Dissolution of Rare Earth Elements from Apatite Ore in Sulfuric Acid Solution

"Rare earth minerals are usually concentrated by flotation, magnetic or gravity separation methods to produce concentrates that are subsequently leached with hydrochloric (HCl), sulfuric acid (H2SO4) or nitric acid (HNO3). About 75 % REEs are lost in gypsum by-product when apatite is dissolved in H2SO4, whereas more than 80% of REE can be extracted from the apatite using HCl and HNO3 leaching processes, respectively. Therefore, the main aim of this study was to find an efficient process of dissolution of rare earth elements (REEs) from apatite ore by sulfuric acid solution due to its lower cost. In order to optimize the dissolution process, effects of different parameters, namely, concentration of H2SO4 (0.05 – 6 M), solid/liquid phase ratio (1:50 – 1:100), temperature (20 – 80 ºC), agitation speed (300 – 900 rpm), and leaching time (0.5 - 6 h) on the dissolution of REEs from apatite ore were examined in various intervals. The contents of main REEs in the apatite ore used in this study were (as % wt): 3 % La, 6 % Ce, 0.6 % Pr, 2.1 % Nd, 0.2 % Sm and 0.3 % Y. X-ray diffraction (XRD) analysis identified fluorapatite and phlogopite as main minerals in the ore. The results obtained from leaching experiments showed that more than 85% of REEs were dissolved from the apatite ore under the optimized conditions, which were: 1 M H2SO4, particle size of -150 + 100 µm, S:L phase ratio of 1:50, agitation speed of 500 rpm at 20 ºC for 1h. The XRD analysis revealed that main mineral compositions of the residues from 1M and 6 M H2SO4 leaching are gypsum (CaSO42H2O) and hemigypsum (CaSO40.5H2O), respectively.INTRODUCTIONThe term rare earth elements (REEs) denote the group of 17 chemically similar metallic elements consisting of the 15 lanthanides, plus yttrium (Y) and scandium (Sc) in the periodic table. These metallic elements are generally divided into two sub-groups; (1) the cerium sub-group, which is called “light rare earth elements” (LREEs), includes the elements from lanthanum (La) to europium (Eu), and (2) the yttrium (Y) sub-group elements, which are known as “heavy rare earth elements” (HREEs), are the remaining lanthanides from gadolinium (Gd) to lutetium (Lu) plus yttrium (Gupta and Krishnamurthy, 2005). The REEs occur together in the minerals due to their chemical and physical similarities, which cause problems of separating them from one another (Abreu and Morais, 2014). Although REEs are relatively abundant in the earth’s crust, they are typically dispersed and rarely occur in concentrated forms, making them economically challenging to obtain. There are a wide variety of rare earth minerals, however economic deposits of REEs in mining are bastnasite (La, Ce) FCO3, monazite (Ce, La, Y, Th) PO4, and xenotime YPO4 (Binnemans, 2013; Xie, et al, 2014). Due to the unique physical, chemical, catalytic, electrical, magnetic and optical properties of REEs, demand of these elements has increased dramatically with the advent of new technologies in electronics, communication, construction, energy and medicine (Jordens, et al, 2013). Since 1990, China has provided about 90 % of REEs worldwide. Japan and United States are the largest consumers of China’s REEs. In 2010, China announced to reduce REEs exports to Japan, as it tended to increase prices of REEs and to reduce a stable supply of REEs in the world market (Humphries, 2013). Therefore, there has been an increase in recent exploration activities intended to reveal new commercial sources of REEs and to bring them into production (Antico, et al, 1996). Apatite is an important host mineral for REEs in igneous and metamorphic rocks and can be used as an ore for those metals (Kanazawa and Kamitani, 2006). Apatite is also the main source of phosphate fertilizers and phosphoric acid (Habashi, 2013; Emsbo, 2015)."