This thesis evaluates the behavior of sulfur oxides in pulverized fuel (PF) fired air and oxy-fuel systems. Sulfur oxides are responsible for certain operational problems and considerable gas cleaning requirements in air as well as oxy-fuel firing. A better understanding of the related issues will allow for a technical and economical optimization of the oxy-fuel combustion technology. A range of experimental investigations studying the stability and retention of sulfur oxides in ashes and deposits, acid gas (SO2, SO3, and HCl) control in air and oxy-fuel combustion by dry sorbent injection, and SO3 formation were conducted. The experimental work is in parts supported by theoretical considerations and thermodynamic equilibrium simulation.
Studies for different coals and lignites showed that in practically relevant oxy-fuel configurations the exclusion of airborne N2 from combustion leads to an increase of the SO2 concentrations in oxy-fuel, compared to air firing, by a factor of about 3.4 to 4.2, referring to dry, and of about 2.9 to 3.5, when referring to wet flue gas conditions. The increased SO2 levels in oxy-fuel combustion are responsible for an increased stability of sulfates in oxy-fuel power boiler systems so that for example the decomposition temperature CaSO4 rises by about 50 to 80°C, depending on flue gas atmospheres. The enhanced stability of sulfates in deposits at high temperatures when operating with increased SO2 levels was experimentally demonstrated. Compared to air firing, a considerable increase of the sulfur retention in the ash by 10 to 12 percentage points has been observed for oxy-fuel recycle combustion of Lusatian lignites. This leads to lower SO2 emissions and higher SO3 levels in process ashes and deposits. The results indicate that for fuels, such as the used lignites, the temperature level at which fouling by sulfatic deposits is problematic may be shifted to higher temperatures in oxy-fuel combustion and that the sintering of deposits by sulfation may be more pronounced. In contrast, in air and oxy-fuel combustion experiments with a hard coal with a low sulfur retention potential differences in the SO3 contents and degrees of sulfation of ashes and deposits were small. Besides higher SO3 contents and sulfation degrees, no other significant changes between the deposit samples from air and oxy-fuel combustion were identified. Experiments on dry sorbent injection in air and oxy-fuel mode showed that an increase of the average flue gas residence time in the furnace by flue gas recirculation and, to a lesser extent, the higher sulfate stability enhance the desulfurization efficiency in oxy-fuel recycle combustion considerably. SO2 capture efficiencies in oxy-fuel recycle combustion of 50% to more than 80% at moderate molar sulfur to calcium ratios between 1.7 and 2.9 were reached, when injecting CaCO3 and Ca(OH)2 together with the fuel or directly to the furnace. Under comparable injection conditions, the oxy-fuel performance was by as much as 29 percentage points higher than in air firing. Also an efficient SO3 and HCl control by DSI could be demonstrated. Experiments on formation of SO3 show that higher SO2 levels in oxy-fuel firing are the most important parameter responsible for the observed increase of the SO3 concentrations.