Thermal decomposition and oxidation of bastnaesite concentrate in inert and oxidative atmosphere

To clearly elucidate the oxidative roasting behaviors of the bastnaesite, the thermal decomposition and oxidation of the bastnaesite concentrate in inert and oxidative atmosphere have been investigated in detail. Experimental data indicated that the initial decomposition temperature of the concentrate under N2 atmosphere is 150 ℃ higher than that under O2 atmosphere,most likely because the oxidation of the cerium induces the decomposition of the concentrate. For the roasted samples under N2 atmosphere at500 ℃ and above,the oxidation efficiency of the cerium is 19.8%-26.8% because of the fact that rareearth fluorocarbonate is first decomposed to form rare-earth oxyfluoride and CO2, and the cerium oxyfluoride is then partially oxidized by the CO2 gas. The rest cerium in these samples can be further oxidized in air at room temperature, with the oxidation efficiency of the cerium gradually increasing to above 80% in 7 d. This can be attributed to the obvious changes in the inner morphology of the roasted samples under N2 atmosphere at high temperatures, which largely induce the diffusion of the air and improves the oxidation activity of CeOF, and further induces the oxidation of CeOF by the air. XRD and XPS techniques were used to further verify the significant differences in the thermal decomposition behaviors of the bastnaesite concentrate under N2 and O2 atmosphere. Moreover, no oxidation of Pr^（3＋） to Pr^（4＋） in the roasted samples under both N2 and O2 atmosphere is observed. This gives an overall understanding of the oxidative roasting of the bastnaesite concentrate without additives.

Aqueous stability of rare earth and thorium elements during hydrochloric acid leaching of roasted bastnaesite

In order to study the aqueous stability of rare earth and thorium elements and the reaction mechanism of hydrochloric acid leaching of roasted bastnaesite,Eh-pH diagrams for La-,Nd-,Ce-,Th-（Cl）-（F）-H2 O systems at 20 ℃ were depicted using HSC Chemistry 6.0 software. Eh-pH diagrams of La-, Ce-,Nd-and Th-Cl-H2 O systems show that trivalent rare earth would be leached into solution by adjusting the acidity of the leaching solution, while tetravalent cerium and thorium would be remained in the leaching residue. And in the case that the pH value of the leaching solution is lower than 2, tetravalent cerium would be partially reduced by chlorine ions（Cl^-）, which is well agreed with the industrial production. It can be inferred from Eh-pH diagrams for the systems La-, Nd-,Ce-, Th-F-H2 O that the leached trivalent rare earth ions（RE^（3＋）） and tetravalent thorium ions（Th^（4＋）） are preferentially combined with fluorine ions（F） to form sediment during non-reductive acid leaching of roasted bastnaesite. However,when controlling the pH value of the leaching solution below 0, fluorine and tetravalent cerium in the roasted bastnaesite would be leached out in the form of soluble [CeF3]~＋ complex. That means the precipitation of REF3 and ThF4·2.5 H2 O can be avoided in the leaching step. According to Eh-pH diagrams for the system Ce-F-Cl-H2 O, [CeF3]~＋ in the leaching solution would be reduced to CeF3 precipitate in the presence of Cl^-, that is to say, tetravalent cerium and fluorine would be firstly leached out to form[CeF3]~＋,which would then be reduced to CeF3 precipitate by Cl^-in the hydrochloric acid leaching process of roasted bastnaesite.