Chromium (Cr) was concentrated as chromium spinel in the vanadium slag produced by pre-oxidizing vanadium-containing hot metal in Pan-steel in China. Due to the chromium-rich Hongge ores used, chromium concentration in this slag was much higher than that in common vanadium slags. To propose a process for effective Cr extraction from the slag, mechanisms of Cr oxidation in Pan-steel vanadium slag under sodium roasting conditions were studied experimentally and with thermodynamic simulations. Chromium slags without vanadium were synthesized in the laboratory to mimick mineralogical characteristics of Pan-steel vanadium slag and characterized by XRD, SEM/EDS and TG-DSC techniques. Conditions for Cr extraction from the chromium slag after sodium roasting by leaching with water were studied and optimized. Results showed that Cr spinel was encapsulated in the silicate phase. During sodium roasting, Cr spinel was oxidized and decomposed after oxidation and decomposition of the olivine phase. Sodium carbonate began to react with chromium oxide, which was produced by decomposition of Cr spinel, at 537°C and large amount of sodium chromate appeared after 800°C. However, multi-component liquid phase (mixture of Na2Cr2O4, Na2CrO4 and Na2CO3) was produced after 1 000°C, which suppressed the conversion of Cr(III) to Cr(VI) by inhibiting oxygen supply. A conversion about 90% was obtained when the chromium slag was roasted at 1 000°C for 2 h with Na2CO3 addition in stoichiometric ratio to total amount of Cr2O3 and SiO2. 96% of Cr in the leaching liquid was recovered as chromium sesquioxide in fine powder form and high purity by reducing and precipitating.
The structure of FeO-SiO 2 -V 2 O 3 slags with compositions of (1-x)(1.5FeO·SiO 2 )·xV 2 O 3 (x = 0-20% mole fraction) was investigated in the molten and quenched states by using molecular dynamics (MD) simulations and Fourier transform infrared (FT-IR) spectroscopy. An empirical potential for the multi-component system has been developed in this work for performing MD simulations. The local atomic structures and the micro-heterogeneity in the molten slag have been systematically investigated using MD simulations. The bond length of V-O varies from 1.92 to 1.96 Å and the averaged coordination number of V (CN V-O ) increases from 4.50 to 4.96 with the addition of V 2 O 3 . The simulation results revealed that the average Si-O-Si bond angle and the degree of polymerization both decrease with increasing amount of V 2 O 3 , implying that V 2 O 3 may behave as a network-modifying basic oxide in the FeO-SiO 2 -V 2 O 3 system. This was further confirmed by the FT-IR spectrum analysis, which shows that the silicate network dissociates with the presence of V 2 O 3 .
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