Hydration products of FBC wastes as SO2 sorbents: comparison between ettringite and calcium hydroxide

Fluidized bed combustion (FBC) enables the in situ capture of SO₂, but generates large amounts of wastes whose composition and physico-chemical properties make both landfilling and reuse in traditional fields of application (e.g., cement and concrete industries) problematic. Reactivation by water hydration of the desulphurizing ability of these residues is considered a viable mean for their recycling: besides Ca(OH)₂, this process can generate other hydration products, such as ettringite. This paper is devoted to a comparison between the behaviour of Ca(OH)₂ and ettringite as SO₂ sorbents. To this end, synthetic preparations (in the particle size range 0.4–0.6 mm) of the two materials were dehydrated and then sulphated in a lab-scale fluidized bed reactor. Sulphation tests were carried out at 850 °C by fluidizing the bed with an SO₂–N₂–O₂ mixture (1800 ppm SO₂) at 0.8 m/s. Calcium conversion degree and fines elutriation rate were evaluated as a function of sulphation time. The propensity of the sorbents to undergo fragmentation was also estimated by particle sizing of in-bed exhausted sorbent particles, with the aid of laser granulometry. Mercury intrusion porosimetry of samples was directed to the assessment of the influence of sorbent dehydration and subsequent sulphation on pore size distribution and porosimetric texture. X-ray diffraction and differential thermal analysis on the synthetic sorbents complemented the characterization. Results showed that dehydration/thermal decomposition brought about a significant increase of the overall porosity for both sorbents, more extensive than it is commonly observed with calcined commercial limestones. Upon sulphation, the two sorbents showed satisfactory degrees of calcium conversion, larger than those usually observed with limestones. Sulphation resulted into a decrease of particle voidage (that of the Ca(OH)₂-based sorbent was negligible after the process). Ettringite was more prone to attrition/fragmentation than calcium hydroxide. Results are discussed with a focus on differences between calcium hydroxide and ettringite and on key-parameters affecting the performance of the two materials as sorbents.