Colloid & Nanoscience Journal

Colloid & Nanoscience Journal

Preparation of Nano-magnetic CuO-Fe3O4/Clinoptilolite as Adsorbant for Removal of Sulfur Compounds from Petrochemical and Petroleum Refinery Wastewater

Document Type : Original Article

Authors
Ali Ashuri 1
Kazem Mahanpoor 1
Farshid Khojasteh 2
Hossein Malekhosseini 1
1 Department of Chemistry, Ar. C., Islamic Azad University, Arak, Iran
2 Department of Mathematic, Ar. C., Islamic Azad University, Arak, Iran
Abstract
A novel magnetic nanocomposite, CuO-Fe₃O₄/Clinoptilolite(CP), was synthesized via a co-precipitation method for the efficient removal of sulfur compounds from spent caustic wastewater. The structural and morphological properties of the adsorbent were comprehensively characterized using FT-IR, SEM, TEM, and BET analyses, while XRD confirmed a crystalline particle size ranging from 48 to 98 nm. Optimization of the adsorption parameters—including pH, contact time, adsorbent dosage, and initial sulfur concentration—was conducted using Response Surface Methodology (RSM) based on a Box–Behnken experimental design. The findings reveal that the CuO-Fe₃O₄/CP composite possesses substantial adsorption capacity for various sulfur species present in refinery wastewater. Under optimized conditions (pH 11, dosage 0.3 g/L, and initial concentration 270 mg/L), the removal efficiency reached 75%. Statistical modeling indicated significant synergistic effects between the variables, with adsorbent dosage and contact time exerting the most profound influence on the adsorption process. Furthermore, the adsorption mechanism was found to align closely with the Langmuir isotherm and pseudo-first-order kinetic models. These results suggest that the developed magnetic nanocomposite is a highly effective and scalable solution for the remediation of sulfur-rich effluents in the petrochemical industry.

Graphical Abstract

Preparation of Nano-magnetic CuO-Fe3O4/Clinoptilolite as Adsorbant for Removal of Sulfur Compounds from Petrochemical and Petroleum Refinery Wastewater
Keywords
Spent caustic
Sulfur compounds
Adsorption
Magnetic CuO-Fe3O4, clinoptilolite
Box&ndash
Behnken design
 
 
[1] E. E. Alter, M. A. Heederick, J. H. Van der Schyf, Sulphide pollutants elimination and degradation in petroleum wastewater by ozonation process, Journal of the Southern African Institute of Mining and Metallurgy 98 (1998) 25–32.
[2] S.D.A. Daflon, I.L. Guerra, M.V. Reynier, C.R. Botta, J.C. Campos, Toxicity identification and evaluation of a refinery wastewater from Brazil (Phase I), Ecotoxicol. Environ. Contam. 10 (2015) 41-45. https://doi.org/10.5132/eec.2015.01.07
 
[3] M. Winter, R. Kickuth, Sulphur compounds—their environmental aspect and their elimination from waste water, Toxicol. Environ. Chem. 20-21 (1989) 507-514. https://doi.org/10.1080/02772248909357415
 
[4] V. Milosevic, F. Naranjo, D. Kosanic, J. Zarczynski, C. Stewart, System and method for treatment of spent caustic wastewater, U.S. Patent US 2015/0068984 A1 (2015).
 
[5] Hjort.M et al., Assessment of oil refinery wastewater and effluent integrating bioassays, mechanistic modelling and bioavailability evaluation, Chemosphere, 287(3)(2022) 132146, 2. https://doi.org/10.1016/j.chemosphere.2021.132146.
[6] L. Zhang, Y. Li, J. Wang, X. Liu, Membrane separation technology for wastewater treatment: A review on recent advances and future perspectives, Separation and Purification Technology 298 (2022) 121607. https://doi.org/10.1016/j.seppur.2022.121607
 
