Oxidative Desulfurization of Model Fuel Using Ni or Mo-based Catalysts Supported on Bio-synthesized γ-Al2O3; Optimization of Synthesis Parameters
DOI:
https://doi.org/10.15377/2410-3624.2026.1.2Keywords:
Ni, Mo, γ-Al2O3, Catalysis, Bio template, Oxidative desulfurization.Abstract
In this study, γ-Al₂O₃ was synthesized via a green sol–gel route using four bio-templates (Pistacia Atlantica gum, glucose, gelatine, and gond katira gum) and applied as support for Ni- and Mo-based oxidative desulfurization (ODS) catalysts. XRD analysis confirmed the selective formation of high-purity γ-Al₂O₃ in all bio-templated samples, while gelatine-assisted alumina exhibited enhanced crystallinity. BET measurements revealed significantly increased surface areas (up to 190 m² g⁻¹) compared to non-templated alumina, and TEM analysis demonstrated uniform nanoparticles below 5 nm. Following metal deposition, FESEM and TEM analyses showed that ultrasound-assisted impregnation effectively reduced agglomeration and improved NiO dispersion over the mesoporous support. This structural refinement was further supported by BET results, which indicated improved accessible surface area in ultrasonically prepared catalysts compared with conventionally impregnated samples. The NiO/γ-Al₂O₃ catalyst prepared under ultrasound achieved 80% DBT conversion, outperforming conventionally impregnated NiO (76%), Mo-based catalyst (65%), and bare alumina (40%), highlighting the critical role of metal–support interaction and dispersion. A central composite design (CCD) approach was employed to optimize five synthesis and operational parameters (sol pH, calcination temperature, gelatine content, NiO loading, and oxidant-to-sulfur ratio). Under optimized conditions (pH 8.7, 685 °C calcination temperature, 3.65 wt.% gelatine, 16.86 wt.% NiO, O/S = 16.41), DBT conversion reached 98.11%, representing a substantial enhancement over the non-optimized ultrasonically prepared catalyst (80%). The optimized catalyst maintained high stability over seven consecutive cycles, with conversion decreasing only from 97.4% to 86.3%, and recovered to 91.5% after regeneration.
References
[1] Boahene PE, Vedachalam S, Dalai AK. Catalytic oxidative desulfurization of light gas oil over Keggin-type phosphomolybdic acid supported on TUD-1 metallosilicates. Fuel. 2022; 317: 123447. https://doi.org/10.1016/j.fuel.2022.123447
[2] Liu D, Quek X-Y, Hu S, Li L, Lim HM, Yang Y. Mesostructured TUD-1 supported molybdophosphoric acid (HPMo/TUD-1) catalysts for n-heptane hydroisomerization. Catal Today. 2009; 147: S51-7. https://doi.org/10.1016/j.cattod.2009.07.017
[3] Wang D, Liu N, Zhang J, Zhao X, Zhang W, Zhang M. Oxidative desulfurization using ordered mesoporous silicas as catalysts. J Mol Catal A Chem. 2014; 393: 47-55. https://doi.org/10.1016/j.molcata.2014.05.026
[4] Wang Y, Hua M, Zhou S, Hu D, Liu F, Cheng H, et al. Regulating the coordination environment of surface alumina on NiMo/Al₂O₃ to enhance ultra-deep hydrodesulfurization of diesel. Appl Catal B Environ Energy. 2024; 357: 124265. https://doi.org/10.1016/j.apcatb.2024.124265
[5] Liu J, Liu Y, Wang Y, Zhang W, Liang S, You F, et al. Regulating the electron affinity of NiMo/Al₂O₃ to enhance ultra-deep hydrodesulfurization of diesel. Appl Catal B Environ Energy. 2025; 378: 125565. https://doi.org/10.1016/j.apcatb.2025.125565
[6] Zhou S, Pan Y, Wang Y, Liang S, Cheng H, Huang Y, et al. Structure-reactivity relationship of Fe-triggered NiMoS active phase for ultradeep hydrodesulfurization of diesel. Chem Eng Sci. 2025; 317: 122071. https://doi.org/10.1016/j.ces.2025.122071
[7] Khodadadi Dizaji A, Mortaheb HR, Mokhtarani B. Complete oxidative desulfurization using graphene oxide-based phosphomolybdic acid catalyst: process optimization by two phase mass balance approach. Chem Eng J. 2018; 335: 362-72. https://doi.org/10.1016/j.cej.2017.10.129
