Application of mesoporous carbon, carbon nanohorns and M-SBA-15 (M=Zr and Ti) as support to Ni-Mo hydrotreating catalysts

近年来，由于越来越严格的环境法规，以及对重质原油砂岩衍生沥青的依赖日益增加，石油行业面临着巨大的挑战。加拿大辛克鲁德有限公司目前每天从油砂中生产25万桶合成原油。重柴油是合成原油的主要成分，它含有较高的硫(4wt%)和氮(0.4wt%)，需要脱除这些硫和氮才能满足下游炼油工艺的要求。用上述加氢催化剂脱除油砂油中的硫虽然相对容易，但脱氮却比较困难。众所周知，Ni-Mo加氢精制催化剂的催化性能在一定程度上取决于所使用的载体。近年来，将孔径扩展到介孔区域的新型分子筛的合成引起了人们越来越大的兴趣。得到的介孔分子筛具有不同的结构和孔径，可以在很宽的范围内(1.6-30 nm)控制。这些新型分子筛为受沸石微孔(通常小于1 nm)限制的大物种的择形传感、吸附和催化提供了巨大的潜力。本研究旨在开发高比表面积、宽孔M-SBA-15(M=Ti、Zr)、介孔碳和碳纳米角(CNHs)担载的高活性Ni-Mo硫化物催化剂，用于阿萨巴斯卡沥青衍生重质柴油(HGO)的加氢脱氮。较高的比表面积、多种孔径的可获得性、不同的表面官能团、易于通过燃烧载体回收金属、降低结焦倾向和抗氮中毒能力有望提高Ni-Mo催化剂的活性。将这些载体用于镍钼加氢精制催化剂，将有利于重质原油大分子中N原子和S原子的脱除。这将帮助参与的行业加拿大辛克鲁德有限公司提高汽油质量，满足下游精炼工艺的要求。这项研究还使加拿大受益于其丰富的石油资源的有效利用。

In recent years, petroleum industries are facing tremendous challenges due to more stringent environmental regulations coupled with increasing reliance on heavy crude oil sands derived bitumen. Syncrude Canada Ltd. currently produces 250,000 bbl/day of synthetic crude oil from the oil sand. The heavy gas oil, which is a major component of this synthetic crude oil contains higher amounts of sulfur ( 4 wt%) and nitrogen ( 0.4 wt. %), which need to be removed to meet specifications of downstream refining processes. Although the removal of sulfur is relatively easy, it is difficult to remove nitrogen from oil sands derived oils with above hydroteating catalyst. It is well known that the catalytic performance of Ni-Mo hydrotreating catalyst depends on the support used to a certain extent, since. Recently there have been growing interests in the synthesis of new molecular sieves extending the pore diameter to the mesoporous region. The mesoporous molecular sieves are obtained with various structures and pore diameters that can be controlled over a wide range (1.6-30nm). These new molecular sieves offer great potential for the shape-selective sensing, adsorption, and catalysis of large species that were limited by the micropores (typically less than 1nm) of zeolites. The present research proposal aims at the development of highly active Ni-Mo sulfide catalysts supported on high surface area, wide pore M-SBA-15 (M=Ti,Zr), mesoporous carbon and Carbon Nano Horns (CNHs) for hydrodenitrogenation (HDN) of Athabasca bitumen derived heavy gas oil (HGO). The high surface area, availability of a large variety of pore sizes, variable surface functional groups, easy metal recovery by the burning of the support, reduced coking propensity, and resistance to nitrogen poisoning are expected to increase the activity of the Ni-Mo catalysts. The use of these supports for NiMo hydrotreating catalyst will facilitate the removal of N and S atoms from the bulky molecules of heavy crude oil. This will help the participating industry, Syncrude Canada Ltd. to improve the quality of gas oil, which will meet specifications of downstream refining processes. This research also benefits Canada by efficient utilization of its vast oil resources.