Synthesis Of Titanium Tetrachloride Through Arbothermal Reduction And Chlorination Of Ilmenite Oncentrate

Titanium oksikarbonitrida (TiOxCyNz) yang di sintesis daripada ilmenit dan pengklorinan pada suhu rendah untuk menghasilkan titanium tetraklorida (TiCl4) telah di kaji pada projek ini. Kesan karbotermal penurunan dan penitridaan pada suhu, masa, suasana dan penambahan plastik polietilena (PET) kedalam arang batu terhadap pembentukan besi (Fe) dan TiOxCyNz daripada ilmenit telah di kaji dalam proses CTRN pada suhu 1100-1250 °C selama 60 ke 180 minit dengan empat nisbah berbeza iaitu PET kepada arang bermula daripada 25% kepada 100%. Mikroskop elektron pengimbasan pancaran (FESEM) dilengkapi dengan analisis spektrum X-ray dispersif tenaga (EDX) menunjukkan bahawa produk yang disintesis oleh 75% PET mempunyai mikrostruktur yang unik di mana zarah Fe sfera secara jelas dipisahkan dari fasa TiO0.02C0.13N0.85. Kadar karbotermal pengurangan dan nitridasi tertinggi untuk sampel yand disintesiskan oleh 75% PET adalah pada 99.15% dan 85.47%. Penyingkiran besi juga dilakukan dengan proses larut lesap pengudaraan jenis Becher pada 70 °C dengan adanya amonium klorida (NH4Cl) dan 0.1 wt% AQ-2 (anthraquinone-2-sulfonat asid natrium garam monohidrat) sebagai pemangkin berkesan. Kecekapan penyingkiran Fe adalah 98.5%, dan kandungan akhir Fe bebas pada TiO0.02C0.13N0.85 mengandungi 0.48 wt% Fe sebagaimana ditentukan oleh analisis ICP-OES. Mekanisme pengklorinan titanium nitrida (TiN) dan ilmenit nitrida telah dikaji secara meluas pada 250 °C - 400 °C. Tahap pengklorinan meningkat dengan kadar sederhana dengan meningkatkan suhu dan pengurangan saiz zarah TiN pada kadar aliran campuran gas N2-Cl2. Pengklorinan TiN yang tertinggi pada 250 °C dan 400 °C adalah 85.6% dan 97.7% dalam 60 minit. Hasil eksperimen ini juga menunjukkan bahawa model teras menyusut dengan mekanisme kawalan campuran mengawal kadar pengklorinan. Permukaan pada reaksi kimia terhadap gas klorin pada permukaan zarah TiN adalah kadar mengawal pada peringkat awal dan, pada peringkat kemudian, penyerapan dalaman (liang) melalui lapisan produk perantaraan adalah langkah mengawal kadar. Tenaga pengaktifan yang jelas (Ea) 10.97 kJ/mole diperolehi untuk pengklorinan TiN. Tahap pengklorinan TiO0.02C0.13N0.85 adalah 93.5% pada 400 °C dalam 60 minit. TiCl4 dengan ketulenan 99% yang telah dihasilkan dari ilmenit Malaysia dan sisa pengklorinan yang mengandungi unsur nadir bumi (REEs) dengan jumlah yang tinggi serta logam. Projek ini menunjukkan bahawa tiga tahap proses yang boleh menjadi kaedah yang boleh dilaksanakan dan kebolehupayaan untuk pengeluaran titanium tetrachlorida yang agak tulen daripada ilmenit. _______________________________________________________________________________________________________ The synthesis of titanium oxycarbonitride (TiOxCyNz) from ilmenite and its chlorination at low temperatures for production of titanium tetrachloride (TiCl4) was investigated in this research. The effects of reduction/nitridation temperature, time, atmosphere and addition of waste polyethylene terephthalate (PET) plastic into coal on the formation of TiOxCyNz and iron (Fe) from ilmenite were investigated in carbothermal reduction and nitridation (CTRN) process at 1100-1250 °C for 60-180 minutes with four different PET-to-coal ratios (C/Ored) ranging from 25 to 100 wt%. Field-emission scanning electron microscopy (FESEM) equipped with energy dispersive X-ray spectrometer (EDX) analyses showed that the product synthesized by 75 wt% PET had a unique microstructure in which spherical Fe particles were distinctly separated from TiO0.02C0.13N0.85 phase. The highest extents of reduction and nitridation of the sample synthesized by 75 wt% PET were 99.15% and 85.47%, respectively. Iron was also removed by an aeration leaching process at 70 °C in the presence of ammonium chloride (NH4Cl) and 0.1 wt% AQ-2 (Anthraquinone-2- sulfonic acid sodium salt monohydrate) as the effective catalysts. The efficiency of Fe removal was 98.5%, and final TiO0.02C0.13N0.85 contained 0.48 wt% Fe as determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES) analysis. The chlorination mechanism of titanium nitride (TiN) and TiOxCyNz were extensively investigated at 250 °C - 400 °C. The extent of chlorination moderately increased with increasing the temperature and decreasing particle size of TiN at constant flow rate of N2-Cl2 gas mixture. The highest extents of chlorination of TiN at 250 °C and 400 °C were about 85.6% and 97.7% in 60 minutes, respectively. The results also indicated that a shrinking core model with mixed-control mechanism governed the chlorination rate. The surface chemical reaction of chlorine gas on the surface of TiN particles was rate controlling in the initial stage and, during later stage, internal (pore) diffusion through the intermediate product layer was rate controlling step. The apparent activation energy (Ea) of about 10.97 kJ/mole was obtained for the chlorination of TiN. The extent of chlorination of TiO0.02C0.13N0.85 was 93.5% at 400 °C in 60 minutes. The TiCl4 with the purity of about 99% was eventually produced from ilmenite and the residue of the chlorination contained high amounts of rear earth elements (REEs) as well as refractory metals. This research demonstrated that a three-step process could be a feasible and sustainable method for production of relatively pure TiCl4 from ilmenite

