• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.20 no.2
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• pp.193-207
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• 2022

Thermodynamically, TRUO_x, REO_x, and SrO_x can be chlorinated using ammonium chloride (NH₄Cl) as a chlorinating agent, whereas uranium oxides (U₃O₈ and UO₂) remain in the oxide form. In the preliminary experiments of this study, U₃O₈ and CeO₂ are reacted separately with NH₄Cl at 623 K in a sealed reactor. CeO₂ is highly reactive with NH₄Cl and becomes chlorinated into CeCl₃. The chlorination yield ranges from 96% to 100%. By contrast, U₃O₈ remains as UO₂ even after chlorination. We produced U/REO_x- and U/SrO_x-simulated fuels to understand the chlorination characteristics of the oxide compounds. Each simulated fuel is chlorinated with NH₄Cl, and the products are dissolved in LiCl-KCl salt to separate the oxide compounds from the chloride salt. The oxide compounds precipitate at the bottom. The precipitate and salt phases are sampled and analyzed via X-ray diffraction, scanning electron microscope-energy dispersive spectroscopy, and inductively coupled plasma-optical emission spectroscopy. The analysis results indicate that REO_x and SrO_x can be easily chlorinated from the simulated fuels; however, only a few of U oxide phases is chlorinated, particularly from the U/SrO_x-simulated fuels.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.798-806
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• 1993

In this study we developed the synthesis of high purity tungsten oxide from tungsten chlorides obtained by the chlorination of scheelite in a fluidized bed reactor. Within a minute of dissolution time, tungsten chlorides were almost dissolved in $H_2O_2$ solution. The proper dissolution conditions for the tungsten chlorides were as follows : $H_2O_2$ concentration 0.5%, dissolution temperature $15^{\circ}C$ and $H_2O_2$ amount to 0.5g tungsten chlorides 30ml. Under above conditions, the tungsten oxide prepared from dissolved product was identified as $WO_3$ and the purity of $WO_3$ was 99.53%.

• 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 Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.19 no.2
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• pp.225-231
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• 2021

The reaction between Li₂CO₃ and Cl₂ was investigated to verify its occurrence during a carbon-anode-based oxide reduction (OR) process. The reaction temperature was identified as a key factor that determines the reaction rate and maximum conversion ratio. It was found that the reaction should be conducted at or above 500℃ to convert more than 90% of the Li₂CO₃ to LiCl. Experiments conducted at various total flow rate (Q) / initial sample weight (W_i) ratios revealed that the reaction rate was controlled by the Cl₂ mass transfer under the experimental conditions adopted in this work. A linear increase in the progress of reaction with an increase in Cl₂ partial pressure (pCl₂) was observed in the pCl₂ region of 2.03-10.1 kPa for a constant Q of 100 mL·min^-1 and W_i of 1.00 g. The results of this study indicate that the reaction between Li₂CO₃ and Cl₂ is fast at 650℃ and the reaction is feasible during the OR process.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.1
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• pp.55-61
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• 2013

The recovery of Zr from Zircaloy-4 (Zry-4) cladding hulls using a chlorination method was demonstrated for complete conversion of Zr into $ZrCl_4$. A chlorination reaction was performed by reacting Zry-4 hulls for 8 h under a 70 cc/min $Cl_2$ + 70 cc/min Ar flow at $380^{\circ}C$. The initial weight of the reactant (51.7 g) decreased to 0.49 g after 8 h of operation, which is only 0.95wt% of the initial weight. The weight of the total reaction products was 121.7 g with a high Zr purity of 99.80wt%. Fe and Sn were identified as major (0.18wt%) and minor (0.02wt%) impurities of the reaction products, respectively. It was also shown that Zr exhibited a high recovery ratio of 96.95wt% with a relatively small experimental loss of 2.34wt%. Observation of the reaction residues revealed that the chlorination reaction was dominant along the longitudinal direction, and surface oxide layers remained as reaction residues. The high purity and recovery ratio of Zr proposed the feasibility of the chlorination technique as an effective hull waste treatment method.

• Journal of Korean Society of Water and Wastewater
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• v.20 no.6
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• pp.813-822
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• 2006

Soluble manganese removal was analyzed as a function of filter media, filter depth, presence or absence of chlorination, and surface manganese oxide concentration in water treatment processes. Sand, manganese oxide coated sand (MOCS), sand+MOCS, and granular activated carbon(GAC) were used as filter media. Manganese removal, surface manganese oxide concentration, turbidity removal, and regeneration of MOCS in various filter media were investigated. Results indicated that soluble manganese removal in MOCS was rapid and efficient, and most of the removal happened at the top of the filter. When filter influent (residual chlorine 1.0mg/L) with an average manganese concentration of 0.204mg/L was fed through a filter column, the sand+MOCS and MOCS columns can remove 98.9% and 99.2% of manganese respectively on an annual basis. On the other hand, manganese removal in sand and the GAC column was minimal during the initial stage of filtration, but after 8 months of filter run they removed 99% and 35% of manganese, respectively. Sand turned into MOCS after a certain period of filtration, while GAC did not. In MOCS, the manganese adsorption rate on the filter media was inversely proportional to the filter depth, while the density of media was proportional to the filter depth.

