Rare earth elements (REEs) are important strategic resources, widely used in various technological fields, especially heavy rare earth elements (HREEs). China has extensive rare earth deposits, with diverse mineral types and a complete range of rare earth elements, characterized by a “heavy south, light north” resource distribution pattern. The rare earth-bearing collophane in the Zhijin area of Guizhou is a typical marine sedimentary phosphorite deposit with large reserves and a high heavy rare earth content. This study investigates the rare earth-bearing collophane in the Zhijin area using X-ray diffraction (XRD), X-ray fluorescence (XRF), and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS) to analyze its mineral composition and occurrence characteristics. In terms of flotation, a reverse flotation process for magnesium removal was adopted. By optimizing the flotation parameters, including grinding fineness, collector dosage, pH regulator dosage, and depressant dosage, the optimal flotation conditions were determined. A further mineralogical analysis was conducted on both the flotation concentrate and tailings. The results show that the main minerals in the rare earth-bearing collophane of Zhijin are fluorapatite and dolomite, with dolomite as the primary gangue mineral, and rare earth elements are mainly hosted in fluorapatite. The optimal flotation conditions were achieved when the grinding fineness was −74 μm with an 83% passing rate, XF-1 was used as the collector at a dosage of 300 g/t, sulfuric acid (H₂SO₄) as the pH regulator at 6 kg/t, and phosphoric acid (H₃PO₄) as the depressant at 3 kg/t. By employing an optimal reagent regime and implementing a reverse flotation process consisting of one roughing and one scavenging stage, a phosphate concentrate was obtained with a P₂O₅ grade of 31.61% and an REO content of 0.161%. The P₂O₅ recovery reached 84.22%, while the REO recovery was 78.65%. Compared to the raw ore, the P₂O₅ grade increased by 11.52 percentage points, and the REO content improved by 0.051 percentage points. Mineralogical analysis of the flotation concentrate and tailings revealed that dolomite was effectively removed by reverse flotation, while rare earth elements were successfully enriched in the phosphate concentrate. In conclusion, this study provides an efficient flotation separation process for rare earth-bearing collophane and dolomite, while also offering technical support for the efficient recovery of rare earth resources. This research has significant theoretical and practical implications.

The efficient recovery of rare earth elements from associated rare-earth-bearing phosphate ores is of paramount importance for expanding the supply of rare earth resources. In contrast to conventional studies that focus on extracting rare earths either from phosphate concentrates or from phosphogypsum generated during the sulfuric acid wet-process, this study takes as its subject the rare-earth-enriched residue—an intermediate product obtained after the selective leaching of phosphorus via the hydrochloric acid route—from a rare-earth-bearing phosphate ore in Zhijin, Guizhou Province. The occurrence states, leaching behavior, and kinetic mechanisms of rare earth elements within this residue were systematically elucidated. Analyses using scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM–EDS) and aberration-corrected scanning transmission electron microscopy (STEM) reveal that rare earth elements are hosted in residual fluorapatite and newly formed CaF₂ through isomorphic substitution. The substitution of REE³⁺ for Ca²⁺ induces lattice contraction in CaF₂, with the interplanar spacing decreasing from 0.27 nm to 0.26 nm. Through single-factor experiments and response surface methodology (RSM) optimization, the optimal leaching conditions were determined to be a temperature of 80 °C, a leaching time of 120 min, a hydrochloric acid dosage of 160% of the theoretical requirement, a solid–liquid ratio of 1:6, and a agitation speed of 500 r·min⁻¹. Under these conditions, the leaching efficiency of rare earth elements reached as high as 92.69%. Kinetic analysis indicates that the leaching process follows the shrinking-core model, with the rate controlled by diffusion through the solid product layer. The apparent activation energy was calculated to be 37.2 kJ·mol⁻¹, characteristic of a diffusion-controlled process. Furthermore, response surface analysis of variance confirms that leaching temperature and time are the most significant factors influencing rare earth leaching. This study elucidates, from multiple perspectives, the leaching mechanism of rare earth elements from enriched residues within a hydrochloric acid system, thereby providing important theoretical support for the efficient recovery and process optimization of rare earth resources from associated phosphate ores.

Rare earth elements (REEs), as significant associated resources in sedimentary phosphate deposits, are commonly processed via the conventional hydrochloric acid wet-process phosphoric acid route (IMI process). In this method, phosphate and rare earth elements are typically leached simultaneously, which subsequently complicates their separation. In this study, a dolomitic rare earth-bearing phosphate concentrate from the Zhijin region of Guizhou Province was selected as the research subject. A stepwise phosphorus-prioritized leaching process was proposed, whereby precise regulation of hydrochloric acid dosage and reaction temperature enabled the preferential leaching of phosphorus (91.27%) and the directed enrichment of rare earth elements in the leaching residue (enrichment ratio of 4.7), thereby achieving efficient phosphorus–rare earth separation at the source. Subsequent process mineralogical analyses of the phosphate concentrate and the leaching residue revealed that rare earth elements occur in fluorapatite predominantly through isomorphic substitution. Following preferential phosphorus leaching, the residual Ca combines with F to form CaF₂, while rare earth elements become concentrated within the leaching residue. Finally, kinetic investigations and response surface analyses demonstrated that the preferential phosphorus leaching process is governed by diffusion through the solid product layer. Among the influencing factors, hydrochloric acid dosage (A), leaching temperature (C), and the interactions between leaching time and the solid–liquid ratio (B, D) were identified as the most significant parameters affecting phosphorus leaching efficiency. This study elucidates, from a mechanistic perspective, the governing principles of phosphorus dissolution and rare earth enrichment within the hydrochloric acid preferential leaching system, thereby providing important theoretical support and technical guidance for simultaneously achieving efficient phosphorus extraction and targeted rare earth enrichment within the hydrochloric acid wet-process phosphoric acid production route.