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Metals 2021, 11, x FOR PEER REVIEW 9 of 18 Metals 2021, 11, 1301 8 of 17 A total of 85.8% of V in vanadium slag was extracted by acidic sodium chlorate solu- tion. V3+ in vanadium slag was oxidized by NaClO3 as a chlorinating agent. The reaction A total of 85.8% of V in vanadium slag was extracted by acidic sodium chlorate Equation is3+as follows in Equation (38) [46]. solution. V in vanadium slag was oxidized by NaClO3 as a chlorinating agent. The reaction Equation is as follows in Equation (38) [46]. 6FeV2O4 + 5NaClO3 + 15H2SO4 = 5NaCl + 6(VO2)2SO4 + 3Fe2(SO4)3 + 15H2O (38) Sun et al. [47] proposed chlorination of vanadium slag by FeCl3. Under the optimal 6FeV2O4 + 5NaClO3 + 15H2SO4 = 5NaCl + 6(VO2)2SO4 + 3Fe2(SO4)3 + 15H2O (38) experimental conditions (827 °C, reactant (vanadium slag)—chlorination agent (FeCl3) Sun et al. [47] proposed chlorination of vanadium slag by FeCl . Under the optimal molar ratio of 1:2, 2 h, oxygen atmosphere), the extraction ratio of va3nadium in vanadium experimental conditions (827 ◦C, reactant (vanadium slag)—chlorination agent (FeCl ) slag is 57%. Du [48] investigated carbochlorination of pre-oxidized vanadium slag. T3he molar ratio of 1:2, 2 h, oxygen atmosphere), the extraction ratio of vanadium in vanadium flow chart of extracting vanadium from vanadium slag by chlorination is shown in Figure slag is 57%. Du [48] investigated carbochlorination of pre-oxidized vanadium slag. The 6. The carbochlorination temperature is about 650 °C. Vanadium is volatile in the form of flow chart of extracting vanadium from vanadium slag by chlorination is shown in Figure 6. VOCl3. VOCl3 was oxidized to V2O5 by O2. The equations of the main reactions involved The carbochlorination temperature is about 650 ◦C. Vanadium is volatile in the form of are (39)–(41). The effect of time, temperature, petroleum coke and chlorine pressure frac- VOCl . VOCl was oxidized to V O by O . The equations of the main reactions involved tion w3 ere stu3died. Under optima2l p5rocess2 conditions (650 °C,120 min, P(Cl2)/P(Cl2 + N2) = are (39)–(41). The effect of time, temperature, petroleum coke and chlorine pressure fraction 0.5, 10% of petroleum coke mass fraction), 18.8% of Fe and 87.5% of V were extracted. werestudied.Underoptimalpr+ocesscond+itions(650◦C,120min,P(Cl)/P(Cl +N)= 222 Wastewater containing high Na and NH4 is scarcely produced in whole process. 0.5, 10% of petroleum coke mass fraction), 18.8% of Fe and 87.5% of V were extracted. (Fe, Mn) (V, Cr, Ti)2O4 (s) + O2 (g) → Fe2O3 (s) + MnO (s) + Cr2O3 (s) + V2O5 Wastewater containing high Na+ and NH4+ is scarcely produced in whole process. (s) + TiO2 (s) (Fe,Mn)(V,Cr,Ti)2O4 (s)+O2 (g)→Fe2O3 (s)+MnO(s)+Cr2O3 (s)+V2O5 (s)+TiO2 (s) (39) 1/3V2O5 (s/l) + 1/2C (s) + Cl2 (g) → 2/3VOCl3 (g) + 1/2CO2 (g) (40) 1/3V2O5 (s/l) + 1/2C (s) + Cl2 (g) → 2/3VOCl3 (g) + 1/2CO2 (g) (40) 1/3Fe2O3 (s) + 1/2C (s) + Cl2 (g) → 2/3FeCl3 (g) + 1/2CO2 (g) 1/3Fe2O3 (s) + 1/2C (s) + Cl2 (g) → 2/3FeCl3 (g) + 1/2CO2 (g) (41) (39) (41) FFigiguurere66. .FFlolowcchhaarrttooffeexxtrtraacctitninggvvaannaaddiuiumfrforomvvaannaaddiuiumslsalaggbbyycacarbrboochchlolorirninaatitoionn. . In order to extract vanadium from vanadium slag, Liu et al. [49–55] proposed to use In order to extract vanadium from vanadium slag, Liu et al. [49–55] proposed to use selective chlorination method to extract vanadium. Because to the existence form and value selective chlorination method to extract vanadium. Because to the existence form and of valuable metal elements (Fe, Mn, V, Cr and Ti) in vanadium slag, NH4Cl was selected value of valuable metal elements (Fe, Mn, V, Cr and Ti) in vanadium slag, NH4Cl was to chlorinate Fe and Mn in vanadium slag. Thermodynamic calculations show that the selected to chlorinate Fe and Mn in vanadium slag. Thermodynamic calculations show iron and manganese in vanadium slag could be chlorinated by hydrogen chloride, but the that the iron and manganese in vanadium slag could be chlorinated by hydrogen chloride, V, Cr and Ti could not be chlorinated in the temperature range from 0 to 1000 ◦C. Under but the V, Cr and Ti could not be chlorinated in the temperature range from 0 to 1000 °C. optimal chlorination conditions, the chlorination ratio of iron and manganese were 72% Under optimal chlorination conditions, the chlorination ratio of iron and manganese were and 95%, respectively. Meanwhile, the enrichment ratio of V, Cr and Ti was obtained as 72% and 95%, respectively. Meanwhile, the enrichment ratio of V, Cr and Ti was obtained 48%. In addition, AlCl3 was selected to chlorinate V, Cr and Ti in vanadium slag. Figure 7 as 48%. In addition, AlCl3 was selected to chlorinate V, Cr and Ti in vanadium slag. Figure shows a flow chart of extracting vanadium from vanadium slag by AlCl3 chlorination. The 7 shows a flow chart of extracting vanadium from vanadium slag by AlCl3 chlorination. chlorination temperature is about 900 ◦C. Vanadium after chlorination exists in the form of The chlorination temperature is about 900 °C. Vanadium after chlorination exists in the VCl3. Metal V was obtained by molten salt electrolysis at 900 ◦C. The effects of reaction form of VCl3. Metal V was obtained by molten salt electrolysis at 900 °C. The effects of temperature, reaction time, mass ratio of AlCl3/slag and mass ratio of salt/AlCl3 on the chlorination ratio of valuable elements were investigated. Under optimal chlorinationPDF Image | Extraction of the Rare Element Vanadium
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