Solvent-Driven Fractional Crystallization Applied to the Desalination of a Concentrated Wastewater by Reverse Osmosis

Authors

  • Edgar Vásquez

    Department of Chemical Engineering, National University of Trujillo, Trujillo 13001, Perú

  • Flavia Hurtado

    Department of Chemical Engineering, National University of Trujillo, Trujillo 13001, Perú

DOI:

https://doi.org/10.30564/jees.v7i8.10526
Received: 16 June 2025 | Revised: 17 July 2025 | Accepted: 30 July 2025 | Published Online: 4 August 2025

Abstract

This paper reports the efficiency of the solvent-driven fractional crystallization (SDFC) process using ethanol, also known as antisolvent crystallization, in the treatment of a concentrated wastewater by reverse osmosis (RO). This experiment evaluated the effects of varying the volumetric mixing ratio of ethanol-to-RO concentrate, in conjunction with the incorporation of Ca(OH)2, on the efficiency of magnesium and boron removal. The incorporation of Ca(OH)2 resulted in an enhancement of the reduction of magnesium and boron concentrations at a mixing ratio of 85:15 (v/v) and a pH of 12. In these conditions, the removal efficiencies achieved for magnesium and boron were 98.64% and 90.82%, respectively. The findings indicate that Ca(OH)2 has a significant impact on enhancing the removal efficiencies of these elements. The RO concentrated wastewater used in this experiment exhibited a salinity of 50,497.200 ppm prior to the SDFC test. The experimental results also showed a 48.10% reduction in salinity and 28.10% salt precipitation at the maximum mixing ratio and pH level examined. The tested process demonstrated significant reduction of scaling ions including calcium, magnesium, and sulfate. Similar behavior was observed for arsenic and manganese. Moderate removal efficiencies were observed for monovalent ions such as chloride, sodium, and potassium. However, the process was no effective for iron and lithium, which showed low removal efficiencies. Based on the results obtained, SDFC technology is seen as a promising technological option for application in the treatment of complex mining wastewaters.

Keywords:

Fractional Crystallization; Antisolvent Crystallization; Scaling Ions; Monovalent Ions

References

[1] Ogunbiyi, O., Saththasivam, J., Al-Masri, D., et al., 2021. Sustainable brine management from the perspectives of the water, energy, and mineral recovery: A comprehensive review. Desalination. 513, 115055. DOI: https://doi.org/10.1016/j.desal.2021.115055

[2] Cipolletta, G., Lancioni, N., Akyol, C., et al., 2021. Brine treatment technologies towards minimun/zero liquid discharge and resource recovery: State of the art and techno-economic assessment. Journal of Environmental Management. 300, 113681. DOI: https://doi.org/10.1016/j.jenvman.2021.113681

[3] Giwa, A., Dufour, V., Al Marzooqi, F., et al., 2017. Brine management methods: Recent innovations and current status. Desalination. 407, 1–23. DOI: https://doi.org/10.1016/j.desal.2016.12.008

[4] Zarzo, D., 2017. 11- Beneficial uses and valorization of reverse osmosis brines, Emerging Technologies for Sustainable. Desalination Handbook. 365–397. DOI: https://doi.org/10.1016/B978-0-12-815818-0.00011-4

[5] Shah, K.M., Billinge, I.H., Chen, X., et al., 2022. Drivers, challenges, and emerging technologies for desalination of high-salinity brines: A critical review. Desalination. 538, 115827. DOI: https://doi.org/10.1016/j.desal.2022.115827

[6] Zhang, X., Zhao, W., Zhang, Y., et al., 2021. A review of resource recovery from seawater desalination brine. Reviews in Environmental Science and Bio/Technology. 20, 333–361. DOI: https://doi.org/10.1007/s11157-021-09570-4.123456789

[7] Sappidi, P., Barbosa, G., Rabideau, B.D., et al., 2021. Molecular simulation of high-salinity brines in contact with diisopropylamine and tripropylamine solvents. Industrial & Engineering Chemistry Research. 60, 7917–7925. DOI: https://doi.org/10.1021/acs.iecr.1c01057

[8] Boo, C., Winton, R.K., Conway, K.M., et al., 2019. Membrane-less and non-evaporative desalination of hypersaline brines by temperature swing solvent extraction. Environmental Science & Technology Letters. 6, 359–364. DOI: https://doi.org/10.1021/acs.estlett.9b00182

[9] Tong, T., Elimelech, M., 2016. The global rise of zero liquid discharge for wastewater management: Drivers, technologies, and future directions. Environmental Science & Technology. 50, 6846–6855. DOI: https://doi.org/10.1021/acs.est.6b01000

[10] Boo, C., Billinge, I.H., Chen, X., et al., 2020. Zero liquid discharge of ultrahigh – salinity brines with temperature swing solvent extraction. Environmental Science & Technology. 54, 9124–9131. DOI: https://dx.doi.org/10.1021/acs.est.0c02555

