• Journal of Powder Materials
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• v.25 no.3
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• pp.213-219
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• 2018

We report a method for preparing rare earth oxides ($Re_xO_y$) from the recycling process for spent Ni-metal hydride (Ni-MH) batteries. This process first involves a leaching of spent Ni-MH powders with sulfuric acid at $90^{\circ}C$, resulting in rare earth precipitates (i.e., $NaRE(SO_4)_2{\cdot}H_2O$, RE = La, Ce, Nd), which are converted into rare earth oxides via two different approaches: i) simple heat treatment in air, and ii) metathesis reaction with NaOH at $70^{\circ}C$. Not only the morphological features but also the crystallographic structures of all products are systematically investigated using field-emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD); their thermal behaviors are also analyzed. In particular, XRD results show that some of the rare earth precipitates are converted into oxide form (such as $La_2O_3$, $Ce_2O_3$, and $Nd_2O_3$) with heat treatment at $1200^{\circ}C$; however, secondary peaks are also observed. On the other hand, rare earth oxides, RExOy can be successfully obtained after metathesis of rare earth precipitates, followed by heat treatment at $1000^{\circ}C$ in air, along with a change of crystallographic structures, i.e., $NaRE(SO_4)_2{\cdot}H_2O{\rightarrow}RE(OH)_3{\rightarrow}RE_xO_y$.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.4
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• pp.303-309
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• 2010

For the pyrochemical process of spent nuclear fuels, recovery of LiCl-KCl eutectic salts is needed to reduce radioactive waste volume and to recycle resource materials. This paper is about recovery of residual LiCl-KCl eutectic salts in radioactive rare earth precipitates (rare earth oxychlorides or oxides) by using a vacuum distillation process. In the vacuum distillation test apparatus, the salts in the rare earth precipitates were vaporized and were separated effectively. The separated salts were deposited in three positions of the vacuum distillation test apparatus or were collected in the filter and it is difficult to recover them. To resolve the problem, a vacuum distillation and condensation system, which is subjected to the force of a temperature gradient at a reduced pressure, was developed. In a preliminary test of the vacuum distillation/condensation recovery system, it was confirmed that it was possible to condense the vaporized salts only in the salt collector and to recover the condensed salts from the salt collector easily.

• Resources Recycling
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• v.28 no.6
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• pp.18-25
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• 2019

In order to recover the cerium contained in the spent nickel metal hydride batteries (NiMH battery), the recovered rare earth complex precipitates from NIMH were converted into rare earth hydroxides through ion exchange reaction to react with NaOH aqueous solution at a reaction temperature of 70 ℃, for 4 hours. Rare earth hydroxides were oxidized by injecting air at 80 ℃ for 4 hours to oxidize Ce³⁺ to Ce⁴⁺. The oxidation rate of cerium was confirmed to be about 25 % through XPS, and the oxidized powder was separated from the rest of the rare earth using the difference in solubility in dilute sulfuric acid. The finally recovered powder has a crystal phase of cerium hydroxide (Ce(OH)₄). The cerium purity of the final product was about 94.6 %, and the recovery rate was 97.3 %.

• Applied Chemistry for Engineering
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• v.18 no.4
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• pp.361-365
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• 2007

The precipitation reaction of some rare earth chlorides ($Ce/Nd/GdCl_3$) in a LiCl-KCl molten salt has been carried out by reaction with oxygen. Identification of rare earth precipitates by reaction with oxygen and effects of oxygen sparging time (max. 420 min) and molten salt temperature ($450{\sim}750^{\circ}C$) on conversion were investigated. In this study, regardless of the oxygen sparging time and the molten salt temperature, oxychlorides (REOCl) for $NdCl_3$ and $GdCl_3$, and an oxide ($REO_2$) for $CeCl_3$ are formed as a precipitate, which are identical with the estimation results of Gibbs free energy of reaction (${\Delta}G_r$). The conversion of rare-earth chlorides into insoluble precipitates was described by using a conversion ratio. The conversion ratio increased exponentially with the oxygen sparging time and finally showed asymptotic value, over 0.999 at $750^{\circ}C$ of the molten salt temperature and over 300 min of sparging time conditions. The conversion ratios were increased with the molten salt temperature. In case of $CeCl_3$, when the sparging time exceed 60 min, the values of the conversion ratio were nearly constant over 0.999 in all experimental temperature conditions.

• Korean Chemical Engineering Research
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• v.47 no.4
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• pp.465-469
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• 2009

Characteristics of oxidation reaction of four lanthanide chlorides(Ce, Nd, Pr and $EuCl_3$) in a oxygen-eutectic(LiCl-KCl) salt bubble column was investigated. From the results obtained from the thermochemical calculations by HSC chemistry software, the most stable lanthanide compounds in the oxygen-used rare earth chlorides system were oxychlorides(EuOCl, NdOCl, PrOCl) and oxides($CeO_2$, $PrO_2$), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides for Eu, Nd and Pr and oxides for Ce and Pr were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two shapes : small cubic(oxide) and large tetragonal (oxychloride) structures. The conversion efficiencies of the lanthanide elements to their molten salt-insoluble precipitates(or compound) were increased with the sparging time and temperature, and Ce showed the best reactivity. In the conditions of $650^{\circ}C$ of the molten salt temperature and 420 min of the sparging time, the conversion efficiencies were over 99% for all the investigated lanthanide chlorides.

