Comparative Study on Cu and Zn Removal from Industrial Wastewater by Chemical Precipitation Using Lime, Caustic Soda and Soda Ash

Document Type : Research Paper


1 Department of Environmental Engineering, Aras International Campos, Jolfa, Iran

2 Faculty of Environment, University of Tehran, Tehran, Iran


The chemical precipitation using lime, caustic soda and soda ash was investigated for the simultaneous removal of Cu and Zn from copper mine industrial wastewater by conducting jar tests in the present study. Jar experiments were performed with a set of polyethylene beakers (500 ml) in order to investigate the effect of two reaction parameters (precipitant doses and initial pH) on the removal of heavy metals. X-ray Diffraction (XRD) and Scanning Electron Microscope (SEM) equipped with X-Ray Energy Diffraction Spectroscopy (EDX) were used to identify the important chemical compounds and to study the surface morphology, chemical composition and particle size of the sludge samples. An increase in the removal of Cu and Zn was observed by increasing the precipitant dose (10-400 mg/L) for each reagent used. Removal efficiency of 90% were obtained for both heavy metal ions. The chemical precipitation efficiency was affected by pH. At high final pH levels (8<pH<10), Cu had higher removal efficiency than Zn by all precipitating agents. In the sludge produced, Zn and Cu were precipitated as amorphous hydroxides including Zn(OH)2 and Cu(OH)2. SEM images showed that the produced sludges have small size and compact structure. EDX analysis determined that in all sludge samples, the content of Cu was higher than Zn. Effluent treatment with soda ash resulted in the sludge production with lower volume and larger particle size. As a result, the use of this precipitating agent can be less expensive for sludge drying steps.


