Enhanced COD Reduction of Olefin Plant Spent Caustic Wastewater Using Easily Recyclable Cu(BDC)/MgO Nanocomposites

Document Type : Research Paper

Authors

1 Polymer Eng. Dept, Faculty of Gas and Petroleum, Yasouj University, Gachsaran, Iran.

2 Chem. Eng. Dept., University of Science and Technology of Mazandaran, Behshahr, Iran.

Abstract

This study explored the photocatalytic degradation process for treating industrial spent caustic wastewater, focusing on reducing chemical oxygen demand (COD). Cu(BDC)/MgO nanocomposites were synthesized via microwave-assisted synthesis and served as efficient photocatalysts. An artificial neural network (ANN) model was developed to estimate COD concentrations and optimize treatment parameters, aiming to achieve superior COD reduction. The research aimed to minimize the hydrogen peroxide-to-COD ratio and to optimize other factors influencing COD removal. The synthesized nanocomposites were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and energy-dispersive X-ray spectroscopy (EDS) elemental mapping. Optimal parameters for achieving a 97.55% COD removal efficiency were identified as a nanocomposite dose of 1.30 g/L, an H2O2/Spent caustic wastewater ratio of 1.50 ml/L, a pH of 3.0, a treatment time of 35 min, and an aeration flow rate of 2.50 L/min. Catalyst recycling studies demonstrated the exceptional recyclability and stability of the Cu(BDC)/MgO nanocomposites, showing they could be reused as catalysts even after five treatment cycles. This highlights the potential for prolonged and sustainable use of these nanocomposites in wastewater treatment processes, effectively reducing COD levels in spent caustic effluents.

