The preparation of α-hemihydrate phosphogypsum (α-HPG) is hindered by a lengthy reaction time due to using traditional electric heating. Microwave heating was proposed for the rapid synthesis of α-HPG in MgCl2 solution. The effects of MgCl2 concentration on the heating rate of solution and conversion rate of α-HPG were investigated; the morphology of α-HPG was regulated by citric acid, and the adsorption mechanism of citric acid on the α-HPG surface was clarified. The results show that α-HPG was successfully synthesized in a MgCl2 solution by microwave heating. Increasing the MgCl2 concentration can improve both the dielectric constant and conductivity of the solution, which is advantageous for the solution to absorb more microwave energy. Consequently, the conversion rate of phosphogypsum (PG) into α-HPG was improved at higher MgCl2 concentrations. In 2.62 mol/L MgCl2 solution, the heating time is shortened to 7 min from room temperature to 95 °C, and PG was converted to α-HPG within 60 min. The morphology of α-HPG could be controlled by chemical adsorption of citric acid onto its terminal surface. In a solution containing 2.62 mol/L MgCl2 and 1.63 × 10-2 mol/L citric acid, PG was completely transformed into α-HPG at 90 min by microwave heating, whereas the reaction time was delayed to 180 min using electric heating. Accordingly, microwave heating is a highly efficient and energy-saving method for the preparation of α-HPG.
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