Bitumen-derived heavy gas oil contains large amounts of sulfur (~4.0 wt.%) and nitrogen (~0.4 wt.%), which need to be lowered before it becomes suitable as a feedstock for refineries. The most widely used upgrading process is hydrotreating, and the conventional catalyst used for hydrotreating is Ni or Co and Mo or W supported on γ-Al2O3. Additionally, environmentally driven regulations impose strict limits on sulfur and nitrogen levels in transportation fuels. Therefore, the main focus of this work was to enhance the activity of a NiMo supported catalyst through its modification and to improve its selectivity to removal of bulky sulfur- and nitrogen-containing compounds from heavy gas oil under industrial hydrotreating conditions. This work was divided into four phases, and this thesis summarizes the research outcomes of each phase.
The first phase examined the effects of chelating ligands, specifically, ethylenediaminetetraacetic acid (EDTA), on hydrotreating activity and the sulfidation mechanism. EDTA was seen to have a beneficial effect on hydrotreating activity. Detailed mechanistic aspects of interactions between support and EDTA, EDTA and metallic species, support and metal, support and active phase, and metallic species and metallic species at different reaction conditions, were also studied. Characterization by XANES revealed that the presence of a chelating agent delayed nickel sulfidation, which was the main cause of improvement in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities. It also showed that EDTA plays a role in redistribution of active phases during sulfidation and favors the formation of octahedral molybdenum oxides.
The second phase studied the effects of support modification and combinations of different supports and EDTA. In this phase, several mesoporous materials, including M-SBA-15 (M= Al, Ti and Zr), mesoporous mixed metal oxides (TiO2-Al2O3, ZrO2-Al2O3 andSnO2-Al2O3) and mesoporous metal oxides (ZrO2, Al2O3), were synthesized and used as support materials for a NiMo catalyst. NiMo/M-SBA-15 catalysts showed higher HDS and HDN activities and, the increase in activity is attributed to incorporation of heteroatoms in an SBA-15 matrix, which resulted in increase in metal support interaction, acidic strength and dispersion of active metals. The addition of EDTA to these catalysts helps in the formation of octahedral molybdenum oxide, which are easily reducible during sulfidation. This is evident from the XANES Mo LIII-edge study of the oxide catalysts. The increase in hydrodenitrogenation (HDN), hydrodesulfurization (HDS) and hydrodearomatization (HDA) activities as compared to that shown by the NiMo/γ-Al2O3 catalyst were also observed on addition of EDTA in large-pore, high-surface-area mesoporous zirconia supported NiMo catalysts. The incorporation of different metal oxides in alumina, as in the case of mixed metal oxides, resulted in a change in acidic strength and metal support interactions. It was observed with acridine-FTIR analysis that the catalysts with higher acidic strength tightly held acridine at high temperatures. This implies that catalysts with higher acidity are prone to inhibition by nitrogen-containing compounds present in feed, which will affect catalytic activity. The HDS and HDN activities for hydrotreating of heavy gas oil suggest that mesoporous alumina and titania-alumina supported catalysts perform better as compared to the conventional NiMo/γ-Al2O3 catalyst. Therefore, the effects of EDTA to Ni molar ratio (EDTA/Ni = 0 to 2) on the activities of the NiMo/MesoAl2O3 and NiMo/MesoTiO2-Al2O3 catalysts were studied, and EDTA was observed to have a negative impact on catalytic activity for these catalysts. This is attributed to a decrease in the active metal dispersion in these catalysts caused by the addition of EDTA. The catalysts NiMo/MesoAl2O3 and NiMo/MesoTiO2-Al2O3 without EDTA showed high active metal dispersion due to their high surface area and ordered structure.
The third phase studied the combined effects of phosphorus and EDTA on the hydrotreating activity of NiMo supported catalysts. The effects of method of phosphorus addition (sequential and co-impregnation method) were also studied. When phosphorus was added using a co-impregnation method, as in the catalyst NiMoP/MesoAl2O3(CI), an increase in HDN, HDA and HDS activities was observed. However, the catalysts containing both EDTA and phosphorus showed a decrease in HDS and HDN activities.
The fourth phase included a kinetic study using the Power Law and L-H models. The catalyst, NiMoP/mesoAl2O3(CI), was found to have higher HDN and HDS activities as compared to a conventional γ-Al2O3 supported catalyst containing phosphorus.
| Identifer | oai:union.ndltd.org:USASK/oai:ecommons.usask.ca:10388/ETD-2015-04-2019 |
| Date | 2015 April 1900 |
| Contributors | Dalai, Ajay K., Adjaye, John D. |
| Source Sets | University of Saskatchewan Library |
| Language | English |
| Detected Language | English |
| Type | text, thesis |
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