Preparation of α-CaSO4·½H2O with tunable morphology from flue gas desulphurization gypsum using malic acid as modifier: A theoretical and experimental study

Abstract

Huge amount of flue gas desulphurization (FGD) gypsum not only occupies the farmland but also causes severe pollution to the surrounding environment. The most effective way to achieve a high-value utilization of FGD gypsum is to prepare short columnar α-calcium sulfate hemihydrate (α-HH) since short columnar crystals show better mechanical strength than needle-like ones. Here, malic acid, a prolific, inexpensive and environment-friendly modifier was explored for the first time to effectively tune the crystal morphology of α-HH prepared from FGD gypsum in glycerol-water-NaCl solutions. When the concentration of malic acid reached 18.54 × 10−4 mol/kg, α-HH crystals with an average aspect (length-to-diameter) ratio of 1.9 (compared to 29.4 in the absence of malic acid) were prepared. The selective complexation of malic acid with Ca active sites on different α-HH crystal planes played a dominant role in the α-HH crystal morphology transformation, which was then explained by the surface broken bonds theory for the first time. The broken bond number per active Ca atom (Nbper Ca) and broken bond density of Ca atoms (DbCa) on the (2 0 4) end plane were larger than those on the (0 2 0) or (2 0 0) side planes. Therefore, the (2 0 4) end plane was more reactive with organics, resulting in the preferential adsorption of malic acid on the end planes, which reduced the specific surface energy of (2 0 4) and led to an increased exposure of this plane and a decreased exposure of (0 2 0) or (2 0 0) side planes in the final α-HH crystals. Consequently, using malic acid as modifier, the α-HH crystal gradually transformed from a needle-like shape to a short columnar one. This work provided important insights into and perspectives for the selection of crystal modifiers and explanation of the mechanism during the preparation of calcium-containing crystals with controllable morphology.