The performance of a novel synthetic Ca-based solid sorbent suitable for the removal of CO2 and SO2 from flue gases in a fluidised bed

Abstract

The extent and mechanism of the sulphation and carbonation of a limestone, dolomite and chalk, have been compared with a novel, synthetic sorbent (85 wt% CaO and 15 wt% Ca12Al14O33), from experiments in a small, electrically-heated fluidised bed. The sorbent particles were either (i) untreated, but then sieved into two particle sizes and reacted with SO 2 of two different concentrations, or (ii) cycled 20 times between (a) carbonation in 14 vol.% CO2 in N2, and (b) calcination, in pure N2, at 750°C. The uptake of SO2 by untreated limestone and dolomite was generally low (< 0.2 g SO2/gsorbent) and dependent on particle size, confirming previous results. In comparison with limestone and dolomite, the untreated chalk and the synthetic sorbent were found to be substantially more reactive with SO2; their final uptake was significantly higher (> 0.5 g SO2/gsorbent) and essentially independent of the particle size. Hg-intrusion porosimetry, performed on calcined sorbents, revealed that the volume inside the pores of limestone and dolomite was entirely in small pores (< 200 nm dia.), confirmed by EDAX analysis. The small pores were easily plugged, hindering the diffusion of SO2 through the particle. On the other hand, calcined chalk and fresh synthetic sorbent possessed large volumes in wide pores (> 200 nm dia.); these bigger pores were not blocked by newly formed CaSO4. This allowed sulphation to proceed uniformly throughout the particle. It was also found that the uptake of SO2 by limestone, dolomite and chalk was substantially lower when the particles had been subjected to cycles of calcination and carbonation in CO2 prior to sulphation; this was attributed to a loss of volume inside the small pores during carbonation and calcination, confirmed by Hg-intrusion porosimetry. The uptake of SO2 by the synthetic sorbent, on the other hand, was much closer to that achieved when it was used untreated, because large pores remained accessible after cycling.