The Recovery of Pure Zinc from Spent Pickling Liquor by Combining Anion Exchange and Electrodeposition
Keywords:spent pickling liquor, anion-exchange separation, Zn electrodeposition, Fe impurity
Zn recovery from spent pickling liquors (SPL) from hot dip galvanization was examined with modelled solutions by combining anion exchange separation and electrodeposition processes. The solution was purified to be suitable for the electrodeposition of Zn with the main goal of eliminating the iron content. The anion-exchange resin bed in a chromatographic column primarily retained Zn, while divalent Fe was removed in the loading and rinsing steps. At the end of the process, the elution of Zn was carried out by a significantly reduced Cl– ion background. In parallel with the purification process, the potentiodynamic study (1 min runs at 40 mV/s polarization speed) of Zn electrodeposition in the series of Fe concentrations was examined. During the separation process, the preliminary reduction of the iron to its divalent state was found to be of utmost importance. The separation of iron could be improved by controlling the preliminary reduction. It was found that the effect of iron concentration on the polarization curves is complex. Initially, hydrogen bubble formation causes inhibition, but at higher iron concentrations a Zn-Fe deposit is soon formed, promoting hydrogen evolution, thereby depressing polarization but also the current efficiency. The loss of the dendritic structure obtained from pure zinc solutions also characterizes the effect of mixed Fe-Zn deposition. In order to recover pure zinc at the cathode, the pre-purification of the Zn electrolyte is essential.
D. D. N. Singh: Pickling, Rinsing and Fluxing of Steels before Galvanizing. National Metallurgical Laboratory, Jamshedpur, 1997.
A. Devi, A. Singhal, R. Gupta and P. Panzade: A study on treatment methods of spent pickling liquor generated by pickling process of steel. Clean Techn. Environ. Policy, Vol. 16, pp. 1515–1527, 13 July 2014, https://doi.org/10.1007/s10098-014-0726-7
M. Regel-Rosocka: A review on methods of regeneration of spent pickling solution from steel processing. Journal of Hazardous Material, Vol. 177, pp. 57–69, 2010. https://doi.org/10.1016/j.jhazmat.2009.12.043
K. H. Lum, G. W. Stevens and S. E. Kentish: Development of a process for the recovery of zinc sulphate from hot-dip galvanizing spent pickling liquor via two solvent extraction steps. Hydrometallurgy, Vol. 142, pp. 108–115, 2014. https://doi.org/10.1016/j.hydromet.2013.11.016
U. Kerney: Treatment of spent pickling acids from hot dip galvanising. Resources, Conservation and Recycling, Vol. 10, pp. 145–151, 1994. https://doi.org/10.1016/0921-3449(94)90047-7
G. Csicsovszki, T. Kekesi and T. I. Torok: Selective recovery of Zn and Fe from spent pickling solutions by the combination of anion exchange and membrane electrowinning techniques. Hydrometallurgy, Vol. 77, pp. 19–28, 2005. https://doi.org/10.1016/j.hydromet.2004.10.020
I. Ortiz, E. Bringas, M. Fresnedo San Roman and A. Miren Urtiaga: Selective separation of zinc and iron from spent pickling solutions by membrane-based solven extraction: process viability. Separation Science and Technology, Vol. 39, No. 10, pp. 2441–2455, 2004, https://doi.org/10.1081/SS-120039320.
A. Arguillarena, M. Margallo, A. Arruti-Fernandez, J. Pinedo, P. Gomez and A. Urtiga: Scale-up of membrane-based zinc recovery from spent pickling acids of hotdip galvanizing. Membranes, Vol. 10, p. 444, 2020. https://doi.org/10.3390/membranes10120444
Z. Liu, X. Yu, G. Xie, Y. Lu, Y. Hou and E. He: Influence of nickel on cathode process of zinc electrowinning. Hydrometallurgy, Vols. 125–126, pp. 29–33, 2012. https://doi.org/10.1016/j.hydromet.2012.05.002
D. Herrero, P. L. Arias, J. F. Cambra and N. Antunano: Studies on impurity iron removal from zinc electrolyte using MnO2-H2O2. Hydrometallurgy, Vol. 105, pp. 370–373, 2011, https://doi.org/10.1016/j.hydromet.2010.11.010.
P. E. Tsakiridis, P. Oustadakis, A. Katsiapi and S. Agatzini-Leonardou: Hydrometallurgical process for zinc recovery from electric arc furnace dust (EAFD). Part II: Downstream processing and zinc recovery by electrowinning. Journal of Hazardous Materials, Vol. 179, pp. 8–14, 2010. https://doi.org/10.1016/j.jhazmat.2010.04.004
S. B. Zueva, F. Farella, V. Innocenzi, I. De Michelis, V. Corradini, N. M. Ippolito and F. Veglio: Recovery of zinc from tratment of spent acid solution from the pickling stage of galvanizing plants. Sustainability, Vol. 13, No. 1, pp. 407–415, 2021. https://doi.org/10.3390/su13010407
B. C. Tripathy, S. C. Das, G. T. Hefter and P. Singh: Zinc electrowinning from acidic sulphate. Part I: Effect of sodium lauryl sulfate. Journal of Applied Electrochemistry, Vol. 27, pp. 673–678, 1997, https://doi.org/10.1023/A:1018431619595
A. R. Ault, E. J. Frazer and G. D. J. Smith: Effect of sodium and potasium sulphate on zinc electrowinning. Journal of Applied Electrochemistry, Vol. 18, pp. 32–37, 1988. https://doi.org/10.1007/BF01016202
M. Regel-Rosocka and M. Wisniewski: Selective removal of zinc (II) from spent pickling solutions in the presence of iron ions with phosphonium ionic liquid Cyphos IL 101. Hydrometallurgy, Vol. 110, pp. 85–90, 2011. https://doi.org/10.1016/j.hydromet.2011.08.012
J. Carrillo-Abad, M. Garcia-Gabaldon, E. Ortega and V. Perez-Herranz: Electrochemical recovery of zinc from the spent pickling baths coming from the hot dip galvanizing industry. Potentiostatic operation. Separation and Purification Technology, Vol. 81, pp. 200–207, 2011.
A. Pathak, A. Roy and M. Manna: Recovery of zinc from industrial waste pickling liquor. Hydrometallurgy, Vol. 163, pp. 161–166, 2016. https://doi.org/10.1016/j.hydromet.2016.04.006
D. Dhak, M. Mahon, A. Asselin and A. Alfantazi: The effects of mixture of acid mist suppression reagents on zinc electrowinning from spent electrolyte solutions. Hydrometallurgy, Vol. 108, pp. 1–10, 2011. https://doi.org/10.1016/j.hydromet.2011.02.002
T. Kékesi and M. Isshiki: Principal of metal purification and purity evaluation. In: Purification process and characterization of ultra high purity metals. Heidelberg: Springer, pp. 39–69, 2002.
T. Kékesi, K. Mimura and M. Isshiki: Ultra-high purification of iron by anion exchange in hydrochloric acid solutions. Hydrometallurgy, Vol. 63, No. 1, pp. 1–13, 2002. https://doi.org/10.1016/S0304-386X(01)00208-0
E. Maranon, Y. Fernandez, F. J Suarez, F. J Alonso and H. Sastre: Treatment of acid pickling bath by means of anionic resins. Industrial & Engineering Chemistry Research, Vol. 39, pp. 3370–3376, 2000, https://doi.org/10.1021/ie0000414
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