Abstract
In this work, a novel strategy based on evaporation and crystallization unit operations, capable of producing hydrochloric acid solution, iron(II) chloride and magnetic iron oxide from waste pickling acid (WPA), is proposed to be an eco-friendly alternative to the methods available in the literature. The suggested approach took into account both the partial recovery of the unused HCl by evaporation/condensation and iron(II) chloride by crystallization at room temperature. It was possible to obtain chemicals with yields above 80 wt% and purity above 97 wt%. Magnetic iron oxide presented magnetic saturation of 70.1 emu/g, magnetic retentivity of 4.3 emu/g and magnetic coercivity of 44.5 Oe, as well as an undetectable level of contamination by metals other than iron and agglomeration of its nanoparticles. The HCl solution presented less than 35 mg/L of iron and zinc. The evapo-crystallization method showed potential to be a mild form of treating WPA and generating three chemicals in the same process.
Graphic Abstract

This is a preview of subscription content, access via your institution.







References
- 1.
Zaferani, S.H., Sharifi, M., Zaarei, D., Shishesaz, M.R.: Application of eco-friendly products as corrosion inhibitors for metals in acid pickling processes: a review. J. Environ. Chem. Eng. 1, 652–657 (2013)
- 2.
Pullar, R.C., Hajjaji, W., Amaral, J.S., Seabra, M.P., Labrincha, J.A.: Magnetic properties of ferrite ceramics made from wastes. Waste Biomass Valori. 5, 133–138 (2013)
- 3.
Jarosz-Krzemińska, E., Helios-Rybicka, E., Gawlicki, M.: Utilization of neutralized spent sulfuric acid pickle liquor from metal treatment in cement production. Int. J. Environ. Sci. Technol. 12, 2901–2908 (2015)
- 4.
McKinley, C., Ghahreman, A.: Hydrochloric acid regeneration in hydrometallurgical processes: a review. Miner. Process. Extr. M. 127, 157–168 (2017)
- 5.
Gálvez, J.L., Dufour, J., Negro, C., López-Mateos, F.: Fluoride speciation in stainless steel pickling liquor. ISIJ Int. 46, 281–286 (2006)
- 6.
Kladnig, W.F.: New development of acid regeneration in steel pickling plants. J. Iron Steel Res. Int. 15, 1–6 (2008)
- 7.
Abiclor: Association of alkali and chlorine derivatives. Statistic Report of January, 2017 (Portuguese) www.abiclor.com.br
- 8.
Regel-Rosocka, M.: A review on methods of regeneration of spent pickling solutions from steel processing. J. Hazard. Mater. 177, 57–69 (2010)
- 9.
Kerney, U.: Treatment of spent pickling acids from hot dip galvanizing. Resour. Conserv. Recy. 10, 145–151 (1994)
- 10.
El Dessouky, S.I., El-Nadi, Y.A., Ahmed, I.M., Saad, E.A., Daoud, J.A.: Solvent extraction separation of Zn(II), Fe(II), Fe(III) and Cd(II) using tributylphosphate and CYANEX 921 in kerosene from chloride medium. Chem. Eng. Process. 47, 177–183 (2008)
- 11.
Mansur, M.B., Rocha, S.D.F., Magalhães, F.S., Benedetto, J.S.: Selective extraction of zinc(II) over iron(II) from spent hydrochloric acid pickling effluents by liquid–liquid extraction. J. Hazard. Mater. 150, 669–678 (2008)
- 12.
Devi, A., Singhal, A., Gupta, R., Panzade, P.: A study on treatment methods of spent pickling liquor generated by pickling process of steel. Clean Technol. Environ. 16, 1515–1527 (2014)
- 13.
Karayannis, V.G., Karapanagioti, H.K., Domopoulou, A.E., Komilis, D.P.: Stabilization/Solidification of Hazardous Metals from Solid Wastes into Ceramics. Waste Biomass Valori. 8, 1863–1874 (2016)
- 14.
Kalla, S., Upadhyaya, S., Singh, K., Baghel, R.: Experimental and mathematical study of air gap membrane distillation for aqueous HCl azeotropic separation. J. Chem. Technol. Biotechnol. 94, 63–78 (2019)
- 15.
Reis, M.T.A., Ismael, M.R.C.: Electroplating, Wastes: Phy. Sci. Rev. 3, 1–24 (2018)
- 16.
Rögener, F., Sartor, M., Bán, A., Buchloh, D., Reichardt, T.: Metal recovery from spent stainless steel pickling solutions. Resour. Conserv. Recy. 60, 72–77 (2012)
- 17.
