Email this article 
Sustainable Liquid-Phase Alkylation of Toluene Using Zeolitic Catalysts: A Comparative Evaluation of Al-Rich Y and Si-Rich Beta Zeolites for Industrial Green Chemistry to Support Sustainable Development Goals (SDGs)
Abstract
The sustainable synthesis of linear alkylbenzenes (LABs), key intermediates for surfactants and detergents, is essential for minimizing environmental impact in the chemical industry. This study investigates the catalytic efficiency and coke deposition behavior of Al-rich Y and Si-rich Beta zeolites for the liquid-phase alkylation of toluene with 1-octene. The experiments varied temperature, catalyst loading, and time-on-stream to optimize conversion and selectivity. Al-rich Y-zeolite achieved 90% of 1-octene conversion and superior monoalkyltoluene selectivity due to its higher acidity and surface area. Thermogravimetric analyses revealed distinct soft and hard coke profiles, with Y-zeolite showing slightly higher coke content. A kinetic model supported an accurate prediction of coke decomposition behavior. These findings highlight the potential of Y-zeolite as a robust, eco-friendly catalyst, aligning with sustainable development goals (SDGs) and promoting sustainable catalytic processes in petrochemical industries.
Keywords
Full Text:
PDFReferences
Kuvayskaya, A., Mohseni, R., and Vasiliev, A. (2022). Alkylation of benzene by long-chain alkenes on immobilized phosphotungstic acid. Journal of Porous Materials, 29(3), 705-711.
Misaki, S., Takabatake, M., Hasegawa, S., Manaka, Y., Chun, W. J., and Motokura, K. (2024). Effect of zeolites on the alkylation of aromatics with alkanes using a Pd nanoparticle/solid acid cooperative catalytic system. Green Carbon, 2(3), 282-290.
Kim, H. S., Lee, H., Park, H., Song, I., and Kim, D. H. (2024). Revealing the two distinctive roles of HY zeolite in enhancing the activity and durability of manganese oxide-zeolite hybrid catalysts for low-temperature NH3-SCR. Applied Catalysis B: Environment and Energy, 355, 124199.
Pan, A., Chojnacka, M., Crowley, R., Göttemann, L., Haines, B. E., and Kou, K. G. (2022). Synergistic Brønsted/Lewis acid catalyzed aromatic alkylation with unactivated tertiary alcohols or di-tert-butylperoxide to synthesize quaternary carbon centers. Chemical Science, 13(12), 3539-3548.
Lee, D. W., and Yoo, B. R. (2014). Advanced metal oxide (supported) catalysts: Synthesis and applications. Journal of Industrial and Engineering Chemistry, 20(6), 3947-3959.
Sohn, S., and Do, P. (2023). Linear alkylbenzenes: An overview of the commercial hf and detal™ process unit alkylation technology (case study). Industrial Arene Chemistry: Markets, Technologies, Sustainable Processes and Cases Studies of Aromatic Commodities, 2, 729-745.
Miceli, M., Frontera, P., Macario, A., and Malara, A. (2021). Recovery/reuse of heterogeneous supported spent catalysts. Catalysts, 11(5), 591.
Al-Sultani, S. H., Al-Shathr, A., and Al-Zaidi, B. Y. (2024). Aromatics alkylated with olefins utilizing zeolites as heterogeneous catalysts: A review. Reactions, 5(4), 900-927.
Al-Zaidi, B. Y., Al-Shathr, A., Shehab, A. K., Shakor, Z. M., Majdi, H. S., AbdulRazak, A. A., and McGregor, J. (2023). Hydroisomerisation and hydrocracking of n-heptane: modelling and optimisation using a hybrid artificial neural network–genetic algorithm (ANN–GA). Catalysts, 13(7), 1125.
Ali, N. S., Salih, I. K., Harharah, H. N., Majdi, H. S., Salih, H. G., Kalash, K. R., and Zendehboudi, S. (2023). Utilization of loaded cobalt onto MCM-48 mesoporous catalyst as a heterogeneous reaction in a fixed bed membrane reactor to produce isomerization product from n-heptane. Catalysts, 13(7), 1138.
Khalil, M., Al-Zaidi, B. Y., Shakor, Z. M., Hussein, S. J., and Al-Shathr, A. (2023). experimental and kinetic study of the catalytic behavior of sulfate-treated nanostructured bifunctional zirconium oxide catalysts in n-heptane hydroisomerization reactions. ChemEngineering, 7(6), 115.
Kadja, G. T., Azhari, N. J., Mardiana, S., Culsum, N. T., and Maghfirah, A. (2023). Recent advances in the development of nanosheet zeolites as heterogeneous catalysts. Results in Engineering, 17, 100910.
