• 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.

• Resources Recycling
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• v.26 no.5
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• pp.54-60
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• 2017

In this study, we investigated the effect of $TiCl_4$ injection time on the Kroll reaction at a given weight ratio of $TiCl_4$ and Mg. The reduction reaction was investigated by measuring the temperature change according to $TiCl_4$ injection time and observing the cross section and appearance of the Ti sponge after the reaction. The temperature increment due to Kroll reaction heat generation was found to be linearly proportional to the $TiCl_4$ feed rate. In the graph of $TiCl_4$ injection time and reduction tank temperature, initial temperature peaks were observed irrespective of the injection conditions. This is interpreted to mean a temporary interruption of reaction due to $MgCl_2$ formation after the initial Kroll reaction. In addition, when the cross section of the sponge was observed, a large amount of spherical Mg particles was observed in $MgCl_2$. We can infer that this is the process of continuously feeding the unreacted Mg surface, so that a continuous Kroll reaction takes place. The sponge appearance showed that the coalescence or growth of the Kroll reacted Ti particles can be controlled by the cooling rate.

• 기계와재료
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• v.21 no.2
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• pp.136-145
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• 2009

최근 타이타늄 제련기술 발달과 함께 원광석에서 고품위 타이타늄 분말을 연속적으로 제조할 수 있는 방법 들이 소개되고 있다. 이들 분말 타이타늄의 제조방법은 기존의 Kroll process에서 제조되는 스폰지를 재용해하여 분말을 만드는 방법에 비하여 원가절감 측면에서 매우 유리하다. 이들 신공정으로 제조된 괴상의 고품위 타이타늄 분말을 이용하여 정형가공을 수행하면 상당한 원가절감이 예상되고, 이에 따라 그 사용량은 급격히 증가되리라 판단된다. 본 지에서는 저가 타이타늄 개발과 관련하여, 최근의 분말 타이타늄의 제조방법에 대하여 소개하고 이를 이용하는 공정기술에 대한 내용을 소개하고자 한다.

• Resources Recycling
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• v.26 no.6
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• pp.3-9
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• 2017

In this study, plasma arc remelting behaviors according to arc current, arc voltage, and types of plasma gas were investigated using Kroll processed Ti sponges as anode. In the discharge pressure range of vacuum pump ($200{\sim}300kgf/cm^2$), the arc voltage did not vary greatly with the increase of discharge pressure at a given arc length. This means that the pressure in the vacuum chamber during operation hardly changes and the atmospheric pressure maintains. Under various conditions of arc currents (700~900A), the arc voltage slightly increased with arc current. The effects of anode materials and operational variables on the arc length-arc voltage relationship were compared with the results in previous studies. When the atmospheric gas changed from argon to helium, double effect of improvement on the output of the steady state was observed. The increase of output in the plasma arc device was accompanied by an increase in the melting rate of the Ti sponge and the quality of the ingot surface was also improved. The plasma arc remelting of the new scrap titanium and the old scrap zirconium alloy could result in the fabrication of an ingot with high surface quality.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.13 no.1
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• pp.11-19
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• 2015

The production of nuclear fuel cladding tube is expected to increase with the nuclear power plant expansion. Zirconium(Zr) scrap that is generated during manufacturing is also expected to increase. Zr electrorefining experiment was carried out in the fluoride salt of LiF-KF-ZrF₄ using multiple electrode for scale up and improving throughput Zr electrorefiner develop-ment. The Zr reduction peak observed at-0.8 V(vs.Ni). Polarization behavior showed that the amount of applied current increases because of decreasing cell resistance as the number of cathode increases. Experimental results showed the highest recovery rate about 98% at lowest current density of 25.64 mA/cm² using 6 electrodes. XRD and TG analysis result show that pure Zr was recovered 99.92% and ICP analysis shows that lower impurity content than conventional impurity content of the Anode(97.8%). Electrorefining consumes energy about 7.15 kWh/kg less than 39.7% compared to the Kroll process using 6 electrode width of 20 mm and height of 65 mm. Because of increasing cell efficiency and recovery rate, using multiple cathode is determined as an efficient technique for scale up electrorefining Zr scrap.