Process of preparing chloride-free KNS compound fertilizers from phosphogypsum waste using a quaternary phase diagram

Abstract

Phosphogypsum (PG), commonly known as calcium sulfate, is a waste by-product generated during the production of phosphoric acid by the wet phosphoric acid process (WPA). It is well known that every year the phosphate industries produce a large quantity of PG around the world (i.e., Currently, global production of this waste is estimated at 300 Mt/ year), but the valorization processes of this waste are limited and low valuable. In this study, we investigated the recycling of PG by-product, which can be considered very promising sources of sulfate ions (SO42-) for the manufacturing of chloride-free KNS compound fertilizer based on potassium-ammonium sulfate ([K1−x(NH4)x]2SO4). The primary objective of this study was to develop a methodology for [K1−x(NH4)x]2SO4 synthesis and its separation process using the quaternary phase diagram K+, NH4+ / Cl-, SO42- - H2O at 25 °C. The experiment results show that it is possible to recover relatively pure (NH4)2SO4 from PG to re‐synthesize in presence of KCl the [K1−x(NH4)x]2SO4 phase, whose high quality and purity were confirmed by the combined use of several analytical and characterization techniques such as X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), and gamma spectrometry analysis. The thermal decomposition was supplemented by Thermo-Gravimetric Analysis (TGA) coupled with Differential Thermal Analysis (DTA). The main findings of this study may assist in developing methods for valorizing PG waste by converting it into valuable fertilizer products, which are particularly suitable for cultivating chloride-sensitive crops. Thus, total or partial substitution of non-renewable resources by PG not only helps to solve the environmental pollution caused by this waste, but also reduces production costs and improves farm economics.