Liang, J., Liang, Z., Zou, R., and Zhao, Y. (2017). Heterogeneous catalysis in zeolites, mesoporous silica, and metal–organic frameworks. Advanced Materials, 29(30), 1701139.
Al-Sultani, S. H., Al-Shathr, A., and Al-Zaidi, B. Y. (2024). Toluene alkylation reactions over y-type zeolite catalysts: an experimental and kinetic study. Reactions, 5(4), 2624-781X.
Liu, Y., Xu, L., Xu, B., Li, Z., Jia, L., and Guo, W. (2009). Toluene alkylation with 1-octene over supported heteropoly acids on MCM-41 catalysts. Journal of Molecular Catalysis A: Chemical, 297(2), 86-92.
Borutskii, P. N., Kozlova, E. G., Podkletnova, N. M., Gil’Chenok, N. D., Sokolov, B. G., Zuev, V. A., and Shatovkin, A. A. (2007). Alkylation of benzene with higher olefins on heterogeneous catalysts. Petroleum Chemistry, 47(4), 250-261.
Armor, J. N. (2011). A history of industrial catalysis. Catalysis Today, 163(1), 3-9.
Degnan Jr, T. F., Smith, C. M., and Venkat, C. R. (2001). Alkylation of aromatics with ethylene and propylene: recent developments in commercial processes. Applied catalysis A: general, 221(1-2), 283-294.
Weitkamp, J. (2000). Zeolites and catalysis. Solid State Ionics, 131(1-2), 175-188.
Shamzhy, M., Opanasenko, M., Concepción, P., and Martínez, A. (2019). New trends in tailoring active sites in zeolite-based catalysts. Chemical Society Reviews, 48(4), 1095-1149.
Lin, M., Zhou, S., Zhang, C., Li, Y., Wang, C., and Shu, X. (2022). An efficient preparation method of Y zeolite-based catalyst for Isobutane-butene alkylation. Fuel, 328, 125371.
Da, Z., Han, Z., Magnoux, P., and Guisnet, M. (2001). Liquid-phase alkylation of toluene with long-chain alkenes over HFAU and HBEA zeolites. Applied Catalysis A: General, 219(1-2), 45-52.
Shakor, Z. M., and Al-Shafei, E. N. (2023). The mathematical catalyst deactivation models: a mini review. RSC Advances, 13(32), 22579-22592.
Devaraj, A., Vijayakumar, M., Bao, J., Guo, M. F., Derewinski, M. A., Xu, Z., and Ramasamy, K. K. (2016). Discerning the location and nature of coke deposition from surface to bulk of spent zeolite catalysts. Scientific Reports, 6(1), 37586.
Al-Shathr, A., Al-Zaidi, B. Y., Shehab, A. K., Shakoor, Z. M., Aal-Kaeb, S., Gomez, L. Q., and McGregor, J. (2023). Experimental and kinetic studies of the advantages of coke accumulation over Beta and Mordenite catalysts according to the pore mouth catalysis hypothesis. Catalysis Communications, 181, 106718.
Mayerová, J., Pawlesa, J., Košová, G., and Čejka, J. (2005). Microporous and mesoporous molecular sieves for alkylation of toluene with olefins. In Studies in Surface Science and Catalysis, 158, 1945-1952.
Fernandes, R. M., and Lachter, E. R. (2005). Evaluation of sulfonic resins for liquid phase alkylation of toluene. Catalysis Communications, 6(8), 550-554.
Ogunbadejo, B., Aitani, A., Čejka, J., Kubů, M., and Al-Khattaf, S. (2016). The effect of alkylation route on ethyltoluene production over different structural types of zeolites. Chemical Engineering Journal, 306, 1071-1080.
Zhou, F., Gao, Y., Wu, G., Ma, F., and Liu, C. (2017). Improved catalytic performance and decreased coke formation in post-treated ZSM-5 zeolites for methanol aromatization. Microporous and Mesoporous Materials, 240, 96-107.
Guisnet, M., and Magnoux, P. (1989). Coking and deactivation of zeolites: influence of the pore structure. Applied Catalysis, 54(1), 1-27.
Brillis, A. A., and Manos, G. (2003). Coke formation during catalytic cracking of C8 aliphatic hydrocarbons over ultrastable Y zeolite. Industrial & Engineering Chemistry Research, 42(11), 2292-2298.
Quintana-Gómez, L., Connolly, M., Shehab, A. K., Al-Shathr, A., and McGregor, J. (2022). “Reverse combustion” of carbon dioxide in water: The influence of reaction conditions. Frontiers in Energy Research, 10, 917943.
