• Korean Journal of Materials Research
• /
• v.29 no.7
• /
• pp.412-424
• /
• 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 $TiO_2$.

• Resources Recycling
• /
• v.25 no.3
• /
• pp.74-81
• /
• 2016

Study on chlorination of ilmenite ore were carried out by using PVC(polyvinyl chloride) as the chlorinating agent in a static bed reactor for selective removal of iron. The effect of amount of PVC and reaction temperature were investigated. It was found that the removal ratio of iron increased with amount of PVC and temperature. After reaction with HCl gas generated from PVC, porous surface of the specimens were observed. As a result, HCl gas could react with iron in the central portion of ilmenite particle through these pores. Examination of data using kinetic model suggest that the selective chlorination rate is controlled by chemical reaction at the interface of particles. The activation energy for the selective chlorination of ilmenite using PVC was calculated as 20.47 kJ/mol.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.2
• /
• pp.472-476
• /
• 2011

Sodium chlorate/hydrochloric acid mixtures were used to chlorinate activated arenes and the $\alpha$-position of ketones. This chlorination method was used to produce selectively mono-, di-, and trichlorinated compounds by controlling the molarity of sodium chlorate. This reagent proved to be much more efficient and easier to handle than chlorine gas.

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

• Applied Chemistry for Engineering
• /
• v.3 no.3
• /
• pp.451-463
• /
• 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% $TiO_2$.

• Bulletin of the Korean Chemical Society
• /
• v.16 no.6
• /
• pp.507-511
• /
• 1995

Catalytic chlorination of chlorobenzene was studied in vapor phase using various solid-acid catalysts such as silica-alumina, alumina, zeolite and a modified clay prepared by impregnating bentonite with ferric chloride. The conversions of both chlorine gas and chlorobenzene showed high over silica-alumina, alumina and modified clay catalysts. However relatively large amounts of polychlorinated benzene derivatives were also observed. The active species of catalytic activity in chlorination of chlorobenzene in vapor phase were proved to be as Lewis acid sites by in-situ IR experiments. The strength of Lewis acid sites which were effective for the vapor-phase chlorination seemed to be having Hammett acidity Ho >-3.0. The selectivity to dichlorobenzenes was proved to be high over the zeolite catalyst due to their shape-selective properties. p-Dichlorobenzene or dichlorobenzene selectivities were improved more or less by changing the reaction conditions.

• Journal of Environmental Health Sciences
• /
• v.32 no.1 s.88
• /
• pp.96-101
• /
• 2006

Chlorination inhibition on the organic removal activity of activated sludge microorganism was investigated in this study. It is well known that chlorination improves the settleability of filamentous bulking sludge through the selective impediment of filamentous microorganisms. However, it is based on the declination of effluent water quality after actual chlorination in dairy wastewater treatment plant. In case of the activated sludge which was exposed in the suggested concentration of chlorine $7.5\;mgCl_2/gVSS/day$ for the filamentous bulking control, decrease of organic uptake rate of $4.9\~24.0\%$, and dentrification rate of $24.8\~30.3\%$ ware shown in comparison to the control group which was not reacted with chlorine. As a result of comparing floc size of activated sludge microorganism, the average of floc diameter in the chlorine exposed group was $150\;{\mu}m$, which displays $25\%$ decrease compared with the control group.

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

• Resources Recycling
• /
• v.27 no.3
• /
• pp.30-38
• /
• 2018

In this study, the behaviors of Fe selective chlorination in ilmenite ore by using PVC or $CO-Cl_2$ gas mixture as reducing agents under the condition of 1173 K, for 60 minutes were investigated. The weight loss ratio was 28% when PVC was applied as the reducing agent. The condensate formed at the outlet of reaction tube was identified as $FeCl_2$ by X-ray diffraction analysis. From these results, it was observed that iron in ilmenite ore reacted with HCl gas and Fe was selectively removed in the form $FeCl_2$. However, when $CO-Cl_2$ gas mixture was used as a reducing agent, the weight reduction ratio was 54%, and the condensate formed at the outlet of reaction tube after the experiment was estimated to be $FeCl_3$. It was observed that the ilmenite ore reacted with the $CO-Cl_2$ gas mixture and was simultaneously removed in the form of $FeCl_3$ and $TiCl_4$. However, the results of X-ray diffraction of ilmenite ore after the reaction showed that Fe was almost removed.

• Bulletin of the Korean Chemical Society
• /
• v.16 no.4
• /
• pp.349-355
• /
• 1995

Bromo-and chlorotrimethylsilane react with selenium dioxide in halocarbon solvents and generate selenium oxybromide and oxychloride, respectively. These in-situ generated oxyhalides turned out to be very efficient for selective bromination and chlorination of aldehydes and ketones. Under carefully controlled reaction conditions, second and third introduction of halogens into carbonyl compounds can be greatly suppressed, and high yields of monohalo compounds were obtained. The product ratios of this halogenation reactions can be best explained if the reactions are assumed to involve intermediate β-ketoselenenyl chlorides.