• Journal of the Korean Chemical Society
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• v.44 no.3
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• pp.229-236
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• 2000

The reaction of 6-chloro-2-hydrazinoquinoxaline 4.oxide(10) with acetylacetone or dibenzoylmethane gave 6-chloro-2-(3,5-disubstituted pyrazol-1-yl)quinoxaline 4-oxides (11) through the intramolecular·cyclization.The chlorination of compound 11 with phosphoryl chloride afforded 3,6-dichloro-2-(3,5-disubstituted pyrazol-1-yl)quinoxalines (12), whose reaction with hydrazine hydrate provided 6-chloro-3-hydrazinodehydes, benzenesulfonyl chloride, substituted benzoyl chlohdes or acyl chlorides gave novel pyrazolylquinoxalines (14-17).

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.18 no.2
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• pp.169-177
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• 2020

Here, the stability of stainless steel 316 (SS-316) was investigated to identify its applicability in the oxide reduction process, as a component in related equipment, to produce a complicated gas mixture composed of O₂ and Cl₂ under an argon (Ar) atmosphere. The effects of the mixed gas composition were investigated at flow rates of 30 mL/min O₂, 20 mL/min O₂ + 10 mL/min Cl₂, 10 mL/min O₂ + 20 mL/min Cl₂, and 30 mL/min Cl₂, each at 600℃, during a constant argon flow rate of 170 mL/min. It was found that the corrosion of SS-316 by the chlorine gas was suppressed by the presence of oxygen, while the reaction proceeded linearly with the reaction time regardless of gas composition. Surface observation results revealed an uneven surface with circular pits in the samples that were fed mixed gases. Thermodynamic calculations proposed the combination of Fe and Ni chlorination reactions as an explanation for this pit formation phenomenon. An exponential increase in the corrosion rate was observed with an increase in the reaction temperature in a range of 300 ~ 600℃ under a flow of 30 mL/min Cl₂ + 170 mL/min Ar.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.12 no.3
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• pp.235-243
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• 2014

Surface oxidation behavior of ZIRLO (ZIRconium Low Oxidation) hulls was investigated using an X-ray photoelectron spectroscopy (XPS) technique. The effects of oxidation time (10-336 h at $500^{\circ}C$) and temperature ($400-700^{\circ}C$ for 10 h) were studied. Deconvolution results of the hulls oxidized at $500^{\circ}C$ revealed that a $ZrO_2$ phase appeared after 24 h (11.86%), and an increase in the $ZrO_2$ ratio was observed when the hulls were oxidized for 336 h (17.93%). On the other hand, the ZrO phase which employed 5.68% in the 10 h oxidized sample disappeared when the oxidation time increased to 24 h. The XPS results also showed that an increase in the oxidation temperature resulted in an increase in the ratio of ZrO, which increased from 0 to 5.68, 8.31, and 9.16% when the oxidation temperature increased from 400 to 500, 600, and $700^{\circ}C$, respectively. $ZrO_2$ phase was observed only in the sample that was oxidized at $700^{\circ}C$. The mechanism of ZrO formation was not conclusive, but it was suggested that a formation of hydroxide might have been accelerated at elevated temperatures leading to a formation of a $Zr(OH)_4$ phase. The relationship between the surface oxidation status of the hulls oxidized at $500^{\circ}C$ and their chlorination reaction feasibility was discussed, and it was suggested that the thickness of the oxide layer is an important parameter that determines the chlorination reaction feasibility.

• Korean Chemical Engineering Research
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• v.44 no.3
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• pp.259-264
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• 2006

The separation and purification of $TaCl_5$is indispensable in the synthetic process of $TaCl_5$by chlorination of tantalum oxide. The reaction products are mainly $TaCl_5$, $NbCl_5$, $TiCl_4$ and $FeCl_2$. However, we need to separate $TaCl_5/NbCl_5$ mixture from the reaction product, because $TaCl_5$ and $NbCl_5$ are easily separated each other by distillation or hydrogen reduction process. In this work, a comparison study was carried out between direct sequence and indirect sequence to obtain $TaCl_5/NbCl_5$ mixture from the reaction product by removing light component, $TiCl_4$ and heavy component, $FeCl_2$ using two distillation columns. It was concluded that the direct sequence gave better results than indirect sequence in the aspect of initial capital costs and the associative operating costs.