Wang, L., Li, Q., Li, Y., Sun, X., Li, J., Shen, J., Han, W., Wang, L.: A novel approach for recovery of metals from waste printed circuit boards and simultaneous removal of iron from steel pickling waste liquor by two-step hydrometallurgical method. Waste Manage. 71, 411–419 (2018)
- 18.
Culcasi, A., Gueccia, R., Randazzo, S., Cipollina, A., Micale, G.: Design of a novel membrane-integrated waste acid recovery process from pickling solution. J. Clean. Prod. 236, 1–13 (2019)
- 19.
Yang, J.-G., Tang, C.-B., Chen, Y.-M., Tang, M.-T.: Separation of antimony from a stibnite concentrate through a low-temperature smelting process to eliminate SO2 emission. Metall. Mater. Trans. B 42, 30–36 (2010)
- 20.
Özdemir, T., Öztin, C., Kıncal, N.S.: Treatment of waste pickling liquors: process synthesis and economic analysis. Chem. Eng. Commun. 193, 548–563 (2006)
- 21.
Leonzio, G.: Recovery of metal sulphates and hydrochloric acid from spent pickling liquors. J. Clean. Prod. 129, 417–426 (2016)
- 22.
Yang, F., Wu, Y., Fang, X., Ma, L.: Experimental and theoretical study on the behaviour of a pickling solution: The role of ferrous ions. J. Clean. Prod. 243, 118631 (2020)
- 23.
Su, P., Zhang, J., Li, Y.: Chemical fixation of toxic metals in stainless steel pickling residue by Na2S·xH2O, FeSO4·6H2O and phosphoric acid for beneficial uses. J. Environ. Sci. 90, 364–374 (2020)
- 24.
Yi, Y., Tu, G., Zhao, D., Tsang, P.E., Fang, Z.: Key role of FeO in the reduction of Cr(VI) by magnetic biochar synthesized using steel pickling waste liquor and sugarcane bagasse. J. Clean. Prod. 245, 118886 (2020)
- 25.
Anastas, P., Eghbali, N.: Green chemistry: principles and practice. Chem. Soc. Rev. 39, 301–312 (2010)
- 26.
Ivanković, A., Dronjić, A., Bevanda, A.M., Talić, S.: Review of 12 Principles of Green Chemistry in Practice. Int. J. Sustain. Green Energy 6, 39–48 (2017)
- 27.
Marco, B.A., Rechelo, B.S., Tótoli, E.G., Kogawa, A.C., Salgado, H.R.N.: Evolution of green chemistry and its multidimensional impacts: a review. Saudi Pharm. J. 27, 1–8 (2019)
- 28.
Fataei, E., Moghaddam, E.M., Abdollahzadeh, M.: Determination of the best coagulant for turbidity and organic matter removal in the coagulation process of ardabil water treatment plant in Iran. Adv. Environ. Biol. 8, 319–324 (2014)
- 29.
Teja, A.S., Koh, P.-Y.: Synthesis, properties, and applications of magnetic iron oxide nanoparticles. Prog. Cryst. Growth Ch. 55, 22–45 (2009)
- 30.
Mei, L., Iizuka, A., Shibata, E.: Recent progress on utilization of metal-rich wastes in ferrite processing: a review. Waste Biomass Valori. 9, 1669–1679 (2017)
- 31.
Campos, E.A., Pinto, S., Oliveira, D.V.B., de Mattos, J.I.S., Dutra, E.D.C.: Synthesis, characterization and applications of iron oxide nanoparticles: a short review. J. Aerosp. Technol. Manag. 7, 267–276 (2015)
- 32.
Long, N.V., Teranishi, T., Yang, Y., Thi, C.M., Cao, Y., Nogami, M.: Iron oxide nanoparticles for next generation gas sensors. Int. J. Metall. Mater. Eng. 1, 1–18 (2015)
- 33.
Cai, Z., Ye, Y., Wan, X., Liu, J., Yang, S., Xia, Y., Li, G., He, Q.: Morphology-dependent electrochemical sensing properties of iron oxide–graphene oxide nanohybrids for dopamine and uric acid. Nanomaterials-Basel 9, 835 (2019)
- 34.
Bail, A., Moisés, M.P., Costa Junior, I.L.: Process for obtaining ferrous chloride and recovery of hydrochloric acid from waste chemical pickling and products obtained-BR1020190158514-Federal Technological University-Parana and Antares Reciclagem. Instituto Nacional da Propriedade Industrial (INPI), July 31, 2019
- 35.
