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Joseph A. DeBarr

Publications and source records attributed to Joseph A. DeBarr.

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Mechanism of SO2 removal by carbon

The reaction of SO 2 with carbon (C) in the presence of O 2 and H 2 O involves a series of reactions that leads to the formation of sulfuric acid as the final product. The rate-determining step in the overall process is the oxidation of SO 2 to SO 3 . Three SO 2 oxidation reactions are possible. Adsorbed SO 2 (C−SO 2 ) can react either with gas phase O 2 or with adsorbed oxygen (C−O complex) to form sulfur trioxide (SO 3 ), or gas phase SO 2 can react directly with the C−O complex. In optimizing the SO 2 removal capabilities of carbon, most studies only assume a given mechanism for SO 2 adsorption and conversion to H 2 SO 4 to be operable. The appropriate SO 2 oxidation step and role of the C−O complex in this mechanism remain to be determined. The ultimate goal of this study was to prepare activated char from Illinois coal with optimal properties for low-temperature (80−150°C) removal of sulfur dioxide from coal combustion flue gas. The SO 2 adsorption capacity of activated char was found to be inversely proportional to the amount of oxygen adsorbed on its surface. A temperature-programmed desorption technique was developed to titrate those sites responsible for adsorption of SO 2 and conversion to H 2 SO 4 . On the basis of these results, a mechanism for SO 2 removal by carbon was proposed. The derived rate expression showed SO 2 adsorption to be dependent only on the fundamental rate constant and concentration of carbon atoms designated as free sites. Recent studies indicate a similar relationship exists between the rate of carbon gasification (in CO 2 or H 2 O) and the number of reactive sites as determined by transient kinetics experiments. Utilizing the concept of active or free sites, it was possible to produce a char from Illinois coal having an SO 2 adsorption capacity surpassing that of a commercial catalytic activated carbon.

Energy and Fuels

Adsorption of SO 2 on bituminous coal char and activated carbon fiber

The SO 2 adsorption behaviors of activated carbons produced from Illinois coal and of commercially prepared activated carbon fibers (ACFs) were compared. There was no relation between surface area of coal-based carbons and SO 2 adsorption, whereas adsorption of SO 2 on the series of ACFs was inversely proportional to N 2 BET surface area. Higher surface area ACFs had wider pores and adsorbed less SO 2 ; thus, pore size distribution is thought to play a significant role in SO 2 adsorption for these materials. Oxidation with HNO 3 and/or H 2 SO 4 , followed by heat treatment at 700−925°C to remove carbon−oxygen complexes, resulted in increased SO 2 adsorption for both coal chars and ACFs. This behavior was explained by an increase in the available number of free sites, previously occupied by oxygen and now available for SO 2 adsorption. The use of nitrogen-containing functional groups on ACFs of proper pore size shows promise for further increasing SO 2 adsorption capacities. Knowledge of the relationship among the number of free sites, pore size, and surface chemistry on corresponding SO 2 adsorption should lead to the development of more efficient adsorbents prepared from either coal or ACFs.

Energy and Fuels