Published at : 21 Jul 2020
Volume : IJtech Vol 11, No 3 (2020)
DOI : https://doi.org/10.14716/ijtech.v11i3.2581
|Kris Tri Basuki||Department of Nuclear Chemical Engineering, Polytechnic Institute of Nuclear Technology (STTN), Jl. Babarsari, Yogyakarta 55821, Indonesia|
|Alfiyatur Rohmaniyyah||Department of Nuclear Chemical Engineering, Polytechnic Institute of Nuclear Technology (STTN), Jl. Babarsari, Yogyakarta 55821, Indonesia|
|Wahyu Rachmi Pusparini||Accelerator Science and Technology Center (PSTA) - National Nuclear Energy Agency (BATAN), Jl. Babarsari, Yogyakarta 55821, Indonesia|
|Andri Saputra||Department of Nuclear Chemical Engineering, Polytechnic Institute of Nuclear Technology (STTN), Jl. Babarsari, Yogyakarta 55821, Indonesia|
Xenotime sand, a byproduct of the tin mining
process of PT Timah, is one of the potential gadolinium (Gd) resources. Because
of similarities in their physical and chemical properties, it is difficult to
separate and purify Gd from rare earth elements (REEs) in xenotime sand (i.e.,
yttrium and dysprosium). In the present work, Gd was separated through an extraction
process using Cyanex 572. The extraction feed solution was prepared by
digesting the REE oxalate in NaOH to obtain REE(OH)3. The effects of
the extraction parameters (i.e., stirring time and rate, feed pH and
concentration, and Cyanex 572 concentration) were examined via a batch
experiment. The optimum results of Gd separation from yttrium concentrate were
achieved when the process conditions included a 250-rpm stirring rate for 30
minutes, a 150×103-ppm
feed concentration at pH 3, and a 30% Cyanex 572 concentration. These
conditions gave distribution coefficient results for Y, Gd, and Dy of about
0.031, 0.827, and 1.060, respectively; separation factors of Gd-Y and Gd-Dy of
about 26.482 and 0.780, respectively; and extraction efficiencies for Y, Gd,
and Dy of about 3.119%, 46.627%, and 53.007%, respectively.
Cyanex 572; Dysprosium; Extraction; Gadolinium; Separation; Yttrium
Gadolinium (Gd), yttrium (Y), and dysprosium (Dy) are included in a group of 17 chemically similar metallic elements called rare earth elements (REEs). Gd has excellent scintillation properties and a high magnetic moment compared with other REEs. In the nuclear industry, gadolinium oxide is used for radiation-shielding ceramic compositions (Gupta and Krishnamurthy, 2005) and control rods (Jaworski and Gawlowski, 2015) as well as in making optical fibers. Gd is also added to optical glasses for use in electro-optical and magneto-optical systems. Gd (1%) in iron, chromium, and related alloys improves resistance to oxidation and high temperatures (Xu et al., 2014). Y is also an important element used in electrical material (Rahmawati et al., 2015), for example, to increase ionic conductivity (Shakthinathan et al., 2012).
Data from 2014 shows that China is the world’s largest REE deposit, containing about 58% of the total global deposit of 154,135 tons. Meanwhile, the Indonesian REE deposit hypothesis shows a very small amount, about <1% of the total world deposit (Gunradi et al., 2019). The main minerals containing REEs found in Indonesia are xenotime, monazite, and zircon, associated with cassiterite obtained from alluvial tin mining. Granite, pegmatite, and metamorphic, ultramafic, and alluvial rocks are among the types of rocks that may contain REEs in Indonesia. These REE minerals are concentrated in the Riau Islands, Bangka Belitung, and parts of West Kalimantan (Virdhian and Afrilinda, 2014; Gunradi et al., 2019). Xenotime sand, a byproduct of the tin mining process of PT Timah, is one of the potential gadolinium resources of REEs. It contains rare earth phosphate minerals such as 29.53% Gd, 7.76% Y, and 2.58% Dy (Atmawinata et al., 2014). In Indonesia, xenotime has not been further processed to obtain pure REEs or to obtain its oxides. If Gd, Y, and Dy can be separated from other materials properly, this will increase xenotime’s economic value.