[8] Luo J, Wang C, Liu J, Wei Y, Chao Y, Zou Y, et al. High-performance adsorptive desulfurization by ternary hybrid boron carbon nitride aerogel. AIChE J. 2021; 67: e17280. https://doi.org/10.1002/aic.17280
[9] Alwan HH. Oxidative desulfurization of a model fuel using MoO₃ nanoparticles supported on carbon nanotubes catalyst: examine most significance variables, optimization, kinetics and thermodynamics study. S Afr J Chem Eng. 2022; 40: 230-9. https://doi.org/10.1016/j.sajce.2022.03.002
[10] Deng C, Zhu H, Huang Y, Liu H, Liu P, Cui P, et al. High temperature oxidizing-resistant magnetic high entropy catalyst for efficient oxidative desulfurization. Catal Today. 2022; 405-406: 66-74. https://doi.org/10.1016/j.cattod.2022.08.002
[11] Li X, Shi J, Wang J, Xi L, Sun R, Zhang F, et al. Preparation of CeVO₄/BNNS catalyst and its application in oxidation desulfurization of diesel oil. Fuel. 2023; 337: 126875. https://doi.org/10.1016/j.fuel.2022.126875
[12] Choi AES, Roces S, Dugos N, Futalan CM, Lin S-S, Wan M-W. Optimization of ultrasound-assisted oxidative desulfurization of model sulfur compounds using commercial ferrate (VI). J Taiwan Inst Chem Eng. 2014; 45: 2935-42. https://doi.org/10.1016/j.jtice.2014.08.003
[13] Abdulhadi SA, Alwan HH. Oxidative desulfurization of model fuel using a NiO-MoO₃ catalyst supported by activated carbon: optimization study. S Afr J Chem Eng. 2023; 43: 190-6. https://doi.org/10.1016/j.sajce.2022.10.010
[14] Akbari Moghadam S, Mazloom G, Akbari A, Banisharif F. Supported vanadium oxide catalyst over HY-zeolite-alumina composite fabricated by extrusion for oxidative desulfurization of dibenzothiophene. Mol Catal. 2022; 532: 112731. https://doi.org/10.1016/j.mcat.2022.112731
[15] Abedini F, Allahyari S, Rahemi N. One-step oxidative-adsorptive desulfurization of DBT on simulated solar light-driven nano photocatalyst of MoS₂-C₃N₄-BiOBr@MCM-41. Adv Powder Technol. 2022; 33: 103611. https://doi.org/10.1016/j.apt.2022.103611
[16] Ettekali N, Allahyari S, Rahemi N, Abedini F. One-pot oxidative-adsorptive desulfurization of model and real fuel using micro-mesoporous SiO₂ aerogel supported MoO₃. Microporous Mesoporous Mater. 2021; 326: 111376. https://doi.org/10.1016/j.micromeso.2021.111376
[17] Ullah R, Tuzen M. Interactions of Ni/ZnO with alumina support and their influence on deep reactive adsorption desulfurization. J Mol Liq. 2022; 365: 120082. https://doi.org/10.1016/j.molliq.2022.120082
[18] Du Y, Hu J, Jin Y, Liu Y, Pan Q, Wang K, et al. Polyethyleneimine-assisted synthesis of ionic liquid-derived Mo-based mesoporous TiO₂ composite with superior oxidative desulfurization activity. J Environ Chem Eng. 2022; 10: 107143. https://doi.org/10.1016/j.jece.2022.107143
[19] Du Y, Zhou L, Liu Z, Lei J, Li J. Ionic liquid-based 3DOM meso/macroporous Mo/TiO₂ materials with superior oxidation desulfurization performance at room temperature. Mater Res Bull. 2020; 126: 110849. https://doi.org/10.1016/j.materresbull.2020.110849
[20] Yu Z, Xun S, Jing M, Chen H, Song W, Chao Y, et al. Construction of 3D TiO₂ nanoflower for deep catalytic oxidative desulfurization in diesel: role of oxygen vacancy and Ti³⁺. J Hazard Mater. 2022; 440: 129859. https://doi.org/10.1016/j.jhazmat.2022.129859
[21] Ghorbani N, Moradi G. Oxidative desulfurization of model and real oil samples using Mo supported on hierarchical alumina-silica: process optimization by Box-Behnken experimental design. Chin J Chem Eng. 2019; 27: 2759-70. https://doi.org/10.1016/j.cjche.2019.01.037
[22] Mohammadzadeh Yengejeh S, Allahyari S, Rahemi N. Efficient oxidative desulfurization of model fuel by visible-light-driven MoS₂-CeO₂/SiO₂-Al₂O₃ nano photocatalyst coating. Process Saf Environ Prot. 2020; 143: 25-35. https://doi.org/10.1016/j.psep.2020.05.042
