Applied Chemical Engineering

Treatment of AL-Diwaniyah Petroleum Refinery Wastewater by Heterogeneous Fenton–Like Using Fe2O3 @ CeO2; 1:2 Ratio /AC Nanocatalyst

Saleem F. Mones

University of Al.Qadissiyah-College of Engineering -Chemical Engineering

Husham M.Al-Tameeemi

University of Al.Qadissiyah-College of Engineering -Chemical Engineering

Rafid K. Abbas

University of Al.Qadissiyah-College of Engineering -Chemical Engineering

Zahraa M. Ghafil

University of Al.Qadissiyah-College of Engineering -Chemical Engineering

DOI: https://doi.org/10.59429/ace.v9i2.5943

Keywords: Petroleum refinery wastewater; heterogeneous Fenton process; Fe2O3; Fenton- Like; CeO2

---

Abstract

In present work, a heterogeneous Fenton process using prepared Fe2O3@ CeO2; 1:2 ratio /AC nanocatalyst was used to treat wastewater discharged from Iraqi petroleum refinery plant. The heterogeneous Fenton process was evaluated for its efficiency in removing COD via application a response surface methodology (RSM) and adopting a batch mode. Three essential operating factors were considered namely catalyst dosage (0.5-1.5 g/l), H2O2 dosage (0.4-1), and pH (3-7). The Fe2O3@ CeO2; 1:2 ratio /AC nanocatalyst was characterized using XRD, FESEM. EDS techniques. Results showed good adhesion property of the prepared nanomaterials with nano size with particle size diameter in range of (31.52- 69.08 nm). The optimum operating conditions were:  catalyst dosage of 1.5 g/l, H2O2 dosage of 0.5878 g/l and pH of 3 in which RE% of 85% was achieved. Results of ANOVA confirmed that the catalyst dosage has the most significant effect on RE% with a contribution of 57.66% followed by pH is 22.03%, and H2O2 dosage is 11.91%. The comparison between the classical Fenton processes with heterogeneous Fenton process (Fenton- Like) showed that higher removal efficiency could be achieved using the heterogeneous Fenton process conferring the importance of application this processes as an alternative, sustainable, and cost-effective processes in the treatment of petroleum wastewaters.

---

References

[1]. Zhang, Y., Gao, M. M., Wang, X. H., Wang, S. G., & Liu, R. T. (2015). Enhancement of oxygen diffusion process on a rotating disk electrode for the electro-Fenton degradation of tetracycline. Electrochimica Acta, 182, 73-80.

[2]. Al-Malack, M. H., & Siddiqui, M. (2013). Treatment of synthetic petroleum refinery wastewater in a continuous electro-oxidation process. Desalination and Water Treatment, 51(34–36), 6580–6591.

[3]. Kavitha, V., & Palanivelu, K. (2004). The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol. Chemosphere, 55(9), 1235–1243.

[4]. Al Hashemi, W., Maraqa, M. A., Rao, M. V., & Hossain, M. M. (2015). Characterization and removal of phenolic compounds from condensate-oil refinery wastewater. Desalination and Water Treatment, 54(3), 660-671.

[5]. Aljuboury, D. A. D. A., Palaniandy, P., Abdul Aziz, H. B., & Feroz, S. A. D. A. (2017). Treatment of petroleum wastewater by conventional and new technologies-A review. Glob. Nest J, 19(3), 439-452.

[6]. Dutta, S., Gupta, B., Srivastava, S. K., & Gupta, A. K. (2021). Recent advances on the removal of dyes from wastewater using various adsorbents: A critical review. Materials Advances, 2(14), 4497-4531.

[7]. Malik M. Mohammed, Ali Akber Amooey& Haider Alwan “Electro Oxidation Process for Wastewater Treatment in Petroleum Refineries”, 2024, Pollution 10 (2), 819-832 [7]

[8]. Kalash, K. R., Al-Furaiji, M. H., Mter, K. A., Alalwan, H. A., Alazraqi, A. R., Sultan, H. I., & Algam, M. H. (2025). Assessment of hybrid treatment process for high-COD oily wastewater following Iraqi discharge regulations: A case study from Baghdad power plant. Indian Chemical Engineer, 1–16. https://doi.org/10.1080/00194506.2025.2579533

[9]. Hassan, A. A., Naeem, H. T., & Hadi, R. T. (2018). Degradation of oily waste water in aqueous phase using solar (ZnO, TiO2 and Al2O3) catalysts. Pakistan Journal of Biotechnology, 15(4), 927-934.

[10]. Xu, M., Wu, C. and Zhou, Y., 2020. Advancements in the Fenton process for wastewater treatment. In Advanced oxidation processes-applications, trends, and prospects. IntechOpen.

[11]. Lama, G., Meijide, J., Sanroman, A. and Pazos, M., 2022. Heterogeneous advanced oxidation processes: current approaches for wastewater treatment. Catalysts, 12(3), p.344.

[12]. Marwa Abd Aljaleel; Hameed Hussein Alwan; “Modeling the Effect of Operation Variables on Copper Ions Removal by Electrocoagulation” 2022 2nd International Conference on Advances in Engineering Science and Technology (AEST)

[13]. Sata Kathum Ajjam et al,; “Nitrate removal from simulated wastewater by electrocoagulation: Impact of operating parameters on removal efficiency and energy consumption”; South African Journal of Chemical Engineering;Volume 55, January 2026, Pages 1-10

[14]. Ahmadreza Yazdanbakhash, et al.,2018 “Performance of granular activated carbon/nanoscale zero-valent iron for removal of humic substances from aqueous solution based on Experimental Design and Response Surface Modeling” Global NEST Journal, Vol 20, No X, pp XX-XX

[15]. Al-Furaiji, M. H., Alalwan, H. A., Sultan, H. I., & Al-Shaeli, M. N. (2021). Synthesis of ZnO–CoO/Al2O3 nanoparticles and its application as a catalyst in ethanol conversion to acetone. Results in Chemistry, 3, 100249. https://doi.org/10.1016/j.rechem.2021.100249.

