a small inside filament. The experiment facts suggested that the heating with inside filament might realize higher temperature zone at local space in the reactor, which was responsible for an increase of the concentration of free radicals, and enhanced the conversion of hydrocarbons even at lower temperature.
Keywords: Hydrothermal process, Hydrocarbon, Heavy oil, Initiation, Filament

1. Introduction

Hydrothermal cracking of heavy oil is a tailor-made combined process of thermal cracking and catalytic hydrogenating that has been developed to produce high quality transportation fuels and middle distillate products from residual oils1), which is composed of the following elementary steps: (1) formation of free radicals proceeding via cleavage of C-C or C-X (heteroatom) bond2),3); (2) production of middle distillate proceeding via -scission of free radicals4); (3) termination of free radical reactions and saturation of C=C bonds proceeding via catalytic hydrogenation.
When reaction temperature increased, the conversion of resid increased, but the selectivities of gaseous hydrocarbons and coke increased tremendously. We have demonstrated that the addition of some initiators, such as element sulfur and di-tert-butyl-peroxide, which might produce free radicals even at lower temperature, enhanced the conversion of resids and increased the yield of distillate5),6). This letter presents an enhancing effect by another initiation method, local heating by an inside filament. The experiment results proved that local heating by inside filament effectively enhanced the conversion of Arabian vacuum residue and its model compound, 1-phenyl dodecane (PhDD).



References

1) Fujimoto, K., Chang, J., Tsubaki, N., Sekiyu Gakkaishi, 43, (1), 25 (2000).
2) Aimoto, K., Nakamura, I., Fujimoto, K., Energy & Fuels, 5, 739 (1991).
3) Beaton, W. I., Bertolacini, R., Catal. Rev.-Sci. Eng., 34 (3&4), 281 (1991).
4) Savage, P. E., Klein, M. T., Ind. Eng. Chem. Res., 26, 488 (1987).
5) Chang, J., Fan, L., Fujimoto, K., Energy & Fuels, 13 (5), 1107 (1999).
6) Chang, J., Fan, L., Fujimoto, K., ACS Prepr. Div. Fuel Chem., 44 (4), 801 (1999).

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2Initiation Effect of Local Heating in Hydro-Thermal Cracking of Resids

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5Enhancement effect of free radical initiator on hydro-thermal cracking of heavy oil and model compound

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