Document Type : Research Paper
Author
Department of Chemical Engineering, College of Engineering, University of Al-Qadisiyah, Iraq.
Abstract
The oxidation process of thiols with air is industrially used to treat light petroleum products in the presence of an alkaline solution and a supported catalyst. A low-cost, traditional dye, cobaltous phthalocyanine salt, was used as the active component for catalyst preparation. The supported catalyst was experimentally prepared by impregnation the activated carbon (dp = 1.971 mm) with the uric dye solution in a laboratory batch unit. The prepared catalyst was tested for the oxidation of thiols present in row kerosene. All kinetic experiments were carried out at constant pressure concurrent fixed-bed unit. The effect of temperature and LHSV on conversion percent was investigated. Attempts were made to correlate the data with first and second-order reactions, and it was found that the first-order kinetics correlates the data well with an activation energy of 24.48 kJ/mol. This indicates that the synthesised catalyst is effective and necessary for the reaction to proceed at moderate temperatures with a sufficient rate. Also, the change of enthalpy and entropy were found to be equal to 21.94 kJ/mol and 0.153 kJ/mol K, respectively, with an average Gibbs free energy change of -24.802 kJ/mol. These values indicate that the reaction is weakly spontaneous and thermodynamically favourable, and could proceed at a suitable rate in the presence of the prepared catalyst. Furthermore, the Thiele modulus and internal effectiveness factor were examined, and it was found that the internal diffusion is the major resistance for the oxidation reaction proceeding, and the oxidation reaction takes place only on the outer layer of the surface of the pellets.
Keywords
- Mohammed Abdulla, H. Hussein Alwan, and A. N. Ghanim, “Study reaction kinetics of fuel model desulfurization by electrochemical oxidation technique,” Al-Qadisiyah Journal for Engineering Sciences, vol. 14, no. 1, pp. 1–5, 2021. [Online]. Available: https://doi.org/10.30772/qjes.v14i1.710
- M. Saasaa, R. Kadhim Abbas, and S. Alsamaq, “Reducing the viscosity of missan heavy crude oil using combinations of low molecular weight hydrocarbon compounds,” Al-Qadisiyah Journal for Engineering Sciences, vol. 15, no. 4, pp. 238–243, 2022. [Online]. Available: https://doi.org/10.30772/qjes.v15i4.878
- P. Pineiro, J. Hoshowski, A. Alhammoud, and B. Svidinskiy, “Characterization of products from the chemical removal of thiol in hydrocarbon streams using dart-ms and nmr spectroscopy,” New J. Chem., vol. 49, pp. 8328–8335, 2025. [Online]. Available: http://dx.doi.org/10.1039/D5NJ01033K
- Zhou, H. Xu, J. Ma, X. Zeng, and Y. Wei, “Sustainable synthesis of thiosulfonates and disulfides by molybdenum-catalyzed selective oxidation of thiols,” Green Chem., vol. 26, pp. 4161–4167, 2024. [Online]. Available: http://dx.doi.org/10.1039/D4GC00074A
- K. Sharma, S. K. Thamida, B. N. K. Reddy, and M. Kumar, “Liquefied petroleum gas: A comprehensive review of its manufacturing and refining routes,” Progress in Petrochemical Science, vol. 7, no. 2, pp. 785–792, 2025. [Online]. Available: https://doi.org/10.2139/ssrn.5261732
- Mantos, C. Ferrone, T. Ohta, P. Choudhury, and S. Chowdhury, “nteraction mechanism of transition metal phthalocyanines on transition metal nitride supports,” SSRN, 2022. [Online]. Available: http://doi.org/10.2139/ssrn.4250689
- J. Pereira Monteiro, M. A. Ferreira Faustino, M. d. G. Pinho Morgado Silva Neves, M. M. Quialheiro Sim˜oes, and E. Sanjust, “Metallophthalocyanines as catalysts in aerobic oxidation,” Catalysts, vol. 11, no. 1, 2021. [Online]. Available: https://www.mdpi.com/2073-4344/11/1/122
- G. Makarov, S. Y. Ketkov, I. D. Grishin, and D. W¨ohrle, “Synthesis of heterometallic binuclear cobalt(ii) phthalocyanines and their catalytic activity in the oxidation of a mercaptan,” Journal of Porphyrins and Phthalocyanines, vol. 27, no. 01n04, pp. 694–701, 2023. [Online]. Available: https://doi.org/10.1142/S1088424623500669
- Giddaerappa, NemakalManjunatha, Shantharaja, MirabbosHojamberdiev, and L. Sannegowda, Tetraphenolphthaleincobalt(ii)phthalocyaninepolymermodified withmultiwalledcarbonnanotubesasanefficientcatalystforthe oxygenreductionreaction,” ACS omega, vol. 7, pp. 14 291–14 304, 2022. [Online]. Available: https://doi.org/10.1021/acsomega.2c01157
- J. Keijzer, N. M. van de Ven, R. Dalebout, T. L. Lohr, J. R. Lockemeyer, P. van den Brink, and P. E. de Jongh, “Influence of alkali and chloride promoters on silver catalysts in ethylene epoxidation,” Journal of Catalysis, vol. 450, p. 116206, 2025. [Online]. Available: https://doi.org/10.1016/j.jcat.2025.116206