Keywords

Main Subjects

References

  1. Liu J, Jiang L, Zhang H, Yao H, Chai J, Wang J, Fang D, Zhang Z, Tie M. Construction of high-proportion dual bismuth-based Z-scheme Bi3O4Cl/Bi2MoO6 photocatalytic system via in-situ growth of Bi2MoO6 on Bi3O4Cl for enhanced photocatalytic degradation of organic pollutants. Journal of Alloys and Compounds. 2023 Sep 15;956:170375. https://doi.org/10.1016/j.jallcom.2023.170375
  2. Li J, Wang Q, Liang J, Li H, Guo S, El-Din MG, Chen C. Enhanced disintegration using refinery spent caustic for anaerobic digestion of refinery waste-activated sludge. Journal of Environmental Management. 2021 Apr 15;284:112022. https://doi.org/10.1016/j.jenvman.2021.112022
  3. Delnavaz M, Khoshvaght H, Sadeghi A, Ghasemipanah K, Aliabadi MH. Experimental, statistical, and financial analysis of the treatment of organic contaminants in naphthenic spent caustic soda using the electrocoagulation process modified by carbon nanotubes. Journal of Cleaner Production. 2021 Dec 10;327:129515. https://doi.org/10.1016/j.jclepro.2021.129515
  4. Hashemi SR, Heydarinasab A, Amoozegar MA. Modified biological treatment of spent caustic effluent from liquefied petroleum gas plants. Chemical Engineering & Technology. 2020 Feb;43(2):380-5. https://doi.org/10.1002/ceat.201900368
  5. Hawari A, Ramadan H, Abu-Reesh I, Ouederni M. A comparative study of the treatment of ethylene plant spent caustic by neutralization and classical and advanced oxidation. Journal of environmental management. 2015 Mar 15;151:105-12. https://doi.org/10.1016/j.jenvman.2014.12.038
  6. Zhang X, Liu T, Zhang Y, Cai Z, Wan Q. Co-operative harmless treatment and neutralization utilization process research of LPG spent caustic coupled chloroaluminate ionic liquid spent catalysts. Journal of Water Process Engineering. 2023 Apr 1;52:103507. https://doi.org/10.1016/j.jwpe.2023.103507
  7. Alipour Z, Azari A. COD removal from industrial spent caustic wastewater: A review. Journal of environmental chemical engineering. 2020 Jun 1;8(3):103678. https://doi.org/10.1016/j.jece.2020.103678
  8. González C, Pariente MI, Molina R, Espina LG, Masa MO, Bernal V, Melero JA, Martinez F. Increasing biodegradability of a real amine-contaminated spent caustic problematic stream through WAO and CWAO oxidation using a high specific surface catalyst from petcoke. Chemical Engineering Journal. 2023 Mar 15;460:141692. https://doi.org/10.1016/j.cej.2023.141692
  9. Ntagia E, Fiset E, Hong LT, Vaiopoulou E, Rabaey K. Electrochemical treatment of industrial sulfidic spent caustic streams for sulfide removal and caustic recovery. Journal of Hazardous Materials. 2020 Apr 15;388:121770. https://doi.org/10.1016/j.jhazmat.2019.121770
  10. Rita AI, Rodrigues CS, Santos M, Sanches S, Madeira LM. Comparison of different strategies to treat challenging refinery spent caustic effluents. Separation and purification technology. 2020 Dec 15;253:117482. https://doi.org/10.1016/j.seppur.2020.117482
  11. Fernandes A, Makoś P, Wang Z, Boczkaj G. Synergistic effect of TiO2 photocatalytic advanced oxidation processes in the treatment of refinery effluents. Chemical Engineering Journal. 2020 Jul 1;391:123488. https://doi.org/10.1016/j.cej.2019.123488
  12. Gholami A, Mousavi SB, Heris SZ, Mohammadpourfard M. Highly efficient treatment of petrochemical spent caustic effluent via electro-Fenton process for COD and TOC removal: optimization and experimental. Biomass Conversion and Biorefinery. 2024 Aug;14(15):17481-97. https://doi.org/10.1007/s13399-023-03772-2
  13. Davarnejad R, Bakhshandeh M. Olefin plant spent caustic wastewater treatment using electro-Fenton technique. Egyptian journal of petroleum. 2018 Dec 1;27(4):573-81. https://doi.org/10.1016/j.ejpe.2017.08.008
  14. Dong C, Fang W, Yi Q, Zhang J. A comprehensive review on reactive oxygen species (ROS) in advanced oxidation processes (AOPs). Chemosphere. 2022 Dec 1;308:136205. https://doi.org/10.1016/j.chemosphere.2022.136205
  15. Hua X, Chen H, Rong C, Addison F, Dong D, Qu J, Liang D, Guo Z, Zheng N, Liu H. Visible-light-driven photocatalytic degradation of tetracycline hydrochloride by Z-scheme Ag3PO4/1T@ 2H-MoS2 heterojunction: degradation mechanism, toxicity assessment, and potential applications. Journal of Hazardous Materials. 2023 Apr 15;448:130951. https://doi.org/10.1016/j.jhazmat.2023.130951
  16. Zhao Y, Chang L, Li Y, He W, Liu K, Cui M, Hameed MU, Xie J. High-gravity photocatalytic degradation of tetracycline hydrochloride under simulated sunlight. Journal of Water Process Engineering. 2023 Jul 1;53:103753. https://doi.org/10.1016/j.jwpe.2023.103753
