The leaching of rare earth elements (REEs) from secondary resources is exponentially increasing to supply the widespread range of high-tech applications of these elements including phosphors lighting materials, catalysis and permanent magnets. Phosphate fertilizer byproducts including phosphogypsum (PG) were identified as a potential alternative resource of REEs, not only to face the expansion of market demand, but also to achieve a sustainable management of REE resources. This study reports the leaching of REEs from PG using methanesulfonic acid (MSA) as a green organo-sulfonic acid in comparison with other acids such as p-toluenesulfonic acid (PTSA) and hydrochloric acid (HCl). MSA achieved the highest leaching efficiency of 78% with low solubility of PG under the operating conditions of 3 M, solid to liquid ratio (S/L) of 1/8, 120 min and 25 °C. The optimized leaching process was also modeled using shrinking core theory to assess the kinetics behavior of the system and to enable the determination of the predominant mechanisms. It was demonstrated that the leaching is governed by a product layer diffusion-controlled model with an activation energy of 2.73 kJ mol⁻¹. The cleaned PG after leaching could greatly meet the quality requirements of the building materials industry.

Organophosphorus compounds (OPC) are a large class of organic compounds that provide a wide range of applications, and their importance has grown steadily in recent years. In each category and family, these compounds have similarities and differences. Due to their immense variety, these chemicals have various properties and, therefore, various applications. In fact, various works have been published recently that present the main applications of OPC, especially in metal extraction. Despite their extemsive range of use, optimizing their performance as extractant agents remains a challenge due to their structural variability and sensitivity to process parameters. This review provides a critical analysis of pentavalent OPCs, focusing on how their chemical nature influences heavy metal extraction efficiency. For the first time, we present a novel classification system for OPCs based on phosphorus valency and heteroatom coordination, offering a framework to guide future research. Our findings reveal that the direct coordination of the phosphorus to heteroatoms such as oxygen, sulfur, and nitrogen has a great influence on the physicochemical characteristics of the extractant and the metal extraction efficiency. This observation is in line with Pearson’s Hard and Soft Acids and Bases (HSAB) theory in the sense that it demonstrates that altering the heteroatom alters the metal affinity of the ligand. As a result, these structural modifications can improve the extraction performance by up to 40% for some heavy metals, highlighting the potential for optimized molecular designs to maximize industrial applications. In the future, this work offers a solid foundation for future studies on the rational design of organophosphorus-based extractants. Using HSAB theory and our novel classification system, researchers can rationally design OPCs for their target metal with unparalleled precision. These results have transformative impacts on metal recovery efficiency-intensive sectors like mining, waste recycling, and clean energy technologies.