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Metals 2021, 11, 1301 6 of 17 Metals 2021, 11, x FOR PEER REVIEW 2V2O5 + 4NaCl + O2 (g) = 4NaVO3 + 2Cl2 (g) V2O3 + 2FeCl3 + O2 (g) = 2VOCl3 (g) + Fe2O3 V2O3 + 3FeCl2 + 1.75O2 (g) = 2VOCl3 (g) + 1.5Fe2O3 7 of 18 (24) (25) (26) V2O3-NaVO3 V2O5-NaVO3 FeCl2 FeCl3 100 0 -100 -200 -300 -400 0 200 400 600 800 1000 1200 1400 Temperature/(oC) Figure 4. Variation of standard Gibbs free energy of reactions 23–26 with temperature. Figure 4. Variation of standard Gibbs free energy of reactions 23–26 with temperature. According to the above thermodynamic analysis, the valence state of vanadium, 4. Application of Chlorination Method reaction temperature, atmosphere and chlorinating agent play a very important role in 4.1. Chlorination Extraction of Vanadium from Vanadium Titanomagnetite the chlorination of vanadium. Thus, the chlorination of vanadium can be achieved by seVleacntaindgiuamp-ptirtoapnriuiamtemcoangdnietitoitnesi.sTmheaifnollylocwominpgowseildlionftriroodnuc(Feet)h,evapnroagdriuesmso(Vfc)halnodrination titanoifuvman(aTdi)iuemle-mcoentas,inwinhgicmhaitsermiaulslt.i-element symbiotic iron ore containing a small amount of cobalt (Co), nickel (Ni), chromium (Cr), scandium (Sc) and gallium (Ga) [31,32]. 4. Application of Chlorination Method The reserves of vanadium-titanium magnetite in the Panzhihua-Xichang regions in China 4.1. Chlorination Extraction of Vanadium from Vanadium Titanomagnetite amount to about 9.66 billion tons [33]. The content of vanadium pentoxide in vanadium- titanium magnetite is 0.1 wt%–2 wt% [34]. Jena et al. [23] proposed that under the action Vanadium-titanium magnetite is mainly composed of iron (Fe), vanadium (V) and of oxygen and water, NaCl as an additive reacts with the vanadium in the vanadium bear- titanium (Ti) elements, which is multi-element symbiotic iron ore containing a small ing titaniferrous magnetite. The roasted samples were leached with hot water. More than amount of cobalt (Co), nickel (Ni), chromium (Cr), scandium (Sc) and gallium (Ga) [31,32]. 90% of V was extracted. The reaction Equations are as follows in Equations (27)–(31). The reserves of vanadium-titanium magnetite in the Panzhihua-Xichang regions in China amount to about 9.66 billion tons [33]. The content of vanadium pentoxide in vanadium- SiO2 + 2NaCl + H2O = Na2SiO3 + 2HCl (27) titanium magnetite is 0.1 wt%–2 wt% [34]. Jena et al. [23] proposed that under the action of oxygenandwater,NaClasanadditivereactswiththevanadiuminthevanadiu(m28b)earing Na2SiO3 + O2 + V2O3 = 2NaVO3 + SiO2 titaniferrous magnetite. The roasted samples were leached with hot water. More than 90% of V was extracted. The reaction Equations are as follows in Equations (27)–(31()2. 9) (30) (27) (31) (28) 2NaCl + 3/2O2 + V2O3 = 2NaVO3 + Cl2 SiO2 + 2NaCl + H2O = Na2SiO3 + 2HCl 3Cl2 + 3V2O3 = 2VOCl3 + 2V2O5 Na2SiO3 + O2 + V2O3 = 2NaVO3 + SiO2 4VOCl3 + 3O2 = 2V2O5 + 6Cl2 (29) 3Cl2 + 3V2O3 = 2VOCl3 + 2V2O5 (30) extraction vanadium from vanadium-rich resources with FeCl2 and FeCl3. Thermody- 2NaCl + 3/2O2 + V2O3 = 2NaVO3 + Cl2 To some extent, the presence of SiO2 and the formation of HCl and Cl2 can promote the extraction of vanadium [23,35,36]. Zheng et al. [37] first calculated the feasibility of 4VOCl3 + 3O2 = 2V2O5 + 6Cl2 (31) namic calculations show that the higher the valence of vanadium in vanadium titanomag- netite, the easier it is to extract vanadium. Therefore, the chlorinated atmosphere was se- To some extent, the presence of SiO2 and the formation of HCl and Cl2 can promote lected as the oxygen atmosphere. The reaction Equations are as follows in Equations (32)– the extraction of vanadium [23,35,36]. Zheng et al. [37] first calculated the feasibility of (36). Under the optimal experimental conditions (827 °C, reactant (vanadium titanomag- extraction vanadium from vanadium-rich resources with FeCl2 and FeCl3. Thermodynamic netite)—chlorination agent (FeCl3) molar ratio of 1:2, 2 h, oxygen atmosphere), the extrac- calculations show that the higher the valence of vanadium in vanadium titanomagnetite, tion ratio of vanadium is 32%. V2O5 + 2FeCl3 = VOCl3 + Fe2O3 (32) ΔGrθ/(kJ/mol)PDF Image | Extraction of the Rare Element Vanadium
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