Because of similarities in REEs’ physical and chemical properties, it is difficult to separate and purify Gd from other REEs (other lanthanides). To separate Gd in high purity, it is necessary to find the most efficient and feasible technology (Fisher and Kara, 2016). High-purity REEs like Gd have received considerable attention in recent years due to various industrial applications, limited supply, significant price fluctuations, and market availability (Hasan et al., 2009; Torkaman et al., 2013).
Many methods, such as solvent extraction, fractional crystallization, ion exchange, and chemical precipitation, are used to purify and separate REEs. A well-known method of purification and separation is solvent extraction (Andriayani et al., 2015; Wahab et al., 2016). On an industrial scale, solvent extraction is the most successful method for the extraction and separation of REEs (Wang et al., 2014). The development of new extractants and more efficient extraction techniques is essential for maintaining a stable supply of REEs to meet rapidly increasing demand on a global scale (Tunsu et al., 2016).
Organophosphorus and amine are extractants commonly used to extract REEs in acid solutions. Cytec Industries, Inc., introduced a new extractant, known as Cyanex 572, which belongs to the type of organophosphorus extractant whose active ingredient is a mixture of phosphinic and phosphonic acid with the active group of POOH. This type of extractant is known for its selectivity to certain metals, and one such extractant is used for the separation of metals from heavy REE groups using the liquid-liquid extraction separation method (solvent extraction). Cyanex 572 is specifically designed to extract heavy REEs under the required operating conditions of low acidity (Cytec, 2014). Cyanex 572 has been studied for extracting REEs and Th from waste residues, including ion-absorbed minerals or fluorescent lamps (Tunsu et al., 2016). Cyanex 572 synergized with n-octyl diphenyl phosphate (ODP) has also been studied for extracting Th from leaching solutions of rare earth residues (Zhou et al., 2019). El-Hefny et al. (2018) used Cyanex 572 to separate Y(III) and Dy(III) in hydrochloric and nitric acid solutions.
extraction was studied by Vijayalakshmi et al.
(2014) using EHEHPA as a solvent and by Taufan
et al. (2008) using DBDTC. Torkaman et al.
(2016) also studied Gd extraction using D2EHPA and Cyanex 301. This study
proposes to investigate the separation of Gd from xenotime sand by an
extraction process using Cyanex 572 solvent in nitric acid solution. Nitric
acid has been used to dilute REE(OH)3
or Gd and other elements in REE(OH)3 (Taufan
et al., 2008).
Based on the results of the present research, the optimum conditions for
the separation of Gd from yttrium concentrate were obtained at a 30-minute
stirring time, a 250-rpm stirring rate, a feed concentration of 150×103 ppm with pH 3, and a
30% Cyanex 572 concentration. The distribution coefficient values of Y, Gd, and
Dy of about 0.031, 0.827, and 1.060, respectively. The separation factor value
of Gd-Y was 26.482, while that of Gd-Dy was 1.5276. The extraction efficiency
values of Y, Dy, and Gd were 3.119%, 53.007%, and 46.662%, respectively.