[7] B.N. Thorat, R.K. Sonwani, Current technologies and future perspectives for the treatment of complex petroleum refinery wastewater: A review, Bioresour. Technol. 355 (2022) 127263. https://doi.org/10.1016/j.biortech.2022.127263
 
[8] R.J. Lewis, R.B. Cope, Chronic low-level hydrogen sulfide exposure and potential effects on human health: A review of the epidemiological evidence, Crit. Rev. Toxicol. 45 (2015) 93-123. https://doi.org/10.3109/10408444.2014.971940
 
[9] P.S. Shaji, et al., Sulfate-reducing bacteria in removal of pollutants: A promising candidate for bioremediation, World J. Microbiol. Biotechnol. 41 (2025) 125. https://doi.org/10.1007/s11274-025-04345-3
 
[10] K.A. Adegoke, et al., New generation adsorbents for water treatment: A review, Heliyon 8 (2022) e09407. https://doi.org/10.1016/j.heliyon.2022.e09407
 
[11] R. Bushra, et al., Exploring the utilization of magnetic composite materials for high-risk contaminant removal from wastewater by adsorption and catalytic processes—A review, Magnetochemistry 10 (2024) 57. https://doi.org/10.3390/magnetochemistry10080057
 
[12] D.W. Breck, Zeolite Molecular Sieves: Structure, Chemistry, and Use, Wiley, New York, NY, USA (1974).
 
[13] Z. Li, et al., Experimental investigation on temperature-dependent H₂S removal performance of CuO/SiO₂ adsorbent, Chem. Eng. J. 515 (2025) 160711.
 
[14] S. Laurent, et al., Magnetic iron oxide nanoparticles: Synthesis, stabilization, vectorization, physicochemical characterizations, and biological applications, Chem. Rev. 108 (2008) 2064-2110. https://doi.org/10.1021/cr068445e
 
[15] R.H. Myers, D.C. Montgomery, C.M. Anderson-Cook, Response Surface Methodology: Process and Product Optimization Using Designed Experiments, 4th ed., Wiley, New York, NY, USA (2016).
 
[16] F.Z. Elamri, et al., Removal of pollutants by olive stones-derived activated carbon@Fe₃O₄ nanocomposites: Effect of calcination temperature on adsorption properties, Inorg. Chem. Commun. 168 (2024) 112942. https://doi.org/10.1016/j.inoche.2024.112942
 
[17] N.B.T. Tran, N.B. Duong, N.L. Le, Synthesis and characterization of magnetic Fe₃O₄/zeolite NaA nanocomposite for the adsorption removal of methylene blue potential in wastewater treatment, J. Chem. 2021 (2021) 6678588. https://doi.org/10.1155/2021/6678588
 
[18] X. Liu, Y. Zhang, Y. Liu, T. Zhang, Green method to synthesize magnetic zeolite/chitosan composites and adsorption of hexavalent chromium from aqueous solutions, Int. J. Biol. Macromol. 194 (2022) 746-754. https://doi.org/10.1016/j.ijbiomac.2021.11.121
 
[19] X. Zhao, et al., Preparation of magnetic hydroxyapatite whisker and its adsorption capacity to cadmium ion, Mater. Today Commun. 38 (2024) 108116. https://doi.org/10.1016/j.mtcomm.2024.108116
 
[20] I. Czekaj, N. Sobuś, Odors adsorption in zeolites including natural clinoptilolite: Theoretical and experimental studies, Materials 17 (2024) 3088. https://doi.org/10.3390/ma17133089
 
[21] M. Zahid, Y. Doszhanov, K. Saurykova, N. Ahmadi, D. Bolatova, M. Kurmanbayeva, A. Aydarbek, R. Ihsas, M. Seitzhanova, D. Akhmetzhanova, A. Kerimkulova, O. Doszhanov, Modification and application of natural clinoptilolite and mordenite from Almaty region for drinking water purification, Molecules 30 (2025) 2021. https://doi.org/10.3390/molecules30092021
 
