Physical activation of oil-sands fluid coke, a dense carbonaceous material, using sulfur dioxide (SO2) was investigated as a means of utilizing a plentiful and inexpensive waste for elemental mercury (Hg) removal. A new model was developed to elucidate physical activation of dense carbonaceous materials. Experiments and model simulations revealed that, during activation with SO2, a sulfur-rich porous layer is formed around the periphery of the coke particles; this porous layer reaches a maximum thickness as a result of diffusion limitations; the maximum porous layer thickness is controlled by activation conditions and determines the maximum achievable specific surface area (SSA). Pre-oxidation in air prior to activation, acid washing after activation and smaller coke particle size all result in higher SSA. The highest SSA achieved was 530 m2/g, the highest yet found for oil-sands fluid coke with physical activation. If present, oxygen out-competed SO2 for carbon during activation. SO2 activation and porous layer formation did not occur until oxygen was depleted. Sulfur added to coke through SO2 activation is mainly in reduced forms which are more thermally stable than elemental sulfur in commercial sulfur-impregnated activated carbons (SIACs). TGA and elemental analyses revealed that only 17% of sulfur was removed at 800°C from SO2-activated coke under inert conditions, compared with 100% from a commercial SIAC.
The role of sulfuric acid (H2SO4) in vapor Hg capture by activated carbon (AC) was studied due to conflicting findings in the recent literature. In the absence of other oxidizing species, it was found that Hg could be oxidized by oxygen which enhanced vapor Hg adsorption by AC and Hg absorption in H2SO4 solution at room and elevated temperatures. At 200°C, AC treated with 20% H2SO4 reached a Hg loading of more than 500 mg/g, which is among the highest Hg capacities yet reported. When oxygen was not present, S6+ in H2SO4 was found to act as an oxidizer of Hg, thus enabling Hg uptake by H2SO4-treated AC at 200°C. Treating the AC with SO2 at 700°C improved the initial rate of Hg uptake, with and without subsequent H2SO4 treatment.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:OTU.1807/36293 |
| Date | 16 August 2013 |
| Creators | Morris, Eric Adde |
| Contributors | Jia, Charles Q. |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | en_US |
| Detected Language | English |
| Type | Thesis |
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