Acid pickling of carbon steel
DOI:
https://doi.org/10.3989/revmetalm.226Keywords:
Hot dip galvanizing, Hydrochloric acid, Iron (II) chloride, Steel pickling, Zinc chlorideAbstract
This study reviews the possibilities of recovering the pickling waters from carbon and galvanised steel. Acid pickling with hydrochloric acid (HCl) is the most widely used chemical process to remove iron oxides from the metal surface without any significant attack on the steel itself. The acid pickling bath contains mainly ferrous chloride (FeCl2) produced by the reaction between the steel and free hydrochloric acid. However, zinc chloride (ZnCl2) is also found in the pickling of carbon steel parts prior to galvanisation, as the hooks and tools used to hang the carbon steel parts are also galvanised and reuse again polluting with Zn the pickling waters. Pickling water recovery or recycling technologies primarily seek the reuse of HCl in two ways. Partially by recovering the unreacted HCl or fully by breaking the FeCl2 bond through Pyrolysis technologies such as fluidised bed and spray roasting which in turn produces another iron oxide by-product. However, the most common by-product produced by pickling water recovery and recycling technologies is ferric chloride (FeCl3), as it is a coagulant widely used in wastewater treatment. However, if the pickling water contains ZnCl2 or other metals, the production of FeCl3 becomes unattractive and the pickling water is neutralised and deposited in landfill sites. This study also discusses a wide range of technologies capable of recovering all or part of the pickling water, including galvanic pickling water, that are usually excluded from circular economy strategies.
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Agrawal, A., Sahu, K.K. (2009). An overview of the recovery of acid from spent acidic solutions from steel and electroplating industries. J. Hazard. Mater. 171 (1-3), 61-75. https://doi.org/10.1016/j.jhazmat.2009.06.099 PMid:19632040
Agrawal, A., Sahu, K.K. (2010). Treatment of chloride waste pickle liquor by solvent extraction for the recovery of iron. Miner. Process. Extr. Metall. Rev. 31 (3), 121-134. https://doi.org/10.1080/08827501003727006
Agrawal, A., Kumari, S., Sahu, K.K. (2011). Studies on solvent extraction of iron(III) as a step for conversion of a waste effluent to a value added product. J. Environ. Manage 92 (12), 3105-3111. https://doi.org/10.1016/j.jenvman.2011.07.026 PMid:21862202
Al-Othman, A., Demopoulos, G.P. (2009). Gypsum crystallization and hydrochloric acid regeneration by reaction of calcium chloride solution with sulfuric acid. Hydrometallurgy 96 (1-2), 95-102. https://doi.org/10.1016/j.hydromet.2008.08.010
Alcaraz, L., Sotillo, B., López, F.A., Alguacil, F.J., Marco, J.F., Fernández, P. (2021). Obtention and Characterization of Ferrous Chloride FeCl2·4H2O from Water Pickling Liquors. Materials 14 (17), 4840. https://doi.org/10.3390/ma14174840 PMid:34500936 PMCid:PMC8432721
Alguacil, F.J., Martínez, S. (2001). Solvent extraction of Zn(II) by Cyanex 923 and its application to a solid-supported liquid membrane system. J. Chem. Technol. Biotechnol. 76 (3), 298-302. https://doi.org/10.1002/jctb.369
Anand, S., Atul, N.V., Manukoda, S.K., Purushottam, K. (2008). An improved process for beneficiation of pickling wastewater with simultaneous recovery of hydrochloric acid and ferrous sulfate (Patent No. 216825). https://www.allindianpatents.com/patents/216825-an-improved-process-for-beneficiation-of-pickling-wastewater-with-simultaneous-recovery-of-hydrochloric-acid-and-ferrous-sulfate.
Bolto, B.A., Pawlowski, L. (1987). Wastewater treatment by ion-exchange. L. Pawlowski (ed.), Ed.Spon Press. 300 pp. ISBN-10: 0419133208.