Andriayani, Raja, S.L., Sihotang, H., Sofyan, N., 2015. Optimization of Silicon Extraction from Tanjung Tiram Asahan Natural Sand through Magnesiothermic Reduction. International Journal of Technology, Volume 6(7), pp. 1174–1183
Atmawinata, A., Ferry, Y., Sakri, W., Roosmariharso, Drajadm, I., Adriano, A., Yus, S., Wartam R., Massarudin, Denny, N., Ari, I.S., Shinta, V., Sih, W., Bayu, P.W., Ardhana, 2014. Review of Strengthening Industrial Structures Mapping the Potential of Rare Earth Metals in Indonesia. Ministry of Industry, Jakarta
Aziz, N., 2017. Effect of Temperature to Adsorption Capacity and Coefficient Distribution on Rare Earth Elements Adsorption (Y, Gd, Dy) Using SIR. Master’s Thesis, Graduate Program, Universitas Gadjah Mada, Yogyakarta
Belabassi, Y., Gushwa, A.F., Richards, A.F., Montchamp, J., 2008. Structural Analogues of Bioactive Phosphonic Acids: First Crystal Structure Characterization of Phosphonothioic and Boranophosphonic Acids. Phosphorus, Sulfur, and Silicon and the Related Elements, Volume 183(9), pp. 2214–2228
Bentouhami, E., Bouet, G.M., Meullemeestre, J., Vierling, F., Khan, M.A., 2004. Physicochemical Study of the Hydrolysis of Rare-Earth Elements (III) and Thorium (IV). C. R. Comptes Rendus Chimie, Volume 7(5), pp. 537–545
Braatz, A.D., Antonio, M.R., Nilsson, M., 2016. Structural Study of Complexes Formed by Acidic and Neutral Organophosphorus Reagents. Dalton Transactions, pp. 1–30
Cytec, 2014. Cyanex 572 Solvent Extraction Reagent. Available Online at: https://www.cy tec.com/sites/default/files/files/Cytec_Cyanex_572_Final.pdf, Accessed on December 28, 2017
Ding, H.J., Niu, Y.N., Xu, Y.B., Yang, W.F., Yuan, S.G., Qinm, Z., Wu, X.L., 2007. Liquid-liquid Extraction of Protactinium (V) using Tri-iso-octylamine. Journal of Radioanalytical and Nuclear Chemistry, Volume 272(2), pp. 263–266
Effendy, N., Basuki, K.T., Biyantoro, D., Perwira, N.K., 2017. Separation of Gadolinium (Gd) Using a Synergistic Mixture of Solvent TOPO and D2EHPA Extraction Method. In: IOP Conference Series: Materials Science and Engineering
El-Hefny, N.E., Gasser, M.S., Emam, Sh.Sh., Mahmoud, W.H., Aly, H.F., 2018. Comparative Studies on Y(III) and Dy(III) Extraction from Hydrochloric and Nitric Acids by Cyanex 572 as a Novel Extractant. Journal of Rare Earths, Volume 36(12), pp. 1342–1350
Fisher, K., Kara, D., 2016. Determination of Rare Earth Elements in Natural Water Samples: A Review of Sample Separation, Preconcentration and Direct Methodologies. Analytica Chimica Acta, Volume 935, pp. 1–29
Gunradi, R., Tampubolon, A., Pardiarto, B., Sunuhadi, D.N., Hilman, P.M., Awaludin, M., Sayekti, B., Faisal, R.M., Hartaja, M.H.W., Sulaeman, Heditama, D.M., Nugraha, R.S., 2019. Rare Earth Elements Potential of Indonesia. Ministry of Energy and Mineral Resources of Indonesia, Bandung
Gupta, C.K., Krishnamurthy, N., 2005. Extractive Metallurgy of Rare-Earths. CRC Press, London
Hasan, M.A., Aglan, R.F., El-Reefy, S.A., 2009. Modeling of Gadolinium Recovery from Nitrate Medium with 8-hydroxyquinoline by Emulsion Liquid Membrane. ?Journal of Hazardous Materials, Volume 166, pp. 1076–1081
Jaworski, J., Gawlowski, G., 2015. Production and Properties of Composite Material Comprising Gd Multiscale Particles. Management and Production Engineering Review, Volume 6(1), pp. 16–30
Kislik, V.S., 2012. Solvent Extraction: Classical and Novel Approaches. Elsevier, Netherlands
Kuila, S.K., Kundu, T.K., 2018. Adsorption Studies of Gadolinium ion on Graphitic Carbon Nitride. In: IOP Conference Series: Materials Science and Engineering
