- Title
- Engineering nanocatalysts using mixed metals for hydrodesulfurization of fuel oil
- Creator
- Majodina, Siphumelele
- Subject
- Port Elizabeth (South Africa)
- Subject
- Eastern Cape (South Africa)
- Subject
- South Africa
- Date Issued
- 2021-12
- Date
- 2021-12
- Type
- Master's theses
- Type
- text
- Identifier
- http://hdl.handle.net/10948/53861
- Identifier
- vital:46021
- Description
- Crude oil is a complex blend containing thousands of hydrocarbons, non-hydrocarbon compounds and heavy metals. These hydrocarbons are mixed with variable quantities of sulfur-, nitrogen-, and oxygen-containing compounds. The combustion of fuel containing organosulfur compounds results in the emission of sulfur oxides (SOx) into the atmosphere. These toxic gases escape into the atmosphere resulting in air pollution, which is a large contributor to global warming. Air pollution also causes pulmonary diseases, allergies and may even lead to human death. It can also cause harm to other living organisms such as animals and food crops. Thus, mandating the reduction of sulfur in organosulfur compounds in fuel to <10 ppmS by the environmental protection agency. Several studies have been conducted to remove sulfur from fuels, most of which have focused on removing refractory sulfur compounds due to the difficulty in removing sulfur in these compounds. However, the currently employed hydrodesulfurization (HDS) catalysts suffer in producing fuels complying with the future standards of fuels quality. Generally, HDS catalysts are made up of metallic components, Co (Ni) and Mo (W), on porous supports, the catalytic activity of these catalysts strongly depends on the amount of NiWS (CoMoS) phases in it and to the extent in which these phases are exposed on the catalyst support surfaces and this is engineered using chelating agents and size of catalysts. To this end, nanosized materials (nanocatalysts) are considered most suitable, as reported active phases of HDS catalysts are exposed, hence improving the hydrodesulfurization of sulfur-containing compounds in fuels. Nanocatalysts results in nanoparticles and when impregnated on a support will results in high surface area, and enhances electronic property, which increases the activity of the catalyst allowing the most refractory sulfur to be removed. The addition of chelating agents such as EDTA, acetic acid, and citric acid further improves the activity of the catalysts by producing more active phases on the catalyst. In this research project, nanocatalysts will be synthesised using mixed metals with and without chelating agents and tested for HDS activity and selectivity towards sulfur using refractory organosulfur compounds in fuels under industrial HDS conditions. This work was divided into two sections, and this dissertation summarizes the research outcomes of each phase. The first section examines the effect of chelating ligands, namely, ethylenediaminetetraacetic acid (EDTA), citric acid (CA), and acetic acid (AA), on CoMo HDS activity and the sulfidation mechanism. In this study, chelating ligands seem to have a beneficial effect on HDS activity. Detailed mechanistic aspects of interactions between chelating ligands and metallic species (Co-chelating ligands) were also studied. Characterization by SC-XRD revealed that the presence of the chelating ligand result in the formation of complex with cobalt, and the effect of this complex was shown by TG-DSC analysis. This showed that the presence of chelating ligand leads a to delay of cobalt sulfidation as the complex decomposes at higher temperatures, which was the main cause of improving HDS activity. It was also shown that chelating ligands play a role in dispersion of metal oxides and sulfided metal oxides (TEM and XPS). XPS results showed low MoS2 phase for CoMo/Al2O3 (45%), while CoMo-EDTA/Al2O3 (63%) catalyst resulted in high MoS2 phases. From all the catalysts, CoMo-CA/Al2O3 (98%) gave the highest catalytic activity, and the increase in activity could be attributed to the formation of octahedral molybdenum oxides as they are easily reducible during sulfidation and result in more dispersed active phases and weak metal-support interaction. The second section examines the effect of a promoter (Rh) and different chelating ligands (EDTA, AA, and CA) on the catalyst RhMo supported with alumina. In this phase, rhodium was used as promoter, the following trend for catalytic activity was observed: RhMo/Al2O3 (88%) > RhMo-AA/Al2O3 (73%) > RhMo-CA/Al2O3 (72%) > RhMo-EDTA/Al2O3 (68%). This could be that the addition of chelating ligand complexed both metallic species retarding sulfidation of both metals, hence lowering the HDS activity. Studies show that it is possible for the citric acid to complex with both promoter and an active metal (Mo), and this might result in the formation of molybdenum dimers, trimers and tetramers which are difficult to sulfide. XPS analysis showed that unchelated catalyst have more MoS2 phases of 63%, hence higher dispersion than the chelated catalyst, this could be the reason for high activity in RhMo/Al2O3 (88%) catalyst.
- Description
- Thesis (MSc) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Format
- computer
- Format
- online resource
- Format
- application/pdf
- Format
- 1 online resource (xvi, 154 pages)
- Format
- Publisher
- Nelson Mandela University
- Publisher
- Faculty of Science
- Language
- English
- Rights
- Nelson Mandela University
- Rights
- All Rights Reserved
- Rights
- Open Access
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| Thumbnail | File | Description | Size | Format | |||
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