Bello Suleiman Sabo, Wang Chao, Zhang Mengjuan, Han Zhennan, Shi Lei, Wang Kangjun, Zhong Ziyi, Su Fabing, Xu Guangwen
Key Laboratory of Chemical and Material Resources, Institute of Industrial Chemistry and Energy Technology, Shenyang University of Chemical Technology Shenyang 110142 China
State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences Beijing 100190 China.
RSC Adv. 2020 Oct 8;10(61):37287-37298. doi: 10.1039/d0ra07419e. eCollection 2020 Oct 7.
Hydrotreatment is an effective upgrading technology for removing contaminants and saturating double bonds. Still, few studies have reported the hydro-upgrading of shale oil, with unusually high sulfur (13200 ppm) content, using the CoMo/AlO catalyst. Here we report an extensive study on the upgrading of shale oil by hydrotreatment in a stirred batch autoclave reactor (500 ml) for sulfur removal and viscosity reduction. From a preliminary optimization of the reaction factors, the best-operating conditions were 400 °C, an initial H-pressure of 5 MPa, and an agitation rate of 800 rpm, a catalyst-to-oil ratio of 0.1, and a reaction time of 1 h. We could achieve a sulfur removal efficiency of 87.1% and 88.2% viscosity reduction under the optimal conditions. After that, the spent CoMo/AlO was repeatedly used for subsequent upgrading tests without any form of pre-treatment. The results showed an increase in the sulfur removal efficiency with an increase in the number of catalyst runs. Ultimately, 99.5-99.9% sulfur removal from the shale oil was achieved by recycling the spent material. Both the fresh and the spent CoMo/AlO were characterized and analyzed to ascertain their transformation levels by XRD, TEM, TG, XPS, TPD and N adsorption analysis. The increasing HDS efficiency is attributed to the continuing rise in the sulfidation degree of the catalyst in the sulfur-rich shale oil. The light fraction component in the liquid products (IBP-180 °C) was 30-37 vol% higher than in the fresh shale oil. The product oil can meet the sulfur content requirement of the national standard marine fuel (GB17411-2015/XG1-2018) of China.
加氢处理是一种用于去除污染物和饱和双键的有效提质技术。然而，很少有研究报道使用CoMo/AlO催化剂对硫含量异常高（13200 ppm）的页岩油进行加氢提质。在此，我们报告了一项在500毫升搅拌间歇式高压釜反应器中通过加氢处理对页岩油进行提质以脱硫和降低粘度的广泛研究。通过对反应因素的初步优化，最佳操作条件为400℃、初始氢气压力5 MPa、搅拌速率800 rpm、催化剂与油的比例为0.1以及反应时间1小时。在最佳条件下，我们可以实现87.1%的脱硫效率和88.2%的粘度降低。之后，将用过的CoMo/AlO重复用于后续提质试验，无需任何形式的预处理。结果表明，随着催化剂运行次数的增加，脱硫效率提高。最终，通过循环使用废催化剂，实现了页岩油99.5 - 99.9%的脱硫率。对新鲜和用过的CoMo/AlO进行了表征和分析，通过XRD、TEM、TG、XPS、TPD和N吸附分析来确定它们的转化水平。加氢脱硫效率的提高归因于富硫页岩油中催化剂硫化程度的持续上升。液体产物（初馏点 - 180℃）中的轻质馏分成分比新鲜页岩油高30 - 37体积%。产物油能够满足中国国家标准船用燃料（GB17411 - 2015/XG1 - 2018）的硫含量要求。