[23] Jangi F, Rahemi N, Allahyari S. Oxidative desulfurization using nanocomposites of heterogeneous phosphotungstic acid over natural zeolites: optimization by central-composite design. Pet Sci Technol. 2023; 41: 104-22. https://doi.org/10.1080/10916466.2022.2039703
[24] Chu L, Guo J, Huang Z, Yang H, Yang M, Wang G. Excellent catalytic performance over acid-treated MOF-808(Ce) for oxidative desulfurization of dibenzothiophene. Fuel. 2023; 332: 126012. https://doi.org/10.1016/j.fuel.2022.126012
[25] Li J, Yang Z, Hu G, Zhao J. Heteropolyacid supported MOF fibers for oxidative desulfurization of fuel. Chem Eng J. 2020; 388: 124325. https://doi.org/10.1016/j.cej.2020.124325
[26] Ganiyu SA, Alhooshani K, Sulaiman KO, Qamaruddin M, Bakare IA, Tanimu A, et al. Influence of aluminium impregnation on activated carbon for enhanced desulfurization of DBT at ambient temperature: role of surface acidity and textural properties. Chem Eng J. 2016; 303: 489-500. https://doi.org/10.1016/j.cej.2016.06.005
[27] Koopi H, Buazar F. A novel one-pot biosynthesis of pure alpha aluminum oxide nanoparticles using the macroalgae Sargassum ilicifolium: a green marine approach. Ceram Int. 2018; 44: 8940-5. https://doi.org/10.1016/j.ceramint.2018.02.091
[28] Manogar P, Morvinyabesh JE, Ramesh P, Jeyaleela GD, Amalan V, Ajarem JS, et al. Biosynthesis and antimicrobial activity of aluminium oxide nanoparticles using Lyngbya majuscula extract. Mater Lett. 2022; 311: 131569. https://doi.org/10.1016/j.matlet.2021.131569
[29] Sifontes ÁB, Ávila E, Gutiérrez B, Rengifo M, Mónaco A, Díaz Y, et al. Relevant aspects of the biosynthesis of porous aluminas using glycosides and carbohydrates as biological templates. Biotechnol Res Innov. 2019; 3: 22-37. https://doi.org/10.1016/j.biori.2019.01.004
[30] Filiciotto L, Tosi P, Balu AM, de Jong E, van der Waal JC, Osman SM, et al. Humins as bio-based template for the synthesis of alumina foams. Mol Catal. 2022; 526: 112363. https://doi.org/10.1016/j.mcat.2022.112363
[31] Sabu U, Rashad M, Logesh G, Kumar K, Lodhe M, Balasubramanian M. Development of biomorphic alumina using egg shell membrane as bio-template. Ceram Int. 2018; 44: 4615-21. https://doi.org/10.1016/j.ceramint.2017.11.173
[32] Ma Y, Wei Q, Ling R, An F, Mu G, Huang Y. Synthesis of macro-mesoporous alumina with yeast cell as bio-template. Microporous Mesoporous Mater. 2013; 165: 177-84. https://doi.org/10.1016/j.micromeso.2012.08.016
[33] Mohandessi M, Rahimpour MR. Bio-template fabrication of nanoporous Ni@Al₂O₃: durable catalyst for biogas reforming reaction. Ceram Int. 2023; 49(5): 7476-88. https://doi.org/10.1016/j.ceramint.2022.10.217
[34] Lü H, Li P, Deng C, Ren W, Wang S, Liu P, et al. Deep catalytic oxidative desulfurization (ODS) of dibenzothiophene (DBT) with oxalate-based deep eutectic solvents (DESs). Chem Commun (Camb). 2015; 51: 10703-6. https://doi.org/10.1039/C5CC03324A
[35] Van Truong T, Kim DJ. Synthesis of high quality boehmite and γ-alumina for phosphorus removal from water works sludge by extraction and hydrothermal treatment. Environ Res. 2022; 212: 113448. https://doi.org/10.1016/j.envres.2022.113448
[36] Zhou Y, Gao Y, Wei S, Pan K, Hu Y. Preparation and characterization of Mo/Al₂O₃ composites. Int J Refract Met Hard Mater. 2016; 54: 186-95. https://doi.org/10.1016/j.ijrmhm.2015.07.033
[37] Mishra YK, Adelung R. ZnO tetrapod materials for functional applications. Mater Today. 2018; 21: 631-51. https://doi.org/10.1016/j.mattod.2017.11.003
[38] Zolghadri S, Honarvar B, Rahimpour MR. Synthesis, application, and characteristics of mesoporous alumina as a support of promoted Ni–Co bimetallic catalysts in steam reforming of methane. Fuel. 2023; 335: 127005. https://doi.org/10.1016/j.fuel.2022.127005