[16]. Al-Tameemi, H.M., Sukkar, K.A. & Abbar, A.H. Electrochemical Treatment of Petroleum Refinery Wastewater Using SnO2 and Graphite Anodes. Pet. Chem. 64, 144–150 (2024). https://doi.org/10.1134/S0965544124020075

[17]. El-Ghenymy, A., Garcia-Segura, S., Rodríguez, R. M., Brillas, E., El Begrani, M. S., & Abdelouahid, B. A. (2012). Optimization of the electro-Fenton and solar photoelectro-Fenton treatments of sulfanilic acid solutions using a pre-pilot flow plant by response surface methodology. Journal of hazardous materials, 221, 288-297.‏

[18]. Evans, M., 2003. Optimization of Manufacturing Processes: A Response Surface Approach. Carlton House Terrace, London.

[19]. Alalwan, H. A., Sultan, H. I., Al-Furaiji, M. H., & Al-Shaeli, M. N. (2022). Using Box–Behnken experimental design for optimization of gas oil desulfurization by electrochemical oxidation technique. Fuel Processing Technology.

[20]. Alalwan, H. A., Sultan, H. I., Al-Furaiji, M. H., & Al-Shaeli, M. N. (2023). Methane activation on metal oxide nanoparticles: Spectroscopic identification of reaction mechanism. Particulate Science and Technology, 41(5), 653–660. https://doi.org/10.1080/02726351.2022.2034567

[21]. Alalwan, H. A., Sultan, H. I., Al-Furaiji, M. H., & Al-Shaeli, M. N. (2023). Spectroscopic investigation of carbon dioxide interactions with transition metal-oxide nanoparticles. Chemical Engineering & Technology, 46(3), 587–594. https://doi.org/10.1002/ceat.202200355

[22]. Alalwan, H. A., Sultan, H. I., Al-Furaiji, M. H., & Al-Shaeli, M. N. (2022). Employing synthesized MgO–SiO2 nanoparticles as catalysts in ethanol conversion to 1,3-butadiene. International Journal of Nanoscience and Nanotechnology, 18(3), 157–166.

[23]. Huizhi Bao, “Structure-activity Relation of Fe2O3–CeO2 Composite Catalysts in CO Oxidation” catalysis letters, Volume 125, pages 160–167, (2008)

[24]. Naife, T.M., 2012. ADSORPTION STUDY OF HYDRODESULPHURIZATION CATALYST. Journal of Engineering, 18(01), pp.38-50.

[25]. Mariana Riboli Nava et al.; “Characterization of CeO2–Fe2O3 Mixed Oxides: Influence of the Dopant on the Structure” Journal of Photochemistry & Photobiology, A: Chemistry (2022).

[26]. Asyah R. Flayyih, Ali H. Abbar, “Treatment of petroleum refinery wastewater by a heterogeneous electro-Fenton process using activated carbon loaded with Fe2O3-CeO2 as a catalyst”, Results in Engineering,Volume 28,2025,

[27]. Zheng-nan Sun, Qi Yang, Dong-li Ji, Lin Zheng., “Degradation of 3,4- Dichlorobenzotrifluoride by Fe3O4/CeO2-H2O2 Heterogeneous Fenton-Like Systems”; PubMed, 2015 Jun;36(6):2154-60.

[28]. Xiaobin Hua et al., 2011 “Adsorption and heterogeneous Fenton degradation of 17_-methyltestosterone on nano Fe3O4/MWCNTs in aqueous solution” Applied Catalysis B: Environmental 107 (2011) 274– 283.

[29]. J. He, W.H. Ma, J.J. He, J.C. Zhao, J.C. Yu, Appl. Catal. B: Environ. 39 (2002) 211–220.

[30]. Y.P. Zhao, H.Y. Hu, Appl. Catal. B: Environ. 78 (2008) 250–258.

[31]. Ghasemi, Z., Younesi, H., & Zinatizadeh, A. A. (2016). Kinetics and thermodynamics of photocatalytic degradation of organic pollutants in petroleum refinery wastewater over nano-TiO2 supported on Fe-ZSM-5. Journal of the Taiwan Institute of Chemical Engineers, 65, 357-366

[32]. De Oliveira, C. P. M., Viana, M. M., & Amaral, M. C. S. (2020). Coupling photocatalytic degradation using a green TiO2 catalyst to membrane bioreactor for petroleum refinery wastewater reclamation. Journal of Water Process Engineering, 34, 101093.‏

[33]. Aljuboury, D.D.A., Palaniandy, P., Abdul Aziz, H.B., Feroz, S., 2015. Evaluating the TiO2 as a solar photocatalyst process by response surface methodology to treat the petroleum waste water, Karbala Inter. J. Mod. Sci. 1, 78–85.

[34]. Nishanth Thomas, Dionysios D. Dionysiou, Suresh C. Pillai, “Heterogeneous Fenton catalysts: A review of recent advances”, Journal of Hazardous Materials,Volume 404, Part B,2021.

[35]. Israa Mohammed, Hameed Hussein Alwan and A. N. Ghanim"Using Box-Behnken experimental design for optimization of gasoil desulfurization by electrochemical oxidation technique”, IOP Conf. Series: Materials Science and Engineering 928 (2020) 022158.