The adsorption and oxidation of SO2 on alumina and
sodium-impregnated alumina has been examined using
thermogravimetric analysis and diffuse reflectance infrared Fourier
transform spectroscopy. Sulfur dioxide
chemisorbs initially at basic sites to form an adsorbed sulfite, which
is quantitatively converted to sulfate on
oxidation. It has been observed that at low coverages, ∼2.6
μmol/m2, sodium acts as a promoter for the
formation of an adsorbed sulfite and sulfate which have structures
similar to those of aluminum sulfite and
sulfate, respectively. At higher sodium loadings, a second type of
adsorbed SO2 is formed, similar to sodium
sulfite and sulfate. The species with the aluminum sulfate
structure appears to be more easily decomposed
than does the sodium sulfate species and accounts for the regenerable
adsorption capacity. Formation of the
sodium sulfate species appears to account for the loss of adsorption
capacity as the number of adsorption/regeneration cycles increases. Oxidation of the sulfite form to the
sulfate form can occur in the absence of
added oxygen, but it is an activated process and begins to occur in
measurable amounts at temperatures
between 150 and 300 °C. Partitioning of adsorbed SO2
between aluminum and sodium forms is not a function
of temperature and depends on only sodium loading.