[39] Allahyari S, Haghighi M, Ebadi A, Hosseinzadeh S. Effect of irradiation power and time on ultrasound assisted co-precipitation of nanostructured CuO-ZnO–Al₂O₃ over HZSM-5 used for direct conversion of syngas to DME as a green fuel. Energy Convers Manag. 2014; 83: 212-22. https://doi.org/10.1016/j.enconman.2014.03.071
[40] Allahyari S, Haghighi M, Ebadi A, Hosseinzadeh S. Ultrasound assisted co-precipitation of nanostructured CuO–ZnO–Al₂O₃ over HZSM-5: effect of precursor and irradiation power on nanocatalyst properties and catalytic performance for direct syngas to DME. Ultrason Sonochem. 2014; 21: 663-73. https://doi.org/10.1016/j.ultsonch.2013.09.014
[41] Allahyari S, Haghighi M, Ebadi A, Qavam Saeedi H. Direct synthesis of dimethyl ether as a green fuel from syngas over nanostructured CuO–ZnO–Al₂O₃/HZSM-5 catalyst: influence of irradiation time on nanocatalyst properties and catalytic performance. J Power Sources. 2014; 272: 929-9. https://doi.org/10.1016/j.jpowsour.2014.07.152
[42] Azami M, Haghighi M, Allahyari S. Sono-precipitation of Ag₂CrO₄–C composite enhanced by carbon-based materials (AC, GO, CNT and C₃N₄) and its activity in photocatalytic degradation of acid orange 7 in water. Ultrason Sonochem. 2018; 40: 505-16. https://doi.org/10.1016/j.ultsonch.2017.07.043
[43] Ekka B, Dhaka RS, Patel RK, Dash P. Fluoride removal in waters using ionic liquid-functionalized alumina as a novel adsorbent. J Clean Prod. 2017; 151: 303-18. https://doi.org/10.1016/j.jclepro.2017.03.061
[44] González-Gómez MA, Belderbos S, Yañez-Vilar S, Piñeiro Y, Cleeren F, Bormans G, et al. Development of superparamagnetic nanoparticles coated with polyacrylic acid and aluminum hydroxide as an efficient contrast agent for multimodal imaging. Nanomaterials (Basel). 2019; 9: 1626. https://doi.org/10.3390/nano9111626
[45] Maheswari N, Muralidharan G. Controlled synthesis of nanostructured molybdenum oxide electrodes for high performance supercapacitor devices. Appl Surf Sci. 2017; 416. https://doi.org/10.1016/j.apsusc.2017.04.094
[46] Ramanathan A, Castro Villalobos MC, Kwakernaak C, Telalovic S, Hanefeld U. Zr-TUD-1: a Lewis acidic, three-dimensional, mesoporous, zirconium-containing catalyst. Chem Eur J. 2008; 14: 961-72. https://doi.org/10.1002/chem.200700725
[47] Kolar T, Mušič B, Korošec RC, Kokol V. Addition of Al(OH)₃ versus AlO(OH) nanoparticles on the optical, thermo-mechanical and heat/oxygen transmission properties of microfibrillated cellulose films. Cellulose. 2021; 28: 9441-60. https://doi.org/10.1007/s10570-021-04129-6
[48] Asadi F, Allahyari S, Rahemi N, Hussain M. One-pot oxidative-adsorptive desulfurization of model fuel and fuel oil using magnetic boron nitride-based catalysts under ultrasonic irradiations. J Ind Eng Chem. 2024; 133: 439-53. https://doi.org/10.1016/j.jiec.2023.12.020
[49] Zhang F, Yan Y, Liu F, Wu Y, Liang S, Cheng H, et al. Regulating the Fe/Mo ratio of FeMoOₓ/LaTiOᵧ to boost aerobic oxidative desulfurization of diesel. J Fuel Chem Technol. 2025; 53: 1255-68. https://doi.org/10.1016/S1872-5813(25)60576-7
[50] Cheng H, Wu Y, Shao S, Liang S, You F, Wu H, et al. Regulating the metal-support interaction of MoO₃/LaTiOₓ to enhance ultra-deep aerobic oxidative desulfurization of diesel. Chem Eng J. 2025; 519: 165375. https://doi.org/10.1016/j.cej.2025.165375
[51] Wang Y, Luan H, Gong J, Hua M, Wu P, Cheng H, et al. Mechanochemical driven oxidative desulfurization of high-sulfur petroleum coke over [Bpy]PMoVₙ coupled with amide-based binary deep eutectic solvents. Chem Eng Sci. 2025; 304: 121021. https://doi.org/10.1016/j.ces.2024.121021
[52] Lin M, Lou H, Qi Z, Chen J, Ye C, Qiu T. D-alanine-bridged phosphotungstic acid/UiO-66 hybrids as efficient catalysts for oxidative desulfurization of fuels. Chem Eng Sci. 2026; 326: 123545. https://doi.org/10.1016/j.ces.2026.123545
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