Bood, C. (2020). Acid retardation: recovery and recycling of acid and metal. Degree Project, Luleå University of Technology.
Brown, C.J. (2006). Regeneration of hydrochloric acid pickle liquors by crystallization. Canadian Institute of Mining, Metallurgy and Petroleum, Chemionex Inc.
Cullivan, B. (2020). Technology Profile: Acid Recovery and Recycle Technologies. Beta Control Systems. http://www.betacontrol.com/sites/default/files/uploads/file/HCl_literature/Acid%20Recovery%20and%20Recycling%20Technologies_Beta%20Control%20Systems%20Z.pdf.
Dahlgren, L. (2010). Treatment of Spent Pickling Acid from Stainless Steel Production: A review of regeneration technologies with focus on the neutralisation process for implementation in Chinese industry. Master of Science Thesis, Royal Institute of Technology, Stocholm.
Directive UE 2018/851 (2018). European Union Directive 2018/851 amending Directive 2008/98/EC on waste, 109 (2018). https://www.eea.europa.eu/policy-documents/directive-eu-2018-851-of.
Devi, A., Singhal, A., Gupta, R., Panzade, P. (2014). A study on treatment methods of spent pickling liquor generated by pickling process of steel. Clean Techn. Environ. Policy 16 (8), 1515-1527. https://doi.org/10.1007/s10098-014-0726-7
Evans, C.D., Monteith, D.T., Fowler, D., Cape, J.N., Brayshaw, S. (2011). Hydrochloric acid: An overlooked driver of environmental change. Environ. Sci. Technol. 45 (5), 1887-1894. https://doi.org/10.1021/es103574u PMid:21288016
Feser, R., Friedrich, A., Scheide, F. (2002). The influence of long term use of inhibitors in hydrochloric acid pickling baths on hydrogen induced stress corrosion cracking. Mater. Corros. 53 (9), 637-646. https://doi.org/10.1002/1521-4176(200209)53:9<637::AID-MACO637>3.0.CO;2-P
Garverick, L. (1994). Corrosion in the petrochemical industry. ASM international.
Gueccia, R., Randazzo, S., Chillura Martino, D., Cipollina, A., Micale, G. (2019). Experimental investigation and modeling of diffusion dialysis for HCl recovery from waste pickling solution. J. Environ. Manage. 235, 202-212. https://doi.org/10.1016/j.jenvman.2019.01.028 PMid:30682673
Gueccia, R., Aguirre, A.R., Randazzo, S., Cipollina, A., Micale, G. (2020). Diffusion dialysis for separation of hydrochloric acid, iron and zinc ions from highly concentrated pickling solutions. Membranes 10 (6), 129. https://doi.org/10.3390/membranes10060129 PMid:32599784 PMCid:PMC7344563
Gueccia, R., Winter, D., Randazzo, S., Cipollina, A., Koschikowski, J., Micale, G.D.M. (2021). An integrated approach for the HCl and metals recovery from waste pickling solutions: pilot plant and design operations. Chem. Eng. Res. Des. 168, 383-396. https://doi.org/10.1016/j.cherd.2021.02.016
Hatch, M., Dillon, J. (1963). Acid Retardation. Simple Physical Method for Separation of Strong Acids from Their Salts. Ind. Eng. Chem. Process Des. Dev. 2 (4), 253-263. https://doi.org/10.1021/i260008a001
Hudson, R.M., Warning, C.J. (1969). Minimizing Fuming during Pickling with Hydrochloric Acid. Sheet. Metal. Ind. 46 (8), 523-525.
Hudson, R.M., Warning, C.J. (1982). Effect of Strip Velocity on Pickling Rate of Hot-Rolled Steel in Hydrochloric Acid. JOM 34 (2), 65-70. https://doi.org/10.1007/BF03339114
Inguru Consultores (2006). Estudio de impacto ambiental proyecto de ampliación de las instalaciones de producción de cloruro férrico - ACIDEKA, S.A., P.I. Lantarón (Álava).
