• Korean Journal of Materials Research
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• v.29 no.7
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• pp.412-424
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• 2019

Global fitting functions for Fe-selective chlorination in ilmenite($FeTiO_2$) and successive chlorination of beneficiated $TiO_2$ are proposed and validated based on a comparison with experimental data collected from the literature. The Fe-selective chlorination reaction is expressed by the unreacted shrinking core model, which covers the diffusion-controlling step of chlorinated Fe gas that escapes through porous materials of beneficiated $TiO_2$ formed by Fe-selective chlorination, and the chemical reaction-controlling step of the surface reaction of unreacted solid ilmenite. The fitting function is applied for both chemical controlling steps of the unreacted shrinking core model. The validation shows that our fitting function is quite effective to fit with experimental data by minimum and maximum values of determination coefficients of $R^2$ as low as 0.9698 and 0.9988, respectively, for operating parameters such as temperature, $Cl_2$ pressure, carbon ratio and particle size that change comprehensively. The global fitting functions proposed in this study are expressed simply as exponential functions of chlorination rate(X) vs. time(t), and each of them are validated by a single equation for various reaction conditions. There is therefore a certain practical merit for the optimal process design and performance analysis for field engineers of chlorination reactions of ilmenite and $TiO_2$.

• Clean Technology
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• v.25 no.2
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• pp.107-113
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• 2019

Numerical model that considered the shrinking core model and elutriation and degradation of particles was developed to predict selective chlorination of ilmenite and carbo-chlorination of $TiO_2$ in a two stage fluidized bed chlorination furnace. It is possible to analyze the fluidized bed chlorination reaction to be able to reflect particle distribution for mass balances and the chlorination reaction. The numerical model showed an accuracy with error less than 6% compared with fluidized bed experiments. The chlorination degree with particle size change was greater with a smaller particle size, and there was a 100 min difference to obtain a chlorination degree of 1 between $75{\mu}m$ and $275{\mu}m$. This was not shown to such a great extent with variation of temperature ($800{\sim}1000^{\circ}C$), and there was only a 10 min difference to obtain a chlorination degree of 0.9. In the first selective chlorination process, the mass reduction rate approached to the theoretical value of 0.4735 after 180 min, and chlorination changed the Fe component into $FeCl_2$ or $FeCl_3$ and showed nearly 1. In the second carbo-chlorination process, the chlorination degree of $TiO_2$ approached 0.98 and the mass fraction reached 0.02 with conversion into $TiCl_4$. In the first selective chlorination process, 98% of $TiO_2$ was produced at 180 min, and this was changed into 99% of $TiCl_4$ after an additional 90 min. Also the mass reduction rate of $TiO_2$ was reduced to 99% in the second continuous carbo-chlorination process.

• Resources Recycling
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• v.29 no.3
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• pp.3-10
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• 2020

The chlorination kinetics of synthetic rutile prepared by selective chlorination of ilmenite with Cl₂ and CO gas mixture were studied in a fluidized bed. Th e effects of reaction temperature, reaction time, and the ratio of Cl₂ and CO partial pressure ($p_{Cl_2}/p_{CO}$) on the conversion rate of TiCl₄ were investigated. The conversion rate of TiC₄ was low under the high $p_{Cl_2}/p_{CO}$ conditions. Moreover, it was considered that the partial pressure of CO gas was more effective than that of Cl₂ gas when comparing the stoichiometric conversion rate and experimental results of high CO partial pressure. Considering the porous structure of particles, the rate controlling step of the chlorination of synthetic rutile was determined to be chemical reaction and the activation energy was calculated as 53.77 kJ/mol.

• Applied Chemistry for Engineering
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• v.4 no.1
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• pp.64-74
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• 1993

The chlorination of the titanium slag from titaniferrous magnetite by the arc-smelting in a fluidized bed reactor was investigated to produce $TiCl_4$ from domestic titaniferrous magnetite. The optimum conditions are as follows : reaction temperature; $950^{\circ}C$, reaction time; 90min, $Cl_2$ gas velocity; 3cm/sec, and petroleum coke-to-titanium slag weight ratio; 0.18. Also the mean diameter of titanium slag and petroleum coke was $44.6{\mu}m$ and $67.9{\mu}m$ respectively. Under these conditions 97.07% of Ti component in the titanium slag was chlorinated and the purity of $TiCl_4$ from this chlorination was 96.2%.

• Korean Chemical Engineering Research
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• v.56 no.2
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• pp.156-161
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• 2018

$TiO_2$ photocatalyst powders were prepared by chlorination method and sol-gel method. Specific surface area and crystalline (i.e., anatase and rutile) of the catalyst varied depending on manufacture conditions and method. TTIP-sol photocatalyst had higher methylene blue (MB) decomposition characteristics than photocatalyst from chlorination method and TBOT-sol. MB removal efficiency from aqueous solution with TTIP-sol photocatalyst was over 90%. Experimental results showed that the $TiO_2$ photocatalyst with a single anatase phase and a large specific surface area had high decomposition characteristics of organic materials.

