Inhibition of nitrogen compounds on the hydrodesulfurization of substituted dibenzothiophenes in light cycle oil |
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| Affiliation: | 1. Beijing Key Laboratory of Membrane Science and Technology & College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, PR China;2. Petrochemicals Research Chair, College of Science, King Saud University, Riyadh 11451, Saudi Arabia;3. Petrochemical Research Institute, Petrochina Company Limited, Beijing 100195, PR China;1. Department of Chemical Engineering, Widya Mandala Surabaya Catholic University, Kalijudan 37, Surabaya 60114, Indonesia;2. Department of Chemical Engineering, National Taiwan University of Science and Technology No. 43, Section 4, Keelung Rd, Da''an District, Taipei City 10607, Taiwan;1. Institute for Energy Research, School of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, PR China;2. Department of Chemistry, University of Tennessee Knoxville, TN 37996, United States;3. Chemical Science Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, United States;4. College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, PR China;1. Laboratoire des Matériaux Polymères Multiphasiques (LMPMP), Université Ferhat ABBAS, Département de Génie des Procédés, Sétif-1, 19000 Sétif, Algeria;2. Khalifa University of Science and Technology, Center for Membrane and Advanced Water Technology (CMAT), Chemical Engineering Department, P.O. Box 54224, Abu Dhabi, United Arab Emirates |
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| Abstract: | The influence of nitrogen compounds on the hydrodesulfurization (HDS) activities of a series of substituted dibenzothiophenes in light cycle oil (LCO) was studied over a NiMo/Al2O3 commercial catalyst. Three types of light cycle oil with nitrogen compounds of different concentrations and chemical natures were used as feed—an original fluid catalytic cracking light cycle oil (LCO), LCO with most of its basic nitrogen removed, and an ultra-low nitrogen LCO. Experiments were conducted in a fixed-bed microreactor at a total pressure of 70 atm, temperatures between 330 and 400 °C, and liquid hourly space velocities (LHSV) in the range of 1.0 to 3.5 h−1. The inhibition effects of nitrogen compounds on the HDS reactivity of the three sulfur groups—total sulfur, hard sulfur, easy sulfur—and 14 specific mono-, di- and tri-alkyl substituted dibenzothiophenes were investigated. The results showed that the HDS rate significantly increased using ultra-low nitrogen LCO. Pseudo first-order rate constants were estimated for the 14 mono-, di- and tri-alkyl substituted dibenzothiophenes. The HDS rates could be classified into three groups based on the position of the substituents. It was found that 4 and 6 substituted dibenzothiophenes had the lowest HDS rates. The HDS rate of the 14 substituted dibenzothiophenes were all increased when the ultra-low nitrogen feed was used. The improvement was greater for 4 and 6 substituted dibenzothiophenes than for those with one of the substituents at either the 4 or 6 positions. This finding indicates that the hydrogenation route is more strongly suppressed than hydrogenolysis route by nitrogen compounds since the hydrogenation route is believed to be the predominant reaction pathway for 4 and 6 alkyl-substituted dibenzothiophenes. |
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