Jung Oh, S., Moon, S.H., Davis, T. (2000). Effects of metal ions on diffusion dialysis of inorganic acids. J. Membr. Sci. 169 (1), 95-105. https://doi.org/10.1016/S0376-7388(99)00333-6
Kerney, U. (1994). Treatment of spent pickling acids from hot dip galvanizing. Resour., Conserv. Recycl. 10 (1-2), 145-151. https://doi.org/10.1016/0921-3449(94)90047-7
Kleingarn, J.-P. (1990). Pickling in hydrochloric acid. Galvano-Organo-Traitements de Surface, 59 (605), 325-331.
Kuron, D. (1986). Hydrogen and corrosion (Issue Festschrift for Prof. Dr. Hubert Graefen on the occasion of his 60. anniversary. Wasserstoff und Korrosion. Festschrift zum 60. Geburtstag von Prof. Dr. Hubert Graefen. Germany, Mater. Corros. 37 (5), p. 294.
Lee, C., Small, D., Adham, Kamal (2006). Energy consumption for iron chloride pyrohydrolysis: A comparison between fluidized beds and spray roasters. Conference COM 2006 Conference of Metallurgists, Montreal Quebec Canada: Proceedings of the COM 2006. Canadian Institute of Mining Metallurgy and Petroleum.
Leonzio, G. (2016). Recovery of metal sulphates and hydrochloric acid from spent pickling liquors. J. Clean. Prod. 129, 417-426. https://doi.org/10.1016/j.jclepro.2016.04.037
Luo, J., Wu, C., Wu, Y., Xu, T. (2013). Diffusion dialysis of hydrochloric acid with their salts: Effect of co-existence metal ions. Sep. Purif. Technol. 118, 716-722. https://doi.org/10.1016/j.seppur.2013.08.014
Marañón, E., Fernández, Y., Súarez, F.J., Alonso, F.J., Sastre, H. (2000). Treatment of acid pickling baths by means of anionic resins. Ind. Eng. Chem. Res. 39 (9), 3370-3376. https://doi.org/10.1021/ie0000414
Meltzer, M. (1990). Metal Bearing Waste Streams: Minimizing, Recycling and Treatment. William Andrew Publishing. USA, 426 pages.
Mishra, R.K., Rout, P.C., Sarangi, K., Nathsarma, K.C. (2010). A comparative study on extraction of Fe(III) from chloride leach liquor using TBP, Cyanex 921 and Cyanex 923. Hydrometallurgy 104 (2), 298-303. https://doi.org/10.1016/j.hydromet.2010.07.003
Naushad, M., Al-Othman, Z.A. (2013). A Book on Ion Exchange, Adsorption & Solvent Extraction. King Saud University, Riyadh, Saudi Arabia.
Özdemir, T., Öztin, C., Kincal, N.S. (2006). Treatment of waste pickling liquors: Process synthesis and economic analysis. Chem. Eng. Commun. 193 (5), 548-563. https://doi.org/10.1080/00986440500192238
Ostovari, A., Hoseinieh, S.M., Peikari, M., Shadizadeh, S.R., Hashemi, S.J. (2009). Corrosion inhibition of mild steel in 1 M HCl solution by henna extract: A comparative study of the inhibition by henna and its constituents (Lawsone, Gallic acid, α-d-Glucose and Tannic acid). Corros. Sci. 51 (9), 1935-1949. https://doi.org/10.1016/j.corsci.2009.05.024
Paatsch, W. (2011). Hydrogen determination and hydrogen embrittlement - Meaning and advantage. Galvanotechnik 102 (1), 48-55.
