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Kinetics of gasification and sulphur capture of oil sand cokes Nguyen, Quoi The


Kinetics of steam gasification of both delayed and fluid cokes, byproducts from thermal cracking processes of Athabasca bitumen, have been studied in laboratory-size stirred and fixed bed reactors. The hydrogen sulphide in the product gas was captured in-situ using calcined dolomite and limestones as acceptors. Experiments were carried out at atmospheric pressure and at temperatures between 800°C and 930°C. The coke particle size ranged from 0.1 to 3.5 mm, and the steam partial pressure was varied from 15.15 to 60.6 kPa. The carbon and sulphur conversions were computed from the knowledge of gas compositions and flowrates and the gasification kinetics of both species established. The effects of sorbent type, particle size, calcination conditions, and Ca/S molar ratios on the extent of sulphur capture during gasification were examined in separate series of experiments. Scanning electron microscopy, surface area analysis, and mercury porosimetry were employed to relate physical structure changes in the solids to experimental kinetic data. The rate of gasification for the delayed coke was generally higher than that for the fluid coke, and both cokes were almost unreactive to steam gasification at temperatures below 800°C. Increased reaction temperatures or reduced particle sizes increased both carbon as well as sulphur conversion. The carbon conversion rates were found to go through maxima as the time of reaction and extent of conversion increased. As the reaction proceeded the surface area of the coke increased to a maximum of about five times its initial value and thenfell off sharply. The extent of carbon conversion alone dictated the specific surface area irrespective of temperature, particle size and steam partial pressure. Both calcined dolomite and calcined limestone were found to be effective in removing sulphur from the product gas. Sorbents possessing a larger specific area or smaller grain size had higher capacity to accept sulphur. At a Ca/S molar ratio of 2.0, the overall sulphur removal was approximately 90% for the first 3 hrs and the H₂S concentration in the produced gas was reduced to about 200 ppm from nearly 1250 ppm. The rate of sorbent conversion from CaO to CaS decreased monotonically with time. Three available kinetic models for gasification - the Random Capillary Model, the Random Pore Model and the Modified Volumetric Model, were tested with the experimental gasification data. Although reasonable fits were obtained for Xc-t results, the sharp drop in rate at high conversion could not be adequately modelled. Rate constants were established for the initial stage of reaction only. The Grain model and Continuous reaction models were tested with the experimental sulphidation results. The sulphidation process was controlled by chemical reaction at low sorbent conversion, and subsequently by diffusion through the product layer at higher conversions. The reaction rate constant and the effective diffusivity were accordingly established as functions of temperature. Values compared favourably with results of sulphidation kinetics done without simultaneous gasification reported in the literature. The results suggest that the gasification process and the sulphur capture process, which occur together in gasifiers with sorbent injection, can be treated independently. Indexing terms: Gasification, Carbon Conversion, Sulphur Conversion, Sulphur Removal, Calcine, Limestone, Dolomite, Hydrogen Sulphide, Sulphidation.

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