• 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 $TiO_2$.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.19 no.2
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• pp.271-278
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• 2021

In this study, a chlorination technique for recycling Li₂ZrO₃, a reaction product of ZrO₂-assisted rinsing process, was investigated to minimize the generation of secondary radioactive pyroprocessing waste. It was found that the reaction temperature was a key parameter that determined the reaction rate and maximum conversion ratio. In the temperature range of 400-600℃, an increase in the reaction temperature resulted in a profound increase in the reaction rate. Hence, according to the experimental results, a reaction temperature of at least 450℃ was proposed to ensure a Li₂ZrO₃ conversion ratio that exceeded 80% within 8 h of the reaction time. The activation energy was found to be 102 ± 2 kJ·mol^-1·K^-1 between 450 and 500℃. The formation of LiCl and ZrO₂ as reaction products was confirmed by X-ray diffraction analysis. The experimental results obtained at various total flow rates revealed that the overall reaction rate depends on the Cl₂ mass transfer rate in the experimental condition. The results of this study prove that the chlorination technique provides a solution to minimize the amount of radioactive waste generated during the ZrO₂-assisted rinsing process.

• Journal of the Korean Chemical Society
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• v.9 no.2
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• pp.81-87
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• 1965

Furfurylacetate was prepared and was chlorinated under various reaction conditions. At the low reaction temperature the chlorination product was composed of the stable trans-tetrachloride (yield, 25∼30%), decomposition product (low chlorine content), and unstable cis-tetrachloride. There were no appreciable quantity of the trichloride. At the high reaction temperature the chlorination products were exclusively decomposed. The reaction conditions, separation scheme, and the configurataion of the product were discussed.

• Journal of the Korean Chemical Society
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• v.12 no.2
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• pp.55-60
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• 1968

Chlorination of aromatic derivatives under UV light and ${\gamma}$-ray irradiation was studied. Ethyl ${\alpha} ,{\beta} -dichloro-{\beta}$-phenyl propionate gave the p-chlorophenyl derivatives when chlorination was done under UV light. The same type of the product was obtained in the reaction where the mole ratio of the ester and chlorine was 1 to 2 and the chlorination was done under ${\gamma}$-ray irradiation. When the mole ratio of the ester and chlorine was 1 to 8, the chlorination reaction under ${\gamma}$-ray irradiation gave a poly-chlorinated derivatives which was identified as a side chain chlorinated p-chlorophenyl derivatives. Ethyl ${\alpha} ,{\beta} -dichloro-{\beta}$-(p-chlorophenyl) propionate gave the same type of the side chain chlorinated p-chloro derivatives by the chlorination under ${\gamma}$-ray irradiation, whereas ethyl ${\alpha} ,{\beta} -dichloro-{\beta}$-(o-chlorophenyl) derivatives gave o,p-dichlorophenyl derivatives. The identifications of the products were based on a radio thin layer chromatography and activation analysis of chlorine contents of product. The chlorination reaction was discussed in regards to the effect of phenyl substituents to the formation of reaction product and the procedures were described.

• Proceedings of the KSME Conference
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• 2000.04b
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• pp.807-812
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• 2000

Chlorination dosage in water treatment plant of field is determined by chlorination demand experiment through two or three hours after raw water was sampled in inflow. It is impossible to continuously control fer real time because sampled water is adapted chlorination dosage after water treatment process had been proceeded. Therefore in this study, we will design informal chlorination demand system this designed system will be experimented as to water quality and accuracy of control in various conditions. Throughout these. experimental results, we will revise the system and revised system is enable to optimal control of chlorination dosage. Finally, We have developed chlorination demand system, which can automatically determination of chlorination dosage to be determined according to variety of raw water quality inflow in water treatment plant.

• 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.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.1
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• pp.69-75
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• 2013

The recovery of Zr from Zircaloy-4 (Zry-4) cladding hulls was demonstrated to investigate the effect of the oxidation process on the reaction rate of the chlorination reaction. In chlorination reaction experiments performed for 6 h, where reaction products were collected every 2 h, it was observed that a significant decrease in the reaction rate was caused by the oxidation process ($500^{\circ}C$, 10 h under an air atmosphere) within the reaction period of 0 - 2 h. The amount of reaction residue increased from 0.95 to 1.65wt% of initial weights in the fresh and Zry-500-10 (Zry-4 hulls oxidized at $500^{\circ}C$ for 10 h under an air atmosphere) hulls, respectively. The purity of the recovered Zr was identical at 99.61wt% for the fresh Zry-4 and Zry-500-10 hulls. Quantitative analysis of the chlorination reaction rate was performed by varying the reaction time from 0.5 to 1.0, 2.0, and 4.0 h. The fitting results showed that the relationship between weight loss and reaction time can be interpreted by a linear line with a slope of 23.35wt%/h for the fresh Zry-4 case, while two linear lines were necessary to fit the results of Zry-500-10. In addition, the slope values were 17.12 and 27.16wt%/h for (0 - 20) and (20 - 100)wt% loss regions, respectively.

• Journal of the Korean Chemical Society
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• v.18 no.4
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• pp.278-288
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• 1974

Starting from p-dichlorobenzene, 2-amino-4-chloroanisole could be prepared via a nitration, a methoxylation, and subsequent reduction. The repeated chlorination of 2-amino-4-chloroanisole resulted 2-amino-3,4,5-trichloroanisole without any isomeric products. The chlorination of 4-chloro-2-nitroanisole could easily give 2,4-dichloro-6-nitroanisole but polychlorination of the product could not be achieved at the atmospherical pressure. The repeated chlorination of 2-amino-4,6-dichloroanisole could give 2-amino-3,4,5,6-tetrachloroanisole, The Schiemann reaction of 2-amino-4-chloroanisole and 2-amino-4,6-dichloroanisole could give 2-fluoro-4-chloroanisole and 2-fluoro-4,6-dichloroanisole, respectively. The repeated chlorination of these fluorochloroanisoles could give 2-fluoro-3,4,5,6-tetrachloroanisole. In each chlorination process, the components of products were examined by means of NMR spectrometry and the chlorination reaction was repeated without isolating each isomeric product. The feasibility of the present routes of preparations was discussed in respects to the conveniency of reaction conditions and respective overall yields of the processes.

• Applied Chemistry for Engineering
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• v.7 no.3
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• pp.453-463
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• 1996

The chlorination of reagent PbS and natural ore galena with $NH_4Cl$ was investigated to find a new extraction metallurgical process of lead. The proper conditions for the chlorination of galena were that reaction temperature ; $425^{\circ}C$, $NH_4Cl$ weight ratio to galena ; 4.0 and reaction time ; 2hrs. Under these conditions, PbS was successfully chlorinated to $PbCl_2$ and the conversion was 90%. And also $NH_4Cl$ was effectively decomposed and was separated $NH_3$ and HCl. HCl was a chlorinating agent and 90% of $NH_3$ was recovered through this chlorination reaction.

• Resources Recycling
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• v.16 no.6
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• pp.34-38
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• 2007

For recycling of tantalum from obsolete condenser, physical separations and chlorination of tantalum scraps with $Cl_2$ and $CCl_4$ were investigated. The recovery ratio of tantalum from obsolete condenser was 98% by using a multidisciplinary process of crushing by stamp mill, wet gravity separation by the shaking table, and air classification. In the chlorination reaction of non-oxidized Ta anode with $Cl_2$, the highest weight loss ratio is at least 60%, while in the chlorination reaction of Ta anode with $CCl_4$, the reaction rate for the oxidized Ta anode is faster than that of the non-oxidized Ta anode.