An Innovative Process for Production of Ti Metal Powder via TiSx from TiN

This work presents a new processing concept for production of Ti metal powder from FeTiO(3)via TiN and TiSx. Because FeTiO3 can be converted to TiN by the carbothermal reduction and nitridation method, TiN was taken as the starting material. Ti2.45S4 and TiS2 powders were completely formed from TiN at 1473 K (1200 degrees C) in 3.6 and 10.8 ks, respectively. Either CS2 or S-2 gas could be used for the sulfurization process. The sulfides were then converted to alpha-Ti metal powders by the Ono and Suzuki (OS) process in molten CaCl2 with a small addition of CaS. Employing S-2 gas in the sulfurization step remarkably reduced the carbon contamination to 0.01 and 0.1 wt pct C after the sulfurization and reduction processes, respectively. alpha-Ti powders with spherical morphology and foil-like Ti sheets containing less than 0.15 wt pct O were obtained from the electrochemical reduction in molten CaCl2-0.5 mol pct CaS. The approach applied here offers a promising strategy to design an innovative process for production of commercial grade Ti powders via TiSx and TiN from FeTiO3 by nitridation, sulfurization, and OS processes

Formation of Titanium Sulfide from Titanium Oxycarbonitride by CS2 Gas

Previously this group reported that a good quality titanium metal powder can be produced from titanium sulfides by electrochemical OS process. In this study, the sulfurization procedure was examined to synthesize titanium sulfide from titanium oxycarbonitride by CS2 gas. The experiments were carried out in the temperature range of 1173 K to 1523 K (900 A degrees C to 1250 A degrees C) in a tube reactor with continuously flowing argon (Ar) as carrier gas of CS2. The formation of titanium sulfide phases from the commercial TiN, TiC, and TiO powders was studied as the initial step. Then, TiO0.02C0.13N0.85 coming from ilmenite was sulfurized to prepare single phase of titanium sulfide. The products were characterized by X-ray diffraction, and the morphology of the sulfides was rigorously investigated, and the sulfur, oxygen, and carbon contents in the products were analyzed. The process was remarkably dependent on the temperature and time. TiN and TiO0.02C0.13N0.85 powders could be fully converted to the single phase of Ti2.45S4 (Ti2+x S-4) at 1473 K (1200 A degrees C) in 3.6 ks. The maximum weight gain of TiN sample was similar to 55.3 pct indicating a full conversion of TiN to Ti2S3 phase. The carbon and oxygen contents in this sulfide prepared from the oxycarbonitride were about 1.8 wt pct C and 1.4 wt pct O, respectively. Therefore, the titanium sulfide could be a promising feedstock for the production of commercial grade titanium powder

Synthesis of Sc sulfides by CS2 sulfurization

Scandium sulfides were synthesized from its stable oxide, Sc2O3, using CS2 gas. Suitable temperature and time for synthesis were examined experimentally using a constant flow rate of gas mixture of Ar and CS2. The high rate of evaporation from liquid CS2 enhanced formation and stoichiometry of sulfides, and eliminated impurity carbon. Most of parts in the sample were converted to Sc2S3 at 1473 K for 7.2 ks, and a transient phase of Sc2O2S was often synthesized after a prolonged time under certain oxygen and sulfur potentials

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

Formation of Titanium Sulfide from Titanium Oxycarbonitride by CS2 Gas

Previously this group reported that a good quality titanium metal powder can be produced from titanium sulfides by electrochemical OS process. In this study, the sulfurization procedure was examined to synthesize titanium sulfide from titanium oxycarbonitride by CS2 gas. The experiments were carried out in the temperature range of 1173 K to 1523 K (900 A degrees C to 1250 A degrees C) in a tube reactor with continuously flowing argon (Ar) as carrier gas of CS2. The formation of titanium sulfide phases from the commercial TiN, TiC, and TiO powders was studied as the initial step. Then, TiO0.02C0.13N0.85 coming from ilmenite was sulfurized to prepare single phase of titanium sulfide. The products were characterized by X-ray diffraction, and the morphology of the sulfides was rigorously investigated, and the sulfur, oxygen, and carbon contents in the products were analyzed. The process was remarkably dependent on the temperature and time. TiN and TiO0.02C0.13N0.85 powders could be fully converted to the single phase of Ti2.45S4 (Ti2+x S-4) at 1473 K (1200 A degrees C) in 3.6 ks. The maximum weight gain of TiN sample was similar to 55.3 pct indicating a full conversion of TiN to Ti2S3 phase. The carbon and oxygen contents in this sulfide prepared from the oxycarbonitride were about 1.8 wt pct C and 1.4 wt pct O, respectively. Therefore, the titanium sulfide could be a promising feedstock for the production of commercial grade titanium powder