[11] Yaqub, M., Lee, W., 2019. Zero - liquid discharge (ZLD) technology for resource recovery from wastewater: A review. Science of the Total Environment. 681, 551–563. DOI: https://doi.org/10.1016/j.scitotenv.2019.05.062

[12] Vásquez, E.E., Román, G., Vargas, J.A., et al., 2024. Ethanol extraction desalination test using pre-treated mine wastewater concentrated by reverse osmosis. Desalination and Water Treatment. 317, 100208. DOI: https://doi.org/10.1016/j.dwt.2024.100208

[13] Foo, Z.H., Stetson, C., Dach, E., et al., 2022. Solvent–driven aqueous separations for hypersaline brine concentration and resource recovery. Trends in Chemistry. 4, 1078–1093. DOI: https://doi.org/10.1016/j.trechm.2022.09.004

[14] Stetson, C., Prodius, D., Lee, H., et al., 2022. Solvent-driven fractional crystallization for atom-efficient separation of metal salts from permanent magnet leachates. Nature Communications. 13, 3789. DOI: https://doi.org/10.1038/s41467-022-31499-7

[15] Barbosa, G.D., Dach, E., Liu, X., et al., 2022. Computational and experimental study of different brines in temperature swing solvent extraction desalination with amine solvents. Desalination. 537, 115863. DOI: https://doi.org/10.1016/j.desal.2022.115863

[16] Baird, R., Eaton, A., Rice, E., 2017. Standard Methods for the Examination of Water and Wastewater, 23rd ed. American Public Health Association: Washington, DC, USA. pp. 166–550.

[17] EPA, 2020. Approved CWA Chemical Test Methods. Available from: https://www.epa.gov/cwa-methods/approved-cwa-chemical-test-methods (cited 20 March 2024).

[18] Qu, Y., Cheng, J., Mao, Z., et al., 2021. A perspective review on mixing effect for modeling and simulation of reactive and antisolvent crystallization processes. Reaction Chemistry & Engineering. 6, 183–196. DOI: https://doi.org/10.1039/D0RE00223B

[19] Cogoni, G., Baratti, R., Romagnoli, J.A., 2013. On the influence of hydrogen bond interactions in isothermal and nonisothermal antisolvent crystallization processes. Industrial & Engineering Chemistry Research. 52, 9612–9619. DOI: https://dx.doi.org/10.1021/ie303414b

[20] Shah, K.M., Dach, E., Winton, R., et al., 2023. Phase equilibria insights into amine-water-NaCl interactions in liquid-liquid biphasic systems for temperature swing solvent extraction desalination. Desalination. 548, 116259. DOI: https://doi.org/10.1016/j.desal.2022.116259

[21] Veolia Water Technologies & Solutions, 2025. Handbook of Industrial Water Treatment. Available from: https://www.watertechnologies.com/handbook/handbook-industrial-water-treatment (cited 10 February 2024).

[22] Guo, J., Luo, S., Liu, Z., et al., 2020. Direct arsenic removal from water using non-membrane, low-temperature directional solvent extraction. Journal of Chemical & Engineering Data. 65, 2938–2946. DOI: https://dx.doi.org/10.1021/acs.jced.9b00936

[23] Yilmaz, A.E., Boncukcuoglu, R., Bayar, S., et al., 2012. Boron removal by means of chemical precipitation with calcium hydroxide and calcium borate formation. Korean Journal of Chemical Engineering. 29, 1382–1387. DOI: https://doi.org/10.1007/s11814-012-0040-1

[24] Bai, C., Wu, Z., Ye, X., et al., 2019. Influence of the pH in reactions of boric acid/borax with simple hydroxyl compounds: Investigation by Raman Spectroscopy and DFT calculations. ChemistrySelect. 4, 14132–14139. DOI: https://doi.org/10.1002/slct.201903740

[25] Ayers, P., Dudeney, A., Kahraman, F., 1981. Solvent extraction of boron with 2-ethyl-1,3 hexanediol and 2-chloro-4-(1,1,3,3-tetramethylbutyl)-6-methylol-phenol. Journal of Inorganic and Nuclear Chemistry. 43, 2097–2100. DOI: https://doi.org/10.1016/0022-1902(81)80556-8

[26] Kiemde, A.F., Marin, J., Flexer, V., Chagnes, A., 2024. Boron extraction by aliphatic mono- and di-hydroxy alcohols from a representative continental brine. Hydrometallurgy. 225, 106280. DOI: https://doi.org/10.1016/j.hydromet.2024.106280

[27] Zhang, R., Xie, Y., Song, J., et al., 2016. Extraction of boron from Salt Lake brine using 2-ethylhexanol. Hydrometallurgy. 160, 129–136. DOI: http://dx.doi.org/10.1016/j.hydromet.2016.01.001

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How to Cite

Vásquez, E., & Hurtado, F. (2025). Solvent-Driven Fractional Crystallization Applied to the Desalination of a Concentrated Wastewater by Reverse Osmosis. Journal of Environmental & Earth Sciences, 7(8), 1–15. https://doi.org/10.30564/jees.v7i8.10526