Eltefat Ahmadi

The Preparation of Iron-Free TiCl4 from Reduced and Nitrided Ilmenite by Polyethylene Terephthalate

In this study, titanium tetrachloride (TiCl4) solution was successfully synthesized from titanium oxycarbonitride (TiOxCyNz) by means of chlorination process at low temperatures. Iron-free TiOxCyNz was prepared by carbothermal reduction and nitridation of Ilmenite (FeTiO3) with coal-75 wt. % PETas a reductant in a H2/N2 gas mixture. Aeration leaching via the Becher process for iron removal with NH4Cl solution was the preferred method for iron removal. The effect of reduction temperature on the synthesis of titanium oxycarbonitride (TiO0.02C0.13N0.85) powder suitable for iron removal has been investigated in the temperature range of 1150–1250°C. The reduced-nitrided ilmenite samples were characterized by XRD and SEM/EDX in terms of phases and morphology. The results showed that iron was formed in spherical and separated particles from TiOCN. Furthermore, the effects of temperature between 350–450°C and soaking time from 1 to 3 hours on the chlorination of iron-free titanium oxycarbonitride have been evaluated. The evaluation was based on design of experiment (DOE) to identify the significant variables on the extent of titanium extraction. DOE analysis based on weight loss validated by ICP tests, indicated a good extraction of titanium and synthesis of TiCl4 at 450°C.

Assessment of titanium carbide chlorination by statistical design

In present study, the effects of the process parameters on chlorination of Titanium Carbide (TiC) was studied. Besides that, process parameters were investigated by using experimental design of experiment (DOE) and statistical analysis. The chlorination of the samples was carried out at temperatures between 400 to 500°C. Effects of three parameters, namely temperature, soaking time, and molar ratio of potassium permanganate (KMnO4) to hydrochloric acid (HCl) were investigated. The interaction, on the rate of chlorination of TiC were statistically evaluated by using DOE. The weight loss (wt. %) was the main response taken into account in this paper. The results of the experimental design indicated that the main significant factor for chlorination of TiC was higher temperature, soaking time and higher molar ratio of KMnO4 to HCl. DOE results have demonstrated that the highest extent of chlorination obtained at the highest weight loss (wt. %) was about 54.59 wt. % at 500°C with a soaking time of 180 minutes and KMnO4 to HCl molar ratio of 0.17 respectively. The amounted to a titanium extraction of about 96.39 %. On the other hand, the lowest wt. lost was 30.76 wt. % and this was obtained at 500°C for 120 minutes with KMnO4 to HCl molar ratio of 0.09 respectively. The results obtained from this work will be employed as a guide for the future studies on chlorination of nitrided/carburized Malaysian ilmenite or titanium oxycarbonitride. The final aim was to produce TiCl4 at low temperatures (≤500°C) using the latter samples. The experimental values are in good agreement with calculations from the statistical model.

Microstructural Study of Leached Nitrided Malaysian Ilmenite with Coal-Polystyrene Reductant

Titanium oxycarbonitride (TiOxCyNz) produced from Malaysian ilmenite consists of impurities such as iron that adversely affect the efficiency of chlorination process. In this paper, the dissolution of iron present in TiOxCyNz was performed using ammonium chloride (NH4Cl) solution at 70 °C from 4-6 hrs. Effects of acid concentration, catalyst amount and leaching time on the rate of iron dissolution were also investigated. Microstructural and/or morphological studies of the raw materials, and products were carried out by X-ray diffraction (XRD), X-ray Fluorescence (XRF), scanning electron microscopy (SEM), and Energy Dispersive X-ray analysis. The results obtained from SEM/EDX analysis for the reduced samples HR15 (15% Polystyrene (PS) + 85% coal (C)), HR25 (25% PS + 75% C) and HR35 (35% PS + 65% C) showed that most of the Titanium oxycarbonitrides were found in the circular shape with increase grain coarsening. Iron dissolution was accelerated with acid concentrations and it increased with increasing leaching time from 4 to 6 hrs. The results also showed that the percentage of Fe removed from titanium oxycarbonitride was ~ 76.85% at 70 °C for 6 hrs with the PS/C ratio of 0.18 and 1 wt. % of glucose as catalyst.

Extraction of titanium from low-iron nitrided Malaysian ilmenite by chlorination

In this paper, production of TiCl4 from low-iron nitrided ilmenite samples at relatively low temperature using chlorine gas generated from the reaction between KMnO4 and HCl has been investigated. The effects of chlorination soaking time, potassium permanganate (KMnO4) to hydrochloric acid (HCl) molar ratio and aluminium powder catalyst in chlorine gas generation on titanium extraction from nitrided Malaysian ilmenite were examined. The low-iron nitrided Malaysian ilmenite contained titanium oxycarbonitride (TiOxCyNz) after carbothermal reduction and nitridation with subsequent leaching. Chlorination process was performed at 500°C for 30 – 60 minutes. Statistical analysis of the data was done by Design of Experiment (DOE) to identify the significant variables and their interactions. The results achieved in this study showed that the highest extent of chlorination was about 98.34% at 500°C for 60 minutes. The lowest extent of chlorination was about 68.51% obtained in KMnO4 to HCl molar ratio of 2.0 and 0.3...

The Effects of Experimental Variables on Iron Removal from Nitrided Malaysian Ilmenite by Becher Process

Iron-free titanium oxycarbonitride (TiOxCyNz) is a promising feedstock for production of titanium tetrachloride (TiCl4) at low temperatures. In this study, the effects of leaching variables such as temperature, time, particle size of staring material and concentration of the leaching solutions were evaluated on iron removal from nitrided Malaysian ilmenite by Becher process. The nitrided ilmenite was prepared by isothermal reduction with graphite at 1200 °C for 3 h in H2-N2 atmosphere. The aerated leaching experiments were conducted at 50–90 °C with addition of 0.3–2.0 wt% of NH4Cl catalyst. The highest extent of iron removal (XFe) was obtained at about 96.2% for the sample leached at 90 °C for 7 h with 2.0 wt% NH4Cl. The iron concentrate and titanium oxycarbonitride product were characterized by ICP-OES, XRD, XRF and SEM-EDX analyses. The results indicated that the aeration leaching process was a successful route to prepare low-iron titanium oxycarbonitride.

Kinetic Modeling of Ilmenite Reduction with Compressed Natural Gas (CNG) Using MATLAB

The reduction of ilmenite by a gas comprising of CNG, hydrogen and nitrogen mixture was investigated by experimental and kinetic modeling in MATLAB. The CNG flow time was varied from 15 to 45 minutes at the temperatures of 1100-1200°C for 1-3 hours. In order to predict the extent of reduction, a shrinking core model (SCM) and crackling core model (CCM) were employed for the kinetic modeling. The results showed that the extent of reduction of 80% was achieved by using a CNG flow time of 45 minutes at 1200°C for 1 hour. The kinetic modeling for non-isothermal SCM at the same conditions gave a predicted value of 87%. The CCM gave a predicted value of about 100% at the same conditions. The non-isothermal SCM showed a closer trend to the experimental results. The deviation between SCM and CCM with the experimental data was attributed to porosity, thermodynamic properties and minute thermal fluctuations within the sample during the reduction process.