Main Subjects

APHA (2005). Standard Methods for the Examination of Water and Wastewater. American Water Works Association (AWWA) and Water Pollution Control Federation (WPCF), 18th ed. Washington DC: American Public Health Association (APHA).
Ayalew, Z. M., Zhang, X., Guo, X., Ullah, S., Leng, S., Luo, X., & Ma, N. (2020). Removal of Cu, Ni and Zn directly from acidic electroplating wastewater by Oligo-Ethyleneamine dithiocarbamate (OEDTC). Separation and Purification Technology, 248, 117114.
Azimi, A., Azari, A., Rezakazemi, M., & Ansarpour, M. (2017). Removal of heavy metals from industrial wastewaters: a review. ChemBioEng Reviews, 4(1), 37-59.
Bagdat, S., Tokay, F., Demirci, S., Yilmaz, S., & Sahiner, N. (2023). Removal of Cd (II), Co (II), Cr (III), Ni (II), Pb (II) and Zn (II) ions from wastewater using polyethyleneimine (PEI) cryogels. Journal of Environmental Management, 329, 117002.
Bai, W., Tang, R., Wu, G., Wang, W., Yuan, S., Xiao, L., & Hu, Z. H. (2023). Co-precipitation of heavy metals with struvite from digested swine wastewater: Role of suspended solids. Journal of Hazardous Materials, 455, 131633.
Balladares, E., Jerez, O., Parada, F., Baltierra, L., Hernández, C., Araneda, E., & Parra, V. (2018). Neutralization and co-precipitation of heavy metals by lime addition to effluent from acid plant in a copper smelter. Minerals Engineering, 122, 122-129.
Bashir, A., Malik, L. A., Ahad, S., Manzoor, T., Bhat, M. A., Dar, G. N., & Pandith, A. H. (2019). Removal of heavy metal ions from aqueous system by ion-exchange and biosorption methods. Environmental Chemistry Letters, 17, 729-754.
Benalia, M. C., Youcef, L., Bouaziz, M. G., Achour, S., & Menasra, H. (2022). Removal of heavy metals from industrial wastewater by chemical precipitation: mechanisms and sludge characterization. Arabian Journal for Science and Engineering, 47(5), 5587-5599.
Byambaa, M., Dolgor, E., Shiomori, K., & Suzuki, Y. (2018). Removal and recovery of heavy metals from industrial wastewater by precipitation and foam separation using lime and casein. Journal of Environmental Science and Technology, 11(1), 1-9.
Chen, Q., Yao, Y., Li, X., Lu, J., Zhou, J., & Huang, Z. (2018). Comparison of heavy metal removals from aqueous solutions by chemical precipitation and characteristics of precipitates. Journal of Water Process Engineering, 26, 289-300.
Dai, Y., Zhang, K., Li, J., Jiang, Y., Chen, Y., & Tanaka, S. (2017). Adsorption of copper and zinc onto carbon material in an aqueous solution oxidized by ammonium peroxydisulphate. Separation and Purification Technology, 186, 255-263.
Daryabeigi Zand, A., Rabiee Abyaneh, M., & Hoveidi, H. (2019). Capability of Reused Waste from Aluminum Industry (Red Mud) in Iran to Improve Compressive Strength of Loose Soil. Pollution, 5(2), 411-418.
Efome, J. E., Rana, D., Matsuura, T., & Lan, C. Q. (2019). Effects of operating parameters and coexisting ions on the efficiency of heavy metal ions removal by nano-fibrous metal-organic framework membrane filtration process. Science of The Total Environment, 674, 355-362.
Fan, H. L., Zhou, S. F., Jiao, W. Z., Qi, G. S., & Liu, Y. Z. (2017). Removal of heavy metal ions by magnetic chitosan nanoparticles prepared continuously via high-gravity reactive precipitation method. Carbohydrate Polymers, 174, 1192-1200.
Handley-Sidhu, S., Mullan, T. K., Grail, Q., Albadarneh, M., Ohnuki, T., & Macaskie, L. E. (2016). Influence of pH, competing ions and salinity on the sorption of strontium and cobalt onto biogenic hydroxyapatite. Scientific Reports, 6(1), 23361.
Hoseinian, F. S., Ramshini, S., Rezai, B., Kowsari, E., & Safari, M. (2023). Toxic heavy metal ions removal from wastewater by ion flotation using a nano collector. Minerals Engineering, 204, 108380.
Hu, H., Li, X., Huang, P., Zhang, Q., & Yuan, W. (2017). Efficient removal of copper from wastewater by using mechanically activated calcium carbonate. Journal of Environmental Management, 203, 1-7.
Huang, J., Yuan, F., Zeng, G., Li, X., Gu, Y., Shi, L., & Shi, Y. (2017). Influence of pH on heavy metal speciation and removal from wastewater using micellar-enhanced ultrafiltration. Chemosphere, 173, 199-206.
Junuzović, H., Begić, S., Selimović, A., Đozić, A., Cvrk, R., & Ahmetović, M. (2019). Efficiency of carbonate precipitation and removal of copper and nickel ions from their monocomponent and two-component aqueous solutions. International Journal for Research in Applied Sciences and Biotechnology, 6(6), 11-15.
Kong, Q., Zhang, X., Ma, K., Gong, Y., Peng, H., & Qi, W. (2023). PEI-modified chitosan/activated carbon composites for Cu (II) removal from simulated pyrophosphate plating rinsing wastewater. International Journal of Biological Macromolecules, 251, 126429.
Li, X., Zhang, Q., & Yang, B. (2020). Co-precipitation with CaCO3 to remove heavy metals and significantly reduce the moisture content of filter residue. Chemosphere, 239, 124660.
Li, D., Zhang, X., Liang, X., Liu, W., Guo, K., Zhang, Z., & Wang, H. (2023). Simultaneous removal and conversion of silver ions from wastewater into antibacterial material through selective chemical precipitation. Arabian Journal of Chemistry, 16(7), 104836.
Liu, Y., Wang, H., Cui, Y., & Chen, N. (2023). Removal of Copper Ions from Wastewater: A Review. International Journal of Environmental Research and Public Health, 20(5), 3885.