Ma, L., Zhao, Z., Dong, Y., Sun, X., 2017. Separation and Purification Technology: A Synergistic Extraction Strategy by Cyanex 572 and Cyanex 923 for Th (IV) Separation. Separation and Purification Technology, Volume 191, pp. 307–313
Nejad, H.H., Kazemeini, M., 2012. Optimization of Platinum Extraction by Trioctylphosphine Oxide in the Presence of Alkaline-Metal Salts. Procedia Engineering, Volume 42, pp. 1302–1312
Rahmawati, F., Permadani, I., Syarif, D.G., Soepriyanto, S., 2015. Electrical Properties of Various Composition of Yttrium Dopedzirconia Prepared from Local Zircon Sand. International Journal of Technology, Volume 8(5), pp. 939–946
Rohiman, A., Buchari., Amran, M.B., Syah, Y.M., Rusnadi, 2008. Syntheses and Performance of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP) on the Extraction of Ce3+, La3+, and Gd3+ by Solvent Impregnated Resin (SIR) Method. In: Proceeding of the International Seminar on Chemistry, ISBN 978-979-18962-0-7, pp. 377–380
Shakthinathan, G., Raju, S., Chandrasekaren, U., 2012. Thermal Characteristic of Yttria-stabilized Zirconia Nano Lubricants. Thermal Science, Volume 16(2), pp. 481–487
Soeezi, A., Rahimi, E., Mohaghegh, N., 2015. Investigating the Effect of Concentration and Stirring Time on Copper Extraction Process from Pregnant Liquid Solution (PLS), Case study: Sungun Copper Mine. International Journal of Research in Chemical, Metallurgical and Civil Engineering, Volume 2, pp. 33–35
Taufan, M., Hastiawan, I., Mulyasih, Y., 2008. Solvent Extraction of Gadolinium as a Complex with Di-n-butyldithiocarbamates. In: Proceeding of the International Seminar on Chemistry 2008, pp. 175–179
Torkaman, R., Moosavian, M.A., Safdari, J., Torab-Mostaedi, M., 2013. Synergistic Extraction of Gadolinium from Nitrate Media by Mixtures of Bis (2,4,4-trimethylpentyl) Dithiophosphinic Acid and Di-(2-ethylhexyl) Phosphoric Acid. Annals of Nuclear Energy, Volume 62, pp. 284–290
Torkaman, R., Torab-Mostaedi, M., Safdari, J., Moosavian, M.A., 2016. Kinetics of Gadolinium Extraction with D2EHPA and Cyanex301 using Single Drop Column. Rare Metals, Volume 35, pp. 487–494
Tunsu, C., Lapp, J.B., Ekberg, C., Retegan, T., 2016. Selective Separation of Yttrium and Europium using Cyanex 572 for Applications in Fluorescent Lamp Waste Processing. Hydrometallurgy, Volume 166, pp. 98–106
Vijayalakshmi, R., Singh, D.K., Kotekar, M.K., Singh, H., 2014. Separation of High Purity Gadolinium for Reactor Application by Solvent Extraction Process. Journal of Radioanalytical and Nuclear Chemistry, Volume 300, pp. 129–135
Virdhian, S., Afrilinda, E., 2014. Characterization of Tin-transport Rare Earth Elements and Potentials of Industrial Development based on Rare Earth Elements. Metal Indonesia, Volume 36(2), pp. 61–69
Wahab, A.A.A., Chang, H.S., Som, A.M., 2016. Stoichiometry of Cu(II) Ion Extraction with Di-2-ethylhexylphosphoric Acid Dissolved in Waste Palm Cooking Oil. International Journal of Technology, Volume 5(5), pp. 530–537
Wang, M.Y., Wang, X.W., Jiang, C.J., Tao, C.F., 2014. Solvent Extraction of Molybdenum from Acidic Leach Solution of Ni-Mo Ore. Rare Metals, Volume 33(1), pp. 107–110
Wang, Y., Li, F., Zhao, Z., Dong, Y., Sun, X., 2015. The Novel Extraction Process based on CYANEX® 572 for Separating Heavy Rare Earths from Ion-adsorbed Deposit. Separation and Purification Technology, Volume 151, pp. 303–308
Xu, K.D., Ren, Z.M., Li, C.J., 2014. Progress in Application of Rare Metals in Supperalloys. Rare Metals, Volume 33(2), pp. 111–126
Yuliusman, 2015. Yttrium Metal Recover from Fluorescent Lamp Waste with Liquid-Liquid Extraction Method using Extraction of Cyanex 272. In: Proceedings of the National Seminar on Chemical Engineering UNPAR, University of Indonesia, Jakarta