Phosphogypsum (PG), a byproduct during the phosphoric acid production process, also known as the wet process, contains complex and diverse impurities, resulting in low utilization and considerable accumulation. This leads to a massive waste of land resources and a series of environmental pollution problems. Given the current urgent ecological and environmental situation, developing impurity removal processes with low energy consumption and high efficiency, exploring valuable resource recovery, preparing high value-added PG products, and broadening the comprehensive utilization ways of PG are significant strategies to promote the sustainable consumption of PG and sustainable development of the phosphorus chemical industry. This review comprehensively summarizes the advantages and disadvantages of existing PG impurity removal and utilization technologies and probes into the future development direction, which provides references and ideas for subsequent PG research.

The increasing demand for rare earth elements (REEs), especially from new and innovative technology, has strained their supply, which makes the exploration of new REE sources necessary, for example, the recovery of REEs from phsophogypsum (PG). PG is a byproduct during the wet production of phosphoric acid, which is an attractive secondary resource for REEs due to a large amount of REEs locked in them. In most cases, REEs contained in PG are mainly encapsulated in the gypsum crystal, leading to a low leaching efficiency. Therefore, it is particularly important to use various methods to enhance the leaching of REEs from PG. In this review, we summarized and classified various enhanced leaching methods for the recovery of REEs from PG, and the advantages and disadvantages of different methods were compared. A joint method of recrystallization and RIL may be a promising enhanced leaching approach for the recovery of REEs from PG. Recrystallization could achieve both the complete REE release and simultaneous preparation of industrial materials with high value added, such as high-strength α-hemihydrate gypsum by phase transformation of PG, and the RIL technology could adsorb the releasing REEs and realize their efficient extraction. Such a combination appears to show significant advantages because of high REE recovery, as well as high value-added product preparation at low cost.

The characterization and leaching mechanism of REEs from phosphogypsum (PG) in HCl was studied in-depth. REEs contained in the PG were 208 ppm, of which Y, La, Ce, and Nd were the four most abundant elements. The modes of occurrence of rare earth elements (REEs) in the PG were quantified using the sequential chemical extraction (SCE) method. Among the five REE occurrence species, the metal oxide form accounted for the largest proportion, followed by the residual, organic matter, and ion-exchangeable fractions, and REEs bound to carbonates were the least. From the comparison of the distributions of REEs and calcium in different occurrence states, it can be determined that REEs contained in the PG were mainly present in the residue state (existed in the gypsum lattice) and the metal oxide state (easily leached). The leaching results show that the suitable leaching conditions were acid concentration of 1.65 mol/L, S/L ratio of 1/10, and reaction temperature of 60 °C. At the condition, the maximum leaching efficiency for ∑REE was 65.6%, of which the yttrium leaching rate was the highest and reached 73.8%. Importantly, A new kinetic equation based on the cylindrical shrinking core model (SCM) was deduced and could well describe REE leaching process from PG. The apparent activation energy for ∑REE leaching was determined to be 20.65 kJ·mol⁻¹.

In order to reveal the influence of ammonium salts on the rare earth leaching process of weathered crust elution-deposited rare earth ores, ammonium acetate, ammonium chloride, and ammonium sulfate were used as leaching agents. The effects of the leaching agent on the rare earth leaching efficiency and the expansion, dissolution, and transformation behavior of clay minerals in the rare earth leaching process were studied. The results showed that rare earth leaching efficiency followed the order ammonium acetate > ammonium chloride > ammonium sulfate, with values of 90.60%, 85.96%, and 84.12%, respectively. The swelling ratio of clay mineral followed the order ammonium acetate < ammonium chloride < ammonium sulfate; the clay mineral swelling ratio was 2.09% when ammonium acetate was the leaching agent. Thermogravimetric analysis showed that the interlayer water content was the lowest when ammonium acetate was used as the leaching agent. Under the conditions of different leaching agents, the clay mineral contents changed from illite and halloysite to smectite and kaolinite. When ammonium acetate was used as the leaching agent, the relative conversion of illite was 1.49%, and that of smectite was only 0.17%. SEM analysis showed that the clay minerals expanded and dissolved obviously when ammonium chloride and ammonium sulfate were used as the leaching agents. Meanwhile, the clay mineral layered structure was relatively complete when ammonium acetate was used as the leaching agent. Therefore, when ammonium acetate was used as the leaching agent, it had the least effect on the swelling, dissolution, and transformation of clay minerals. This can provide a theoretical basis for the safe production of weathered crust elution-deposited rare earth ore, and for the screening of green and efficient leaching agents.