Flue gas desulfurization studies using absorbent prepared from coal fly ash

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Date
2004-09
Authors
Lee, Keat Teong
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Abstract
Flue gas desulfurization (FOD) technology utilizing absorbent synthesized from coal fly ash, calcium oxide (CaO) and calcium sulfate (CaS04) was studied. It was found that the absorbent surface area and total pore volume were the only absorbent properties that have significant influence on the desulfurization capacity of the absorbent. Apart from that, it was found that the total pore volume of the absorbent was linearly correlated to the surface area of the absorbent. The comparison between the absorbent preparation method (water and steam hydration) showed that water hydration method was more favorable in producing absorbent with higher surface area. A modeling-optimization approach using neural network-genetic algorithm was used to optimize the absorbent preparation variables to obtain absorbent with the highest surface area. The results obtained indicated that a maximum surface area of 62.2 m2/g could be obtained using Sg of CaO, 13.lg of coal fly ash and S.Sg of CaS04 at a hydration period of 10 hr. The absorbent prepared under these conditions was coded as the reference absorbent. The desulfurization capacity of the reference absorbent was found to easily outperform its base components. The reference absorbent exhibited 100% removal of sulfur dioxide (S02) for 30 min. X-ray Diffraction showed that calcium aluminum silicate hydrated compounds were the reactive species in the absorbent that reacted/absorbed S02 and calcium sulfite/sulfate were the products of the desulfurization reaction. The effect of various operating conditions such as feed concentration of S02 (SOO to 2000 ppm), feed concentration of NO (0 to 750 ppm), reaction temperature (60 to 300°C), relative humidity (0 to 70%), absorbent particle size (200 to 600 ~m) and space velocity (3,500 to 11,300 hr-I) on the desulfurization activity of the absorbent were reported. Smaller absorbent particle size and lower feed concentration of S02 were found to increase the desulfurization capacity of the absorbent. Although higher reaction temperature favored higher desulfurization capacity, but an increase of reaction temperature beyond 200°C gave no advantage. Contradictory, the relative humidity of the feed gas must be above 40% before it could give a positive effect on the desulfurization capacity. On the other hand, the presence of oxygen (02) and nitrogen oxide (NO) in the feed gas was found to be necessary to produce calcium sulfate (CaS04) instead of calcium sulfite (CaS03) as the final product of the desulfurization reaction. The kinetics of the desulfurization process was studied using thermogravimetric analysis. The desulfurization reaction was characterized by a substantial decrease in the rate of reaction at the initial period of reaction time. A one step global reaction model based on almost second order (n=2.2) reaction was found to fit the kinetic data. The activation energy and frequency factor for the desulfurization reaction were found to be 22.9 kJ/mol and 64.4 min-I respectively. A mathematical model based on the material balance for the gaseous and solid phase using partial differential equations to describe the absorption of S02 from a moving gas stream to the absorbent-bed of changing composition was proposed to represent the desulfurization reaction. The rate expression employed in the model was based on the one step global reaction rate equation. The kinetic parameters of the mathematical model were obtained by fitting the model to a series of experimental desulfurization reaction carried out under isothermal conditions at various operating parameters. The partial differential equations were solved using finite difference method. The model was found to give a very good description of the experimental data with error less than 10%.
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The total pore volume of the absorbent was linearly correlated , to the surface area of the absorbent
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