  17. Wei Y, Zhao J, Liu Z, Zhang L, Cui Q, Wang H. Study on wet oxidation process and mechanism for ethylene spent caustic. Environmental Technology. 2022 Jul 29;43(17):2637-46. https://doi.org/10.1080/09593330.2021.1892200
  18. Ahmadpour A, Asl AH, Fallah N. Synthesis and photocatalytic studies of TiO2-clinoptilolite on spent caustic wastewater treatment. Particulate Science and Technology. 2018 Oct 3;36(7):791-8. https://doi.org/10.1080/02726351.2017.1302534
  19. Sarkodie B, Amesimeku J, Frimpong C, Howard EK, Feng Q, Xu Z. Photocatalytic degradation of dyes by novel electrospun nanofibers: a review. Chemosphere. 2023 Feb 1;313:137654. https://doi.org/10.1016/j.chemosphere.2022.137654
  20. Xu P, Ding C, Li Z, Yu R, Cui H, Gao S. Photocatalytic degradation of air pollutant by modified nano titanium oxide (TiO2) in a fluidized bed photoreactor: Optimizing and kinetic modeling. Chemosphere. 2023 Apr 1;319:137995. https://doi.org/10.1016/j.chemosphere.2023.137995
  21. AlSalhi MS, Devanesan S, Asemi NN, Aldawsari M. Construction of SnO2/CuO/rGO nanocomposites for photocatalytic degradation of organic pollutants and antibacterial applications. Environmental Research. 2023 Apr 1;222:115370. https://doi.org/10.1016/j.envres.2023.115370
  22. Fouda A, Hassan SE, Saied E, Hamza MF. Photocatalytic degradation of real textile and tannery effluent using biosynthesized magnesium oxide nanoparticles (MgO-NPs), heavy metal adsorption, phytotoxicity, and antimicrobial activity. Journal of Environmental Chemical Engineering. 2021 Aug 1;9(4):105346. https://doi.org/10.1016/j.jece.2021.105346
  23. Zhu Z, Xia H, Li H. Boosting photocatalytic degradation efficiency of tetracycline by a visible-light-activated NiMoO4/g-C3N4 heterojunction photocatalyst in the water environment. Solid State Sciences. 2023 May 1;139:107164. https://doi.org/10.1016/j.solidstatesciences.2023.107164
  24. Chandrasekar M, Subash M, Perumal V, Panimalar S, Aravindan S, Uthrakumar R, Inmozhi C, Isaev AB, Muniyasamy S, Raja A, Kaviyarasu K. Specific charge separation of Sn doped MgO nanoparticles for photocatalytic activity under UV light irradiation. Separation and Purification Technology. 2022 Aug 1;294:121189. https://doi.org/10.1016/j.seppur.2022.121189
  25. Scott T, Zhao H, Deng W, Feng X, Li Y. Photocatalytic degradation of phenol in water under simulated sunlight by an ultrathin MgO coated Ag/TiO2 Chemosphere. 2019 Feb 1;216:1-8. https://doi.org/10.1016/j.chemosphere.2018.10.083
  26. Prabhu PS, Kathirvel P, Maruthamani D, Ram SG. Enhanced photocatalytic activity of methylene blue dye by DIFS synthesized pure and Mn doped MgO nanostructures. Optik. 2023 Jul 1;283:170869. https://doi.org/10.1016/j.ijleo.2023.170869
  27. Zheng X, Gou Y, Peng H, Mao Y, Wen J. Nonthermal plasma sulfurized CuInS2/S-doped MgO nanosheets for efficient solar-light photocatalytic degradation of tetracycline. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2021 Sep 20;625:126900. https://doi.org/10.1016/j.colsurfa.2021.126900
  28. Ratnam MV, Karthikeyan C, Rao KN, Meena V. Magnesium oxide nanoparticles for effective photocatalytic degradation of methyl red dye in aqueous solutions: optimization studies using response surface methodology. Materials Today: Proceedings. 2020 Jan 1;26:2308-13. https://doi.org/10.1016/j.matpr.2020.02.498
  29. Chahar D, Kumar D, Thakur P, Thakur A. Visible light induced photocatalytic degradation of methylene blue dye by using Mg doped Co-Zn nanoferrites. Materials Research Bulletin. 2023 Jun 1;162:112205. https://doi.org/10.1016/j.materresbull.2023.112205
  30. Ali AA, El Fadaly EA, Deraz NM. Auto-combustion fabrication, structural, morphological and photocatalytic activity of CuO/ZnO/MgO nanocomposites. Materials Chemistry and Physics. 2021 Sep 15;270:124762. https://doi.org/10.1016/j.matchemphys.2021.124762
  31. An X, Chen Y, Ao M, Jin Y, Zhan L, Yu B, Wu Z, Jiang P. Sequential photocatalytic degradation of organophosphorus pesticides and recovery of orthophosphate by biochar/α-Fe2O3/MgO composite: A new enhanced strategy for reducing the impacts of organophosphorus from wastewater. Chemical Engineering Journal. 2022 May 1;435:135087. https://doi.org/10.1016/j.cej.2022.135087
  32. Su X, Cao N, Feng J, Li W, Ding X, Li Z, Gao M, Hu L, Zhang H, Ren Y, Wei T. The enhanced photocatalytic performance of the amorphous carbon/MgO nanofibers: Insight into the role of the oxygen vacancies and 1D morphology. Applied Surface Science. 2023 Apr 15;616:156470. https://doi.org/10.1016/j.apsusc.2023.156470
  33. Mylarappa M, Raghavendra N, Surendra BS, Kumar KS, Kantharjau S. Electrochemical, photocatalytic and sensor studies of clay/MgO nanoparticles. Applied Surface Science Advances. 2022 Aug 1;10:100268. https://doi.org/10.1016/j.apsadv.2022.100268