• Resources Recycling
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• v.29 no.4
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• pp.3-14
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• 2020

Titanium sponge is industrially produced by the Kroll process. In order to understand the importance of the emerging smelting and recycling process, it is necessary to review the conventional production process of titanium. Therefore this paper provides a general overview of the conventional titanium manufacturing system mainly by the Kroll process. The Kroll process can be divided into four sub-processes as follows: (1) Chlorination of raw TiO₂ with coke, by the fluidized bed chlorination or molten salt chlorination (2) Magnesium reduction of TiCl₄ and vacuum distillation of MgCl₂ and Mg by reverse U-type or I-type with reduction-distillation integrated retorts (3) Electrolysis process of MgCl₂ by monopolar cells or multipolar cells to electrolyze into chlorine gas and Mg. (4) Crushing and melting process in which sponge titanium is crushed and then melted in a vacuum arc furnace or an electron beam furnace Although the apparatus and procedures have improved over the past 80 years, the Kroll process is the costly and time-consuming batch operation for the reduction of TiCl₄ and the separation of MgCl₂.

• Applied Chemistry for Engineering
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• v.3 no.3
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• pp.451-463
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• 1992

A selective chlorination of titaniferrous magnetite in a fluidized bed reactor was investigated to find the optimum condition for selective removal of Fe component from low grade titaniferrours magnetite ore and to produce a rutile substitute from titaniferrous magnetite ore. The optimum chlorination condition was determined to be a temperaure of $950^{\circ}C$, 2hr of reaction time, reducting agent(petroleum coke) to titaniferrous magnetite weight ratio of 0.12, and $Cl_2$ gas velocity of 5cm/sec. Under the above mentioned condition, 99% of Fe in titaniferrous magnetite was removed and the reaction residue which became rutile substitute was identified as rutile by x-ray diffraction and was found to contain 70% $TiO_2$.

• Journal of environmental and Sanitary engineering
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• v.19 no.2
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• pp.1-6
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• 2004

In Bok-Jeong water treatment plant, chlorination is the only technique used for disinfection of drinking water. This disinfecting treatment leads to the formation of trihalomethanes (THMs). This study was carried out to investigate the possibility of improving removal efficiency of THM precursor in the conventional water treatment processes by $TiO_2$ photocatalytic oxidation. Removal efficiencies of DOC, $UV_{254}$, THMFP were low in the conventional water treatment processes. With application of $TiO_2$ photocatalyst, DOC, $UV_{254}$, THMFP were reduced more effectively. As the $TiO_2$ photocatalytic reaction time increased, the removal efficiencies of DOC, $UV_{254}$, THMFP were increased. The $TiO_2$ photocatalytic removal efficiencies of DOC, $UV_{254}$, THMFP were increased with increasing $TiO_2$ dosage. However, over 0.6g/l of $TiO_2$ dosage, the efficiency reached a plateau.

• Journal of Korean Society of Water and Wastewater
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• v.27 no.1
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• pp.83-89
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• 2013

Microbiological treatment, chlorination, and ozonation are usually used for water treatment. However, there is weakness that these methods can't decompose and eliminate recalcitrant organic pollutants perfectly. It is possible to eliminate recalcitrant organic pollutants when photocatalysis of $TiO_2$ is used. In this study, the removal efficiencies of organic pollutants by using photocatalyst of $TiO_2$ in the slightly polluted golf club water hazard and a river were investigated. The amount of $TiO_2$ was divided into three categories of 1 g/L, 2 g/L and 4 g/L in order to investigate the adequate amount of $TiO_2$ and the removal efficiency. UV light was used as a light source for the reaction of photocatalyst. As a conclusion in this study, the efficiency of turbidity removal was increased in proportion to the amount of $TiO_2$ until 4 hours. After then the turbidity was gradually decreased. Finally, the optimum concentration of $TiO_2$ was 4 g/L. The efficiency of COD removal was increased in proportion to the amount of $TiO_2$ regardless of time.

• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.325-331
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• 2016

Anatase particles of titanium dioxide were prepared from $TiCl_4$ aqueous solution by using an electro-dialysis [ED] process. For the preparation of an aqueous solution of $TiCl_4$ precipitates, $TiCl_4$ liquid frozen in ice was transferred to a neck flask and then hydrolyzed using deionized [DI] $H_2O$. During the hydrolysis of the $TiCl_4$ solution at $0^{\circ}C$, a slurry solution of $TiOCl_2$ was obtained and the color changed from red to orange. The ED process was applied for the removal of chlorine content in the slurry solution. Two kinds of hydrolyzed slurry solution with lower [$Ti^{4+}$] and higher [$Ti^{4+}$] were sampled and the ED process was applied for the samples according to the removal time of [$Cl^-$]. With de-chlorination, the solution status changed from sol to gel and the color quickly changed to blue. Finally, white crystalline powders were formed and the phase was confirmed by XRD to be anatase crystallites. The morphology of the hydrous titania particles in the solution was observed by FE-SEM. The hydrous titania particles were nano-crystalline, and easily coagulated with drying.