 
[22] Z. Wei, C. Li, Y. Wang, X. Zhao, H. Li, Recyclable magnetic Fe₃O₄-supported copper oxide as efficient catalyst for oxidation of 5-hydroxymethylfurfural to 2,5-furanediformic acid, Catalysts. 15 (2025) 1120. https://doi.org/10.3390/catal15121120
 
[23] G.E. Box, D.W. Behnken, Some new three level designs for the study of quantitative variables, Technometrics. 2 (1960) 455–475. https://doi.org/10.1080/00401706.1960.10489916
 
[24] M.A. Al-Ghouti, D.A. Da’ana, Guidelines for the use and interpretation of adsorption isotherm models: A review, J. Hazard. Mater. 393 (2020) 122383. https://doi.org/10.1016/j.jhazmat.2020.122383
 
[25] V.K. Gupta, I. Ali, T.A. Saleh, A. Nayak, S. Agarwal, Chemical treatment technologies for waste-water recycling—an overview, RSC Adv. 2 (2012) 6380–6388. https://doi.org/10.1039/c2ra21077a
 
[26] G. Crini, E. Lichtfouse, L.D. Wilson, N. Morin-Crini, Conventional and non-conventional adsorbents for wastewater treatment, Environ. Chem. Lett. 17 (2019) 195–213. https://doi.org/10.1007/s10311-018-0785-9
 
[27] P. Tripathi, V.C. Srivastava, A. Kumar, Optimization of an azo dye batch adsorption parameters using Box–Behnken design, Desalination. 249 (2009) 1273–1279. https://doi.org/10.1016/j.desal.2008.11.008
 
[28] B. Sadeghalvad, A.R. Azadmehr, H. Motevalian, Statistical design and kinetic and thermodynamic studies of Ni(II) adsorption on bentonite, J. Cent. South Univ. 24 (2017) 1529–1536. https://doi.org/10.1007/s11771-017-3557-y
 
[29] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and platinum, J. Am. Chem. Soc. 40 (1918) 1361–1403. https://doi.org/10.1021/ja02242a004
 
[30] H. Freundlich, Über die Adsorption in Lösungen, Zeitschrift für Physikalische Chemie. 57 (1907) 385–470. https://doi.org/10.1515/zpch-1907-5723
 
[31] M.J. Temkin, V. Pyzhev, Kinetics of ammonia synthesis on promoted iron catalysts, Acta Physiochimica URSS. 12 (1940) 327–356.
 
[32] I. Ben Hariz, F. Al Ayni, L. Monser, Removal of sulfur compounds from petroleum wastewater through adsorption on modified activated carbon, Water Sci. Technol. 70 (2014) 1376–1382. https://doi.org/10.2166/wst.2014.384
 
[33] S. Ben Youssef, T. Chouikhi, A.B. Lamine, Cotton Spinning Waste as a Microporous Activated Carbon: Application to Remove Sulfur Compounds in a Tunisian Refinery Company, Sustainability. 15 (2022) 654. https://doi.org/10.3390/su15010654
 
[34] L. Chen, Y. Wang, Y. Lang, W. Wen, Z. Li, H. Zhao, Y. Li, Enhanced removal of sulfur-containing ions post persulfate advanced oxidation: Interfacial adsorption-mediated foam fractionation process by amphiphilic graphene oxide, Water Res. 289 (2026) 124923. https://doi.org/10.1016/j.watres.2025.124923
 
[35] W.H. Hoidy, A.H. Al-Obaidy, E.A. Al-Mulla, Synergistic AC–ZnO/Al₂O₃ composite: a dual-function adsorbent for simultaneous petroleum desulfurization and aqueous pollutant removal, Pure Appl. Chem. 97 (2025) 445–458. https://doi.org/10.1515/pac-2025-061
Colloid & Nanoscience Journal
Volume 4, Issue 1
Winter 2026

  • Receive Date 11 June 2026
  • Revise Date 13 July 2026
  • Accept Date 18 July 2026