Indirect mineral carbonation of titanium-bearing blast furnace slag coupled with recovery of TiO_2 and Al_2O_3

Large quantities of CO2 and blast furnace slag are discharged in the iron and steel industry. Mineral carbonation of blast furnace slag can offer substantial CO2 emission reduction and comprehensive utilization of the solid waste. This paper describes a novel route for indirect mineral carbonation of titanium-bearing blast furnace （TBBF） slag, in which the TBBF slag is roasted with recyclable （NH4）2SO4 （AS） at low temperatures and converted into the sulphates of various valuable metals, including calcium, magnesium, aluminium and titanium. High value added Ti-and Al-rich products can be obtained through stepwise precipitation of the leaching solution from the roasted slag. The NH3 produced during the roasting is used to capture CO2 from flue gases. The NH4HCO3 and （NH4）2CO3 thus obtained are used to carbonate the CaSO4-containing leaching residue and MgSO4-rich leaching solution, respectively. In this study, the process parameters and efficiency for the roasting, carbonation and Ti and Al recovery were investigated in detail. The results showed that the sulfation ratios of calcium, magnesium, titanium and aluminium reached 92.6%, 87% and 84.4%, respectively, after roasting at an AS-to-TBBF slag mass ratio of 2：1 and 350℃ for 2 h. The leaching solution was subjected to hydrolysis at 102℃ for 4 h with a Ti hydrolysis ratio of 95.7%and the purity of TiO2 in the calcined hydrolysate reached 98 wt%. 99.7% of aluminium in the Ti-depleted leaching solution was precipitated by using NH3. The carbonation products of Ca and Mg were CaCO3 and （NH4）2Mg（CO3）2·4H2O, respectively. The latter can be decomposed into MgCO3 at 100-200℃ with simultaneous recovery of the NH3 for reuse. In this process, approximately 82.1% of Ca and 84.2% of Mg in the TBBF slag were transformed into stable carbonates and the total CO2 sequestration capacity per ton of TBBF slag reached up to 239.7 kg. The TiO2 obtained can be used directly as an end product, while the Al-rich precipitate and the two carbonation products can act, respectively, as raw materials for electrolytic aluminium, cement and light magnesium carbonate production for the replacement of natural resources.

Effects of MgO and TiO_2 on the viscous behaviors and phase compositions of titanium-bearing slag

The effects of MgO and TiO_2 on the viscosity, activation energy for viscous flow, and break-point temperature of titanium-bearing slag were studied. The correlation between viscosity and slag structure was analyzed by Fourier transform infrared（FTIR） spectroscopy. Subsequently, main phases in the slag and their content changes were investigated by X-ray diffraction and Factsage 6.4 software package. The results show that the viscosity decreases when the MgO content increases from 10.00wt% to 14.00wt%. Moreover, the break-point temperature increases, and the activation energy for viscous flow initially increases and subsequently decreases. In addition, with increasing TiO_2 content from 5.00wt% to 9.00wt%, the viscosity decreases, and the break-point temperature and activation energy for viscous flow initially decrease and subsequently increase. FTIR analyses reveal that the polymerization degree of complex viscous units in titanium-bearing slag decreases with increasing MgO and TiO_2 contents. The mechanism of viscosity variation was elucidated. The basic phase in experimental slags is melilite. Besides, as the MgO content increases, the amount of magnesia–alumina spinel in the slag increases. Similarly, the sum of pyroxene and perovskite phases in the slag increases with increasing TiO_2 content.