- Gupta, A. Jana, and M. e. a. Chakraborty, “Treating crude oil storage tank sludge by catalytic process and recovering valuable hydrocarbons,” Chemical Papers, vol. 75, no. 8, pp. 4285–4296, 2021. [Online]. Available: https://doi.org/10.1007/s11696-021-01564-4
- Zuo, Z. Wan, Z. Liao, C. Wang, C.-H. Tan, S. Huo, and L. Zong, “Enantioselectivity and reactivity enhancement by 1, 1, 3, 3-tetramethylguanidine in bisguanidinium-catalyzed asymmetric alkylation for construction of indole alkaloid marine natural products,” ACS Catalysis, vol. 13, no. 24, pp. 15 708–15 714, 2023. [Online]. Available: https://doi.org/10.1021/acscatal.3c03812
- Ertekin and M. D. Symes, “Metal-phthalocyanine complexes as electrocatalysts for the multi-electron reduction of carbon dioxide,” Applied Catalysis A: General, vol. 666, p. 119388, 2023. [Online]. Available: https://doi.org/10.1016/j.apcata.2023.119388
- Lee and A. e. a. Shin, H.AND Rasouli, “Supramolecular tuning of supported metal phthalocyanine catalysts for hydrogen peroxide electrosynthesis,” Nature Catalysis, vol. 6, pp. 234–243, 2023. [Online]. Available: https://doi.org/10.1038/s41929-023-00924-5
- Szymczak and M. Kryjewski, “Porphyrins and phthalocyanines on solid-state mesoporous matrices as catalysts in oxidation reactions,” Materials, vol. 15, no. 7, p. 2532, 2022. [Online]. Available: https://doi.org/10.3390/ma15072532
- P. Zou and A.-B. Yu., “Evaluation of the packing characteristics of mono-sized non-spherical particles,” Powder technology, vol. 88, no. 1, pp. 71–79, 1996. [Online]. Available: https://doi.org/10.1016/0032-5910(96)03106-3
- Chen, Y. Chen, X. Hao, Q. Wen, X. Wang, A. Liu, D. Gao, K. Hu, N. A. Samak, M. Yang, and J. Xing, “New insights into the role of reaction–diffusion behavior in the bio-desulfurization: Relieving thiol-induced inhibition,” Chemical Engineering Journal, vol. 508, p. 160632, 2025. [Online]. Available: https://doi.org/10.1016/j.cej.2025.160632
- Motahari, M. Abdollahi-Moghaddam, and A. Rashidi, “Mechanism study and determination kinetic of catalytic oxidation of mercaptans in merox process,” South African Journal of Chemical Engineering, vol. 33, pp. 116–124, 2020. [Online]. Available: https://doi.org/10.1016/j.sajce.2020.06.003
- A. Al Hussien Qatta and A. K. Mohammad, “Coated material (graphene oxide coated sand) as a new approach in wastewater treatment field: Equilibrium and thermodynamic studies,” Al-Qadisiyah Journal for Engineering Sciences, vol. 14, no. 1, pp. 30–40, 2021. [Online]. Available: https://doi.org/10.30772/qjes.v14i1.692
- Akhmadullin, A. Gubaidullin, E. Kharlampidi, R. Kurbankulov, F. Nigmatullin, U. Dao, F. Khamidullin, G. Akhmadullina, Y. Hoang, and Y. Vasseghian, “Bivalent copper oligopyrocatecholate as a novel heterogeneous catalyst for the oxidative degradation of mercaptan in caustic solution: Synthesis, characterization, and kinetic study,” Environmental Research, vol. 207, p. 112171, 2022. [Online]. Available: https://doi.org/10.1016/j.envres.2021.112171
- Eyring, “”the theory of absolute reaction rates.”,” Transactions of the Faraday Society, vol. 34, pp. 41–48, 1938. [Online]. Available: https://doi.org/10.1039/TF9383400041
- Y. Dursun, M. K. Murshed, and G. Dursun, “Intraparticle diffusion effects on the photodegradation of astrazon orange g dye using tio2 photocatalyst: Optimization via response surface methodology,” Chemical Engineering Research and Design, vol. 220, pp. 426–437, 2025. [Online]. Available: https://doi.org/10.1016/j.cherd.2025.07.020
- Rieder, E. A. J. F. Peters, and J. A. M. Kuipers., “Particle scale impact of the reaction rate on the effective diffusion in coarse porous media,” Chemical Engineering Science, vol. 268, p. 118427, 2023. [Online]. Available: https://doi.org/10.1016/j.ces.2022.118427
- Zhu, S. S. Araya, X. Cui, and S. K. Kar, “The role of effectiveness factor on the modeling of methanol steam reforming over cuo/zno/al2o3 catalyst in a multi-tubular reactor,” International Journal of Hydrogen Energy, vol. 47, no. 14, pp. 8700–8715, 2022. [Online]. Available: https://doi.org/10.1016/j.ijhydene.2021.12.223
- Q. Rios, B. Antunes, A. E. Rodrigues, I. Portugal, and C. M. Silva, “Revisiting isothermal effectiveness factor equations for reversible reactions,” Catalysts, vol. 13, no. 5, p. 889, 2023. [Online]. Available: https://doi.org/10.3390/catal13050889
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