Meng, S., Wen, S., Han, G., Wang, X., & Feng, Q. (2022). Wastewater treatment in mineral processing of non-ferrous metal resources: A review. Water, 14(5), 726.
Moazeni, K., Mirzaei, M., Baghdadi, M., & Torabian, A. (2023). Sequential Treatment of Textile Industry Wastewater Using Electrocoagulation and Photo electro-Fenton Processes. Water, Air, & Soil Pollution, 234(7), 413.
Monea, M. C., Löhr, D. K., Meyer, C., Preyl, V., Xiao, J., Steinmetz, H., & Drenkova-Tuhtan, A. (2020). Comparing the leaching behavior of phosphorus, aluminum and iron from post-precipitated tertiary sludge and anaerobically digested sewage sludge aiming at phosphorus recovery. Journal of Cleaner Production, 247, 119129.
Onutai, S., Kobayashi, T., Thavorniti, P., & Jiemsirilers, S. (2019). Porous fly ash-based geopolymer composite fiber as an adsorbent for removal of heavy metal ions from wastewater. Materials Letters, 236, 30-33.
Patel, P. K., Pandey, L. M., & Uppaluri, R. V. (2023). Adsorptive removal of Zn, Fe, and Pb from Zn dominant simulated industrial wastewater solution using polyvinyl alcohol grafted chitosan variant resins. Chemical Engineering Journal, 459, 141563.
Pohl, A. (2020). Removal of heavy metal ions from water and wastewaters by sulfur-containing precipitation agents. Water, Air, & Soil Pollution, 231(10), 503.
Prokkola, H., Nurmesniemi, E. T., & Lassi, U. (2020). Removal of metals by sulphide precipitation using Na2S and HS- solution. ChemEngineering, 4(3), 51.
Quiton, K. G. N., Huang, Y. H., & Lu, M. C. (2022). Recovery of cobalt and copper from single-and co-contaminated simulated electroplating wastewater via carbonate and hydroxide precipitation. Sustainable Environment Research, 32(1), 1-22.
Rybarczyk, P., & Kawalec-Pietrenko, B. (2021). Simultaneous removal of Al, Cu and Zn ions from aqueous solutions using ion and precipitate flotation methods. Processes, 9(2), 301.
Serrano, L. Z., Lara, N. O., Vera, R. R., & Cholico-González, D. (2021). Removal of Fe (III), Cd (II), and Zn (II) as Hydroxides by Precipitation–Flotation System. Sustainability, 13(21), 11913.
Shah, K., Gupta, K., & Sengupta, B. (2017). Selective separation of copper and zinc from spent chloride brass pickle liquors using solvent extraction and metal recovery by precipitation-stripping. Journal of Environmental Chemical Engineering, 5(5), 5260-5269.
Shrestha, R., Ban, S., Devkota, S., Sharma, S., Joshi, R., Tiwari, A. P., & Joshi, M. K. (2021). Technological trends in heavy metals removal from industrial wastewater: A review. Journal of Environmental Chemical Engineering, 9(4), 105688.
Song, W., Zhang, X., Zhang, L., Yu, Z., Li, X., Li, Y., & Yan, L. (2023). Removal of various aqueous heavy metals by polyethylene glycol modified MgAl-LDH: Adsorption mechanisms and vital role of precipitation. Journal of Molecular Liquids, 375, 121386.
Sun, Y., Zhou, S., Pan, S. Y., Zhu, S., Yu, Y., & Zheng, H. (2020). Performance evaluation and optimization of flocculation process for removing heavy metal. Chemical Engineering Journal, 385, 123911.
Stec, M., Jagustyn, B., Słowik, K., Ściążko, M., & Iluk, T. (2020). Influence of high chloride concentration on pH control in hydroxide precipitation of heavy metals. Journal of Sustainable Metallurgy, 6, 239-249.
Taseidifar, M., Makavipour, F., Pashley, R. M., & Rahman, A. M. (2017). Removal of heavy metal ions from water using ion flotation. Environmental Technology & Innovation, 8, 182-190.
Wang, W., Hua, Y., Li, S., Yan, W., & Zhang, W. X. (2016). Removal of Pb (II) and Zn (II) using lime and nanoscale zero-valent iron (nZVI): a comparative study. Chemical Engineering Journal, 304, 79-88.
Wang, L. P., & Chen, Y. J. (2019). Sequential precipitation of iron, copper, and zinc from wastewater for metal recovery. Journal of Environmental Engineering, 145(1), 04018130.
Wu, R. (2019). Removal of Heavy Metal Ions from Industrial Wastewater Based on Chemical Precipitation Method. Ekoloji Dergisi, 107, 2443-2452.
Yadav, M., Singh, G., & Jadeja, R. N. (2021). Physical and chemical methods for heavy metal removal. Pollutants and Water Management: Resources, Strategies and Scarcity. United States: John Wiley & Sons Ltd.
Zand, A. D., & Abyaneh, M. R. (2019). Equilibrium and kinetic studies in remediation of heavy metals in landfill leachate using wood-derived biochar. Desalination and Water Treatment, 141, 279-300.
Zendelska, A., Trajanova, A., Golomeova, M., Golomeov, B., Mirakovski, D., Doneva, N., & Hadzi-Nikolova, M. (2022). Comparison of Efficiencies of Neutralizing Agents for Heavy Metal Removal from Acid Mine Drainage. Journal of Mining and Environment, 13(3), 679-691.
Zhang, Y., & Duan, X. (2020). Chemical precipitation of heavy metals from wastewater by using the synthetical magnesium hydroxy carbonate. Water Science and Technology, 81(6), 1130-1136.
Zhang, H., Chen, J., Ni, S., Bie, C., Zhi, H., & Sun, X. (2022). A clean process for selective recovery of copper from industrial wastewater by extraction-precipitation with p-tert-octyl phenoxy acetic acid. Journal of Environmental Management, 304, 114164.
Zhu, Y., Fan, W., Zhou, T., & Li, X. (2019). Removal of chelated heavy metals from aqueous solution: A review of current methods and mechanisms. Science of the Total Environment, 678, 253-266.