Palatý, Z., Žáková, A. (2006). Competitive transport of hydrochloric acid and zinc chloride through polymeric anion-exchange membrane. J. Appl. Polym. Sci. 101 (3), 1391-1397. https://doi.org/10.1002/app.22748
Regel, M., Sastre, A.M., Szymanowski, J. (2001). Recovery of Zinc(II) from HCl Spent Pickling Solutions by Solvent Extraction. Environ. Sci. Technol. 35 (3), 630-635. https://doi.org/10.1021/es001470w PMid:11351740
Regel-Rosocka, M., Sastre, A.M., Szymanowski, J. (2002). Zinc (II) extraction from hydrochloric acid solutions with basic and solvating extractants. XVII-Th ARS SEPARATORIA-Borówno.
Regel-Rosocka, M. (2010). A review on methods of regeneration of spent pickling solutions from steel processing. J. Hazard. Mater. 177 (1-3), 57-69. https://doi.org/10.1016/j.jhazmat.2009.12.043 PMid:20056321
Saji John, K., Saji, J., Reddy, M.L.P., Ramamohan, T.R., Rao, T.P. (1999). Solvent extraction of titanium(IV) from acidic chloride solutions by Cyanex 923. Hydrometallurgy 5 (1), 9-18. https://doi.org/10.1016/S0304-386X(98)00066-8
Sinha, M.K., Pramanik, S., Sahu, S.K., Prasad, L. B., Jha, M.K., Pandey, B.D. (2016). Development of an efficient process for the recovery of zinc and iron as value added products from the waste chloride solution. Sep. Purif. Technol. 167, 37-44. https://doi.org/10.1016/j.seppur.2016.04.049
Sittig, M. (1981). Handbook of toxic and hazardous chemicals. Noyes Data Corp., Park Ridge, NJ. https://www.osti.gov/biblio/5444143.
Staley, H.F. (1926a). The Theory of Pickling of Sheet Iron and Steel for Enameling Purposes. J. Am. Ceram. Soc. 9 (12), 787-796. https://doi.org/10.1111/j.1151-2916.1926.tb17958.x
Staley, H.F. (1926b). The theory of pickling of sheet iron and steel for enameling purposes. J. Am. Ceram. Soc. 9 (12), 787-796. https://doi.org/10.1111/j.1151-2916.1926.tb17958.x
Stocks, C., Wood, J., Guy, S. (2005). Minimisation and recycling of spent acid wastes from galvanizing plants. Resour., Conserv. Recycl. 44 (2), 153-166. https://doi.org/10.1016/j.resconrec.2004.11.005
Tang, J., Pei, Y. Hu, Q., Pei, D., Junpeng Xu, J. (2016) The Recycling of Ferric Salt in Steel Pickling Liquors: Preparation of Nano-sized Iron Oxide. Procedia Environ. Sci., 31, 778-784. https://doi.org/10.1016/j.proenv.2016.02.071
Tang, B., Su, W., Wang, J., Fu, F., Yu, G., Zhang, J. (2012). Minimizing the creation of spent pickling liquors in a pickling process with high-concentration hydrochloric acid solutions: Mechanism and evaluation method. J. Environ. Manage. 98 (1), 147-154. https://doi.org/10.1016/j.jenvman.2011.12.027 PMid:22266479
Tomaszewska, M., Gryta, M., Morawski, A.W. (2001). Recovery of hydrochloric acid from metal pickling solutions by membrane distillation. Sep. Purif. Technol. 22-23, 591-600. https://doi.org/10.1016/S1383-5866(00)00164-7
Treischel, C. (1919). The cause and control of blistering in sheetsteel enameling. J. Am. Ceram. Soc. 2 (10), 774-781. https://doi.org/10.1111/j.1151-2916.1919.tb17472.x
Turgoose, S., Bullough, W. (2013). Pickling in Acid. In Corrosion. Third Edition, Vol 2, pp. 14-23.
Yang, F., Wu, Y., Fang, X., Ma, L. (2020). Experimental and theoretical study on the behaviour of a pickling solution: The role of ferrous ions. J. Clean. Prod. 243, 118631. https://doi.org/10.1016/j.jclepro.2019.118631
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