  34. Bateni A, Valizadeh K, Salahshour Y, Behroozi AH, Maleki A. Fabrication and characterization of pectin-graphene oxide-magnesium ferrite-zinc oxide nanocomposite for photocatalytic degradation of diclofenac in an aqueous solution under visible light irradiation. Journal of Environmental Management. 2022 Dec 15;324:116358. https://doi.org/10.1016/j.jenvman.2022.116358
  35. Liu Y, Zhang L, Liu T, Wang J. Photocatalytic selective oxidation of ammonium to dinitrogen by FeOx-MgO activated persulfate under solar-light irradiation. Chemical Engineering Journal. 2023 Feb 15;454:140499. https://doi.org/10.1016/j.cej.2022.140499
  36. Arif S, Nawaz M, Siddique S, Ayub R, Saleem S. Synthesis, characterization and photocatalytic activity of Mg1−xCuxO nanoparticles for wastewater treatment. Materials Today 2022 Dec 1;33:104361. https://doi.org/10.1016/j.mtcomm.2022.104361
  37. Abdollahi B, Farshnama S, Asl EA, Najafidoust A, Sarani M. Cu (BDC) metal–organic framework (MOF)-based Ag2CrO4 heterostructure with enhanced solar-light degradation of organic dyes. Inorganic Chemistry Communications. 2022 Apr 1;138:109236. https://doi.org/10.1016/j.inoche.2022.109236
  38. Sadjadi S, Koohestani F. Palladated composite of Cu-BDC MOF and perlite as an efficient catalyst for hydrogenation of nitroarenes. Journal of Molecular Structure. 2022 Feb 15;1250:131793. https://doi.org/10.1016/j.molstruc.2021.131793
  39. Silva BC, Irikura K, Flor JB, Dos Santos RM, Lachgar A, Frem RC, Zanoni MV. Electrochemical preparation of Cu/Cu2O-Cu (BDC) metal-organic framework electrodes for photoelectrocatalytic reduction of CO2. Journal of CO2 2020 Dec 1;42:101299. https://doi.org/10.1016/j.jcou.2020.101299
  40. Alamgholiloo H, Zhang S, Ahadi A, Rostamnia S, Banaei R, Li Z, Liu X, Shokouhimehr M. Synthesis of bimetallic 4-PySI-Pd@ Cu (BDC) via open metal site Cu-MOF: Effect of metal and support of Pd@ Cu-MOFs in H2 generation from formic acid. Molecular Catalysis. 2019 Apr 1;467:30-7. https://doi.org/10.1016/j.mcat.2019.01.031
  41. Sadjadi S, Koohestani F. Composite of magnetic carbon quantum dot-supported ionic liquid and Cu-BDC (CCDC no. 687690) MOF: A triple catalytic composite for chemical transformations. Journal of Solid State Chemistry. 2022 Apr 1;308:122888. https://doi.org/10.1016/j.jssc.2022.122888
  42. Zhao L, Xia W. Stainless steel membrane UF coupled with NF process for the recovery of sodium hydroxide from alkaline wastewater in chitin processing. Desalination. 2009 Dec 15;249(2):774-80. https://doi.org/10.1016/j.desal.2009.01.036
  43. Nasr Esfahani K, Farhadian M, Solaimany Nazar AR. Interaction effects of various reaction parameters on the treatment of sulfidic spent caustic through electro-photo-Fenton. International Journal of Environmental Science and Technology. 2019 Nov;16:7165-74. https://doi.org/10.1007/s13762-018-2126-8
  44. Mosleh S, Khaksar H. Cu-BDC MOF/CNFs hybrids for rapid CO2 capture in a circulating fluidized bed via temperature swing adsorption process. Chemical Engineering Science. 2024 Apr 5;287:119773. https://doi.org/10.1016/j.ces.2024.119773
  45. Hasan IF, Basim HS, Ibrahim RK, Saadoon NM, Saadoon MM. Effect of MgO-NPs on the Morphology and Function of Kidney in Male Albino Mice. Journal of Nanostructures. 2025 Oct 1;15(4):1690-9. https://doi.org/10.22052/JNS.2025.04.016
  46. American Public Health Association. APHA standard methods for the examination of water and wastewater. Standard methods for the examination of water & wastewater. Washington, DC: American Public Health Association. 2005.
  47. Sadjadi S, Koohestani F. Palladated composite of Cu-BDC MOF and perlite as an efficient catalyst for hydrogenation of nitroarenes. Journal of Molecular Structure. 2022 Feb 15;1250:131793. https://doi.org/10.1016/j.molstruc.2021.131793
  48. Li Z, Xia H, Li S, Pang J, Zhu W, Jiang Y. In situ hybridization of enzymes and their metal–organic framework analogues with enhanced activity and stability by biomimetic mineralisation. 2017;9(40):15298-302. https://doi.org/10.1039/C7NR06315F
  49. James MS, Garg A. Performance of electro-Fenton process for the treatment of synthetic sulphidic spent caustic waste stream generated from petroleum refineries. Chemosphere. 2024 Jan 1;346:140572. https://doi.org/10.1016/j.chemosphere.2023.140572
Journal of Chemical and Petroleum Engineering
Volume 60, Issue 1
June 2026
Pages 89-107

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History

  • Receive Date: 08 March 2025
  • Revise Date: 16 February 2026
  • Accept Date: 12 April 2026

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