• 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.

• Journal of Powder Materials
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• v.28 no.2
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• pp.164-172
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• 2021

Titanium is the ninth most abundant element in the Earth's crust and is the fourth most abundant structural metal after aluminum, iron, and magnesium. It exhibits a higher specific strength than steel along with an excellent corrosion resistance, highlighting the promising potential of titanium as a structural metal. However, titanium is difficult to extract from its ore and is classified as a rare metal, despite its abundance. Therefore, the production of titanium is exceedingly low compared to that of common metals. Titanium is conventionally produced as a sponge by the Kroll process. For powder metallurgy (PM), hydrogenation-dehydrogenation (HDH) of the titanium sponge or gas atomization of the titanium bulk is required. Therefore, numerous studies have been conducted on smelting, which replaces the Kroll process and produces powder that can be used directly for PM. In this review, the Kroll process and new smelting technologies of titanium for PM, such as metallothermic, electrolytic, and hydrogen reduction of TiCl₄ and TiO₂ are discussed.

• Korean Journal of Metals and Materials
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• v.50 no.10
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• pp.745-751
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• 2012

The Kroll process for magnesium reduction of titanium tetrachloride is used for mass production of titanium sponge. The present study was conducted in a lab scale reactor to develop a better understanding of the mechanism of titanium sponge formation in the Kroll reactor with respect to reaction degrees and the feeding rate of $TiCl_4$. The $MgCl_2$ produced during the initial stage of the reaction was not sunk into the molten magnesium, but covered the surface of the molten magnesium. As a result, subsequently fed $TiCl_4$ reacted with Mg exposed on the edge of molten $MgCl_2$ in the crucible. Therefore, titanium sponge grew toward the center of the crucible from the edge. The temperature of the molten magnesium increased remarkably with the increasing feeding rate of $TiCl_4$. Consequently, fed $TiCl_4$ reacted at the upper side of the crucible with evaporated Mg, and produced titanium on the upper surface of the crucible wall, which increased considerably with the feeding rate of $TiCl_4$.

• Resources Recycling
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• v.25 no.4
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• pp.68-79
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• 2016

Titanium is the ninth most abundant element in the Earth's crust. It is also the forth most abundant structural metal after aluminum, iron and magnesium. Titanium is conventionally produced by the Kroll process. New processes to produce metallic titanium have been currently developed by many researchers in the world. In this study, the existing technologies, including both commercial and developmental processes, categorized into three groups: those by metallothermic reduction of $TiCl_4$ and $TiO_2$, those by electrolytic reduction of $TiO_2$ and hydrogen reduction of Ti compounds. Their mechanisms for reduction and their features are summarized and discussed in the view of industrial application.

• 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.