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

注意:本論文已在《ACS Prepr. Div. Fuel Chem., New Orleans, USA,》 44 (4), pp.801.發表
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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 (βscission). (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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作者點評:

      從反應機理上可以將石油煉制工藝分為兩大類:加氫和脫碳。加氫工藝包括加氫處理和加氫裂化等。脫碳工藝包括催化裂化、熱裂化和焦化等。但其目的都是提高產品的H/C比,脫除硫、氮、氧和金屬等雜原子。針對國際上對中間餾分油需求量不斷增大的趨勢,我們創造性的提出了以多產中間餾分油為目標的加氫熱裂化新方法。
    本文采用模型化合物十二烷基苯(1-phenyldodecane)和二苯基丙烷對加氫裂化、熱裂化和加氫熱裂化反應進行比較,采用色譜-質譜聯用對反應產物進行了表征。2003.5.


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