A new method of altered ilmenite processing has been studied. In this method, sulfuric acid is used as the reaction medium of the process, and fluoride ions are activators of the dissolving process of the rutile part of the ore raw material. The regression model of the sulfate–fluoride leaching process was developed and analyzed by using the response surface method of 23 matrix. The obtained model is adequate and well describes the studied process. The influence of Ti:F molar ratio, temperature, and sulfuric acid concentration on the leaching process are investigated in this work in order to optimize the studied process. It is experimentally proved that leaching at temperatures above 100 °C, at a molar ratio of Ti:F of more than 1:2, and the use of solutions of sulfuric acid with concentrations of more than 85 wt.% is not optimal because the extraction degree of titanium is reduced. The intensification of the process of sulfuric acid leaching by dividing the main stage of chemical dissolution of ilmenite into two stages was proposed. This method allows to leach up to 95.9% of titanium, which is 1.6–1.9 times higher in comparison with the classical technology of leaching altered ilmenite.
Rutile decomposition by sulfuric acid, including the formation of two salts, Ti(SO4)2/TiOSO4, is thermodynamically modelled. It is shown that TiO2 can spontaneously dissolve in H2SO4 solutions. However, titania is considered as an inert (ballast) phase component of titanium-containing raw materials due to the decelerated separate nature of such chemical transformations. It is concluded that the hampered related kinetics of dissolution can be attributed to the lability of Ti(IV) cations/the specific engineered features of the hierarchical crystalline structure. It is suggested that the breaking of Ti–O–Ti bonds without additional mechanical strains in crystal lattice geometry becomes more advantageous when smaller negative anions/fluoride ions can be used. The analysis of sulfate-fluoride extraction leaching of titanium confirmed that a decrease in the Gibbs energy in the presence of F occurs. It is indicated by kinetic research studies that the addition of corrosive sodium reagent (NaF) reduces the activation by 45 kJ/mol, which results in intensification. A mechanism is proposed for the interactions involving the Ti–O–Ti cleavage on the surface/the H2SO4-induced Ti dioxide degradation on the sites of defects. Moreover, F acts as a homogeneous/heterogeneous bifunctional catalyst.
The kinetics of the sulfuric acid leaching of altered ilmenite, mechanisms, and process intensification methods were studied. The effect of changing the chemical composition during grinding was determined. The content of ilmenite and pseudorutile decreased from 5.3% to 3.1% and from 90.2% to 63.1%, respectively. Rutile increased from 4.5% to 28.7%, while a pseudobrookite new phase appeared in the amount of 5.1% after 2 h of grinding. It was found that the modification of raw material by sulfuric acid led to the increase of the decomposition rate, and at the same time, decreased when the ore was utilized due to an increase of insoluble TiO2 content. Isothermal conditions were evaluated with H2SO4 concentration varying from 50 to 96%. The data obtained were described with the approximation of the contracting sphere model. It was shown for the first time that H2SO4 > 85 wt% causes a sharp constant decrease of titanium. Correlating these phenomena allows for the consideration of H2SO4·H2O as reagents, rather than H2SO4 molecules. It was experimentally proven that at a temperature above 190 °C, the Ti leaching degree dropped, which is explained by the formation of polymerized TiOSO4. Finally, it was shown that adding NaF reduced the activation energy to 45 kJ/mol.
The effect of pressure in a plasma reactor on the synthesis of mixtures of H2O2 and ClO 2 - has been studied. The yield of oxidants, selectivity for chlorites, the rate of the process, and its energy consumption have been treated as optimization parameters. Functional dependences of the optimal time of the plasma treatment of NaCl solutions on the reactor pressure with respect to parameters, such as the process selectivity and chlorite yield, have been determined.