Optimization and Kinetics of Zirconium Oxychloride (ZOC) Dissolution Using HNO3


Maria Veronika Purwani(1), Muzakky Muzakky(2*)

(1) Center for Accelerator Science and Technology - National Nuclear Energy Agency, Jl. Babarsari No. 21, POB 6101 ykbb, Yogyakarta 55281, Indonesia
(2) Center for Accelerator Science and Technology - National Nuclear Energy Agency, Jl. Babarsari No. 21, POB 6101 ykbb, Yogyakarta 55281, Indonesia
(*) Corresponding Author


The design of chemical reactor can not be separated from the optimization data and reaction kinetics obtained from the experimental measurement. Through the idea of making the dissolution reactor design, the purpose of this research is to obtain optimization data and dissolution kinetics of Zirconium Oxide Chloride (ZOC) using HNO3. The design of the solvent reactor is required to make the feedstock in the liquid-liquid extraction process continuously. The extraction process is a mini-pilot plant unit as a nuclear-grade zirconia manufacture. The dissolution optimization was carried out by dissolving ZOC solids of zircon sand processed products using HNO3 in a container with some variation of contact time, HNO3 concentration and temperature. While the kinetics data was gained by extracting from the optimization data obtained based on the formula of reaction orders. The investigation result with 6 gr of ZOC and 6M HNO3 concentration obtained the best contact optimum time of 2 minutes and the conversion number (α) of 0.96. The dissolution reaction mechanism was estimated in accordance with the reaction of order 1 with the  k value of 1.5879 minutes-1. It was predicted that the reaction mechanism of ZOC dissolution in HNO3 begins with diffuse control and is followed by chemical reaction control. With increasing conversion temperature, the conversion will increase to 0.98, while the reaction also follows the reaction order 1. The optimum temperature at 60 °C, and the correlation between temperature (T) with the calculated reaction rate constant (k) according to the Arrhenius formula yielded an equation of ln k = - 4191,6 / T + 13,903 or k = 13,903.e- 4191,6 / T, with the frequency factor A = 1091430 and the activation energy E = 34,848 kJ / mole.


Keywords: ZOC, mini pilot plant, optimization, kinetics, Arrhenius

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[1] Setyawan, W., 2015, Pengembangan teknologi pengolahan pasir zirkon lokal Indonesia menjadi produk zirkonium grade industri dan nuklir untuk mendukung MP3EI, Laporan akhir Program Insinas Riset SiNas, PSTA-Batan, Yogyakarta.

[2] Wang, L.Y., and Lee. M.S., 2014, Separation of zirconium and hafnium from nitric acid solutions with LIX 63, PC 88A and their mixture by solvent extraction, Hydrometallurgy, 150, 153–160.

[3] Biswas, R.K., Habib, M.A., and Islam, M.R., 2010, A novel method for processing of Bangladeshi zircon: Part II: Leaching of zircon-caustic fused mass by hydrochloric acid, Hydrometallurgy, 103 (1-4), 130–135.

[4] Liu, J., Song, J., Qi, T., Zhang, C., and Qu., J., 2016, Controlling the formation of Na2ZrSiO5 in alkali fusion process for zirconium oxychloride production, Adv. Powder Technol., 27 (1), 1–8.

[5] Biyantoro, D., Isyuniarto, and Masrukan, 2016, Pemisahan Zr-Hf secara sinambung menggunakan mixer settler, Urania, 22 (3), 155–166.

[6] Cox, R.P., and Bayer, G.H., 1955, Separation of hafnium from zirconium using tributyl phosphate, Ames Laboratory ISC Technical Reports, 109, Iowa State University.

[7] Pandey, G., Mukhopadhyay, S., Renjith, A.U., Joshi, J.M., and Shenoy, K.T., 2016, Recovery of Hf and Zr from slurry waste of zirconium purification plant using solvent extraction, Hydrometallurgy, 163, 61–68.

[8] Banda, R., and Lee, M.S., 2015, Solvent extraction for the separation of Zr and Hf from aqueous solutions, Sep. Purif. Rev., 44 (3), 199–215.

[9] Aliakbari, M., Saberyan, K., Noaparast, M., Abdollahi, H., and Akcil, A., 2014, Separation of hafnium and zirconium using TBP modified ferromagnetic nanoparticles: Effects of acid and metals concentrations, Hydrometallurgy, 146, 72–75.

[10] Biswas, R.K., Habib, M.A., and Hayat, M.A., 2004, Kinetics of solvent extraction of zirconium (IV) from chloride medium by D2EPHA in kerosene using the Lewis cell technique: A comparison with single drop technique, Pak. J. Sci. Ind. Res., 47 (5), 325–331.

[11] Murali, R., Augustine, E., Ganesh, S., Desigan, N., Pandey, N.K., Mallika, C., Mudali, U.K., and Joshi, J.B., 2016, Kinetics of extraction of zirconium with TBP, The 7th DAE-BRNS Biennial Symposium on Emerging Trends in Separation Science and Technology, SESTEC-2016, Indian Institute of Technology Guwahati, Assam, India, 17-20 May 2016.

[12] Barba, A., Jarque, J.C., Orduña, M., and Gazulla, M.F., 2015, Kinetic model of the dissolution process of a zirconium white frit. Influence of the temperature, J. Eur. Ceram. Soc., 35 (2), 751–764.

[13] Pandey, N.K., Murali, R., Augustine, E., Ganesh, S., and Joshi, J.B., 2017, Kinetics of interphase transfer of zirconium between nitric acid and tributyl phosphate solutions, J. Radioanal. Nucl. Chem., 314 (3), 1991–2001.

[14] Levenspiel, O., 1999, Chemical Reaction Engineering, 3rd ed., John Wiley & Sons, New York.

[15] Gharabaghi, M., Irannajad, M., and Azadmehr, A.R., 2013, Leaching kinetics of nickel extraction from hazardous waste by sulphuric acid and optimization dissolution conditions, Chem. Eng. Res. Des., 91 (2), 325–331.

[16] Safari, V., Arzpeyma, G., Rashchi, F., and Mostoufi, N., 2009, A shrinking particle-shrinking core model for leaching of a zinc ore containing silica, Int. J. Miner. Process., 93 (1), 79–83.

[17] Pandey, N.K., Augustine, E., Murali, R., Desigan, N., Mudali, U.K., and Joshi J.B., 2016, Kinetics of extraction of nitric acid into binary mixture of tri-n-butyl phosphate and normal paraffin hydrocarbon, Chem. Eng. Res. Des., 111, 492–503.

[18] Salmi, T., Grénman, H., Wärnå, J., and Murzin, D.Y., 2013, New modelling approach to liquid-solid reaction kinetics: From ideal particles to real particles, Chem. Eng. Res. Des., 91 (10), 1876–1889.

[19] Ayanda, O.S., Adekola, F.A., and Baba, A.A., 2011, Comparative study of the kinetics of dissolution of laterite in some acidic media, JMMCE, 10 (15), 1457–1472.

[20] Miller, J.N., and Miller, J.C., 2010, Statistics and Chemometrics for Analytical Chemistry, 6th ed., Pearson Education Limited, Harlow, UK.

DOI: https://doi.org/10.22146/ijc.38288

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