Dorigon, L., Frota, J.P.R.A., Kreutz, J.C., Giona, R.M., Moisés, M.P., Bail, A.: Synthesis and characterization of mesoporous silica-coated magnetite containing cetyltrimethylammonium bromide and evaluation on the adsorption of sodium dodecylbenzenesulfonate. Appl. Surf. Sci. 420, 954–962 (2017)
- 36.
World Health Organization (WHO) (2008) Guidelines for Drinking-Water Quality, 3rd edition Incorporating the First and Second Addenda. WHO Press, Geneva
- 37.
Weast, R.C. (ed.): Handbook of Chemistry and Physics. 69th ed. Boca Raton, FL: CRC Press Inc., p. B-97 (1988–1989)
- 38.
Mohameed, H.A., Ulrich, J.: Influence of the pH-value on the growth and dissolution rate of potassium chloride. Cryst. Res. Technol. 31, 27–31 (1996)
- 39.
Lide, D. R. ed., CRC Handbook of Chemistry and Physics, Internet Version 2005, http://www.hbcpnetbase.com, CRC Press, Boca Raton, FL (2005).
- 40.
Morgan, B., Lahav, O.: The effect of pH on the kinetics of spontaneous Fe(II) oxidation by O2 in aqueous solution-basic principles and a simple heuristic description. Chemosphere 68, 2080–2084 (2007)
- 41.
Louvain, N., Fakhry, A., Bonnet, P., El-Ghozzi, M., Guérin, K., Sougrati, M., Jumas, J., Willmann, P.: One-shot versus stepwise gas–solid synthesis of iron trifluoride: investigation of pure molecular F2 fluorination of chloride precursors. Cryst. Eng. Commun. 15, 3664–3671 (2013)
- 42.
Salviano, L.B., Cardoso, T.M.S., Silva, G.C., Silva, M.S.S., Dantas, F.A.M.: Microstructural assessment of magnetite nanoparticles (Fe3O4) obtained by chemical precipitation under different synthesis conditions. Mat. Res. 21, 1–7 (2018)
- 43.
Song, H.-K., Sonkaria, S., Khare, V., Dong, K., Lee, H.-T., Ahn, S.-H., Adams, J.M.: Pond sediment magnetite grains show a distinctive microbial community. Microbial Ecol. 70, 168–174 (2015)
- 44.
Bhagwat, S., Singh, H., Athawale, A., Hannoyer, B., Jouen, S., Lefez, B., Kundaliya, D., Pasricha, R., Kulkarni, S., Ogale, S.: Low temperature synthesis of magnetite and maghemite nanoparticles. J. Nanosci. Nanotechnol. 7, 4294–4302 (2007)
- 45.
Reichel, V., Kovács, A., Kumari, M., Bereczk-Tompa, É, Schneck, E., Diehle, P., Pósfai, M., Hirt, A.M., Duchamp, M., Dunin-Borkowski, R.E., Faivre, D.: Single crystalline superstructured stable single domain magnetite nanoparticles. Sci. Rep-UK 7, 1–8 (2017)
- 46.
Cao, D., Li, H., Pan, L., Li, J., Wang, X., Jing, P., Cheng, X., Wang, W., Wang, J., Liu, Q.: High saturation magnetization of γ-Fe2O3 nano-particles by a facile one-step synthesis approach. Sci. Rep-UK 6, 1–9 (2016)
- 47.
Ter Horst, J.H., Schmidt, C., Ulrich, J.: Fundamentals of Industrial Crystallization.&Nbsp;Handbook of Crystal Growth, pp. 1317–1349. Elsevier, Amsterdam (2015)
Acknowledgements
We would like to thank Mr. Almir Trindade and Mr. Rodrigo Pimenta Giacomini from Antares Company (Brazil) for the fellowship and financial support. In addition, we thank Professor Ronie Galeano from DIREC-AP (UTFPR) for the administrative support.
Author information
Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Cunha, T.N.D., Trindade, D.G., Canesin, M.M. et al. Reuse of Waste Pickling Acid for the Production of Hydrochloric Acid Solution, Iron(II) Chloride and Magnetic Iron Oxide: An Eco-Friendly Process. Waste Biomass Valor 12, 1517–1528 (2021). https://doi.org/10.1007/s12649-020-01079-1
Received:
Accepted:
Published:
Issue Date:
Keywords
- Industrial waste
- Waste valorization
- Recycling
- Waste pickling acid
- Iron oxides