Sulfuric acid baking and leaching of rare earth elements, thorium and phosphate from a monazite concentrate: Effect of bake temperature from 200 to 800 °C

Abstract

Monazite, a rare earth and thorium bearing phosphate mineral, is one of the major minerals used for the production of rare earth elements. Although sulfuric acid baking is one of the main processing routes for extraction of rare earth elements from monazite, the chemistry involved is not well understood. In this study, a combination of chemical analysis and standard characterisation techniques (XRD, SEM-EDS, FT-IR and TG-DSC) was used to identify reaction processes occurring during the sulfuric acid baking of monazite between 200 and 800°C. The effects of these reactions on the leachability of the rare earths, thorium and phosphate were also examined. It was observed that the sulfation reaction of monazite with acid was virtually complete after baking at 250°C for 2 h, resulting in >90% solubilisation of rare earth elements, thorium and phosphate. After baking at 300°C, a thorium phosphate type precipitate was formed during leaching, leading to a sharp decrease in extraction of thorium and phosphate, but the leaching of rare earth elements reached nearly 100%. The EDS and FT-IR analyses of this precipitate were indicative of a thorium pyrophosphate. As the bake temperature was further increased to 400-500°C, extraction of thorium, phosphorus and the rare earth elements decreased due to formation of insoluble thorium-rare earth polyphosphates. The formation of these polyphosphates is thought to be related to dehydration of orthophosphoric acid produced in the initial reaction of monazite with sulfuric acid. Between 650 and 800°C, monazite was partially re-formed, leading to a further decrease in rare earth extraction to 55%. The re-forming of monazite appeared to be due to a reaction between the thorium-rare earth polyphosphates and rare earth sulfates.

Evaluation of the Acid Baking Technique to Decrease the Phosphorus Content of the Iron Ore

“…Similar approaches have been reported [14][15][16][17] . Processes of acid baking at different temperatures were developed 14 . Initially, acid baking was used at a low temperature, which resulted in the solubilization of rare earth and impurities during leaching 15 .…”

Extraction of Rare Earth Elements from Phospho-Gypsum: Concentrate Digestion, Leaching, and Purification

“…Therefore, these parameters were chosen for the first baking stage. According to the statistical model, phosphorus and thorium are immobilized in the residue at temperatures above 400 • C, which is in line with other investigations [18]. Therefore, a series of tests was conducted to test different settings for the second baking stage.…”

“…In the sulfuric acid route, the monazite concentrate is mixed with concentrated sulfuric acid and is then digested in rotary kilns at 250-600 • C for 2-5 h to convert the REEs to water soluble sulfates according to Equation (2) [12,17]. Depending on the process parameters, thorium is also mobilized according to Equation (3) or converted to insoluble thorium pyrophosphates, which remain in the residue after leaching [17,18]. To complete the REE and thorium sulfate formations, 250 • C is sufficient.…”

“…The formation of thorium pyrophosphates is favored by high temperatures but is accompanied by decreasing REE yields. Therefore, to maximize REE yield and thorium immobilization, [18] suggests to hold the temperature at 250 • C before increasing the temperature to 400-500 • C.…”

“…According to literature, the baking temperature has a strong influence on the sulfuric acid digestion with regard to the REE yield and impurity control. Temperatures between 250 and 600 • C are described [12,18]. To study the effect of temperature, 250 • C and 600 • C were chosen for the preliminary tests.…”