• Proceedings of the Korean Powder Metallurgy Institute Conference
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• 2006.09b
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• pp.1048-1049
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• 2006

Rapidly solidified ribbon-consolidation processing was applied for preparation of high strength bulk Mg-Zn-Gd alloys. Mg alloys have been used in automotive and aerospace industries. Rapid solidification (RS) process is suitable for the development of high strength Mg alloys, because the process realizes grain-refinement, increase in homogeneity, and so on. Recently, several nanocrystalline Mg-Zn-Y alloys with high specific tensile strength and large elongation have been developed by rapidly solidified powder metallurgy (RS P/M) process. Mg-Zn-Y RS P/M alloys are characterized by long period ordered (LPO) structure and sub-micron fine grains. The both additions of rare earth elements and zinc remarkably improved the mechanical properties of RS Mg alloys. Mg-Zn-Gd alloy also forms LPO structure in -Mg matrix coherently, therefore, it is expected that the RS Mg-Zn-Gd alloys have excellent mechanical properties. In this study, we have developed high strength RS Mg-Zn-Gd alloys with LPO structure and nanometer-scale precipitates by RS ribbon-consolidation processing. $Mg_{97}Zn_1Gd_2$ and $Mg_{95.5}Zn_{1.5}Gd_3$ and $Mg_{94}Zn_2Gd_4$ bulk alloys exhibited high tensile yield strength (470 MPa and 525 MPa and 566 MPa) and large elongation (5.5% and 2.8% and 2.4%).

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.65-70
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• 2010

The distillation rate on LiCl-KCl eutectic salt under different vacuums from 0.5-50 mmHg was first investigated by using both a non-isothermal and a isothermal thermogravimetric (TG) analysis. Based on the non-isothermal TG data, distillation rate equations as a function of the temperature could be derived. Calculated flux by these model flux equations was in agreement with the distillation rate obtained from isothermal TG analysis. A distillation rate of $10^{-4}-10^{-5}$ mole $cm^{-2}sec^{-1}$ is obtainable at temperatures less than 1300K and vacuums of 0.5-50 mmHg. About a 99% salt distillation efficiency was obtained after an hour at a temperature above 1150 K under 50 mmHg in a small scale distillation test system. An increase in the vaporizing surface area is relatively effective for removing residual salt in the remaining particles, when compared to that for the vaporizing time. Over 99.95% of total distillation efficiency was obtained for a 1-h distillation operation by increasing the inner surface area from $4.52cm^2$ to $12.56cm^2$.

• Economic and Environmental Geology
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• v.34 no.1
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• pp.39-53
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• 2001

Environmental pollution of the Tohyun mine creek area was investigated on the basis of geology, mineralogy and geochemistry. In soils and sediments of the mine area, ${Al_2}{O_3}/{Na_2O}$ and ${K_2}O/{Na_2}O$ ratios are partly negative correlation against ${SiO_2}/{Al_2}{O_3}$, respectively. Geochemical characteristics of some trace and rare earth elements such as V/Ni, Ni/Co, La/Ce, Th/Yb, Th/U, La/Th, ${La_N}/{Yb_N}$, La/Sc and Sc/Th are revealed a narrow range and homogeneous compositions may be explained by simple source lithology. These results suggest that sediments source of the host shale around the mine area could be originated by basic to intermediate igneous rocks. Mineral compositions of soil and sediment near the mine area were partly variable mineralogy, which are composed of quartz, mica, feldspar, chlorite, clay minerals and some pyrite. Soils and sediments with highly concentrated heavy minerals, gravity separated mineralogy, are composed of some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, goethite and various kinds of hydroxide minerals on the polished sections. As normalized by bed rock composition, average enrichment indices of major elements in sediments, precipitates, farmland soils and paddy soils are 1.0, 1.7, 0.9 and 0.8, respectively. Maximum concentration of environmental toxic elements in the mine creek are detected with Ag = 186 ppm, As = 17,100 ppm, Bi = ]27 ppm, Cd = 77 ppm, Cu = 12,299 ppm, Pb = 8,897 ppm, Sb = 1,350 ppm, W = 599 ppm and Zn = 12,250 ppm, which are increasing with total FeO increasing, and extremely high concentrations of surface sediments and precipitates near the waste rock dump. These toxic elements (As, Bi, Cd, Cu, Pb, Sb, W and Zn) of the samples, normalizing by host rock concentration, revealed that average enrichment index is 106.0 for sediments, 279.6 for precipitates, 3.5 for farmland soils and 1.6 for paddy soils. However, on the basis of EPA values, enrichment indices of all the samples are 40.7, 121.4, 1.3 and 0.6, respectively.