Liang, B., Liu, M. N., An, N., Ren, F., Luo, Q. X., Chen, H., and Hao, Q. Q. (2024). Achieving long-lived MWW zeolite catalyst for alkylation of benzene with 1-dodecene: Insights into confinement effect of surface cavities and underlying mechanism. Chemical Engineering Journal, 489, 151109.
Shen, H., Liu, M., Li, J., Li, X., Xie, S., Chen, F., AND Zhu, X. (2021). Promising strategy to synthesize ZSM-5@ Silicalite-1 with superior catalytic performance for catalytic cracking reactions. Industrial & Engineering Chemistry Research, 60(25), 9098-9106.
Ghanbari-Siahkali, A., Philippou, A., Dwyer, J., and Anderson, M. W. (2000). The acidity and catalytic activity of heteropoly acid on MCM-41 investigated by MAS NMR, FTIR and catalytic tests. Applied Catalysis A: General, 192(1), 57-69.
Golding, C. G., Lamboo, L. L., Beniac, D. R., and Booth, T. F. (2016). The scanning electron microscope in microbiology and diagnosis of infectious disease. Scientific Reports, 6(1), 26516.
Sombatchaisak, S., Praserthdam, P., Chaisuk, C., AND Panpranot, J. (2004). An alternative correlation equation between particle size and structure stability of H− Y zeolite under hydrothermal treatment conditions. Industrial & Engineering Chemistry Research, 43(15), 4066-4072.
Tianying, N. I. U., Yingxia, L. I., Jianwei, L. I., and Biaohua, C. H. E. N. (2009). Synthesis of zeolite beta by the vapour-phase transport method using tetraethylammonium bromide as the organic template. Chinese Journal of Catalysis, 30(3), 191-195.
Shakor, Z., Alasseel, A., and Al‐Shafei, E. (2024). The structure of deposited coke on hydrocracking and reforming catalysts: Coke deactivation and kinetics. The Canadian Journal of Chemical Engineering, 102(8), 2876-2891.
Al-Karim, A. A., Shakor, Z. M., Al-Sheikh, F., and Anderson, W. A. (2022). Experimental and kinetic study of vacuum residue cracking over zirconium based catalysts. Reaction Kinetics, Mechanisms and Catalysis, 135(2), 847-865.
Hussein, Z. A., Shakor, Z. M., Alzuhairi, M., and Al-Sheikh, F. (2023). Thermal and catalytic cracking of plastic waste: a review. International Journal of Environmental Analytical Chemistry, 103(17), 5920-5937.
Hussein, Z. A., Shakor, Z. M., Alzuhairi, M., and Al-Sheikh, F. (2023). Kinetic and thermodynamic study of the pyrolysis of plastic waste. Environmental Processes, 10(2), 27.
Biney, P. O., Gyamerah, M., Shen, J., and Menezes, B. (2015). Kinetics of the pyrolysis of arundo, sawdust, corn stover and switch grass biomass by thermogravimetric analysis using a multi-stage model. Bioresource Technology, 179, 113-122.
Burra, K. R. G., and Gupta, A. K. (2019). Modeling of biomass pyrolysis kinetics using sequential multi-step reaction model. Fuel, 237, 1057-1067.
Al-Shathr, A., Shakor, Z. M., Al-Zaidi, B. Y., Majdi, H. S., AbdulRazak, A. A., Aal-Kaeb, S., and McGregor, J. (2022). Reaction kinetics of cinnamaldehyde hydrogenation over Pt/SiO2: comparison between bulk and intraparticle diffusion models. International Journal of Chemical Engineering, 2022(1), 8303874.
Al-Shathr, A., Shakor, Z. M., Majdi, H. S., AbdulRazak, A. A., and Albayati, T. M. (2021). Comparison between artificial neural network and rigorous mathematical model in simulation of industrial heavy naphtha reforming process. Catalysts, 11(9), 1034.
AlKhafaji, K. S., Shakor, Z. M., Al-Zaidi, B. Y., and Hussein, S. J. (2022). Preparation and characterization of metakaolin-based catalysts for gasoil hydrodesulfurization purposes. Arabian Journal for Science and Engineering, 47(5), 6283-6296.
Da, Z., Magnoux, P., and Guisnet, M. (1999). Liquid phase alkylation of toluene with 1-heptene over a HFAU zeolite: evidence for transalkylation between toluene and non-desorbed products. Applied Catalysis A: General, 182(2), 407-411.
Pérez-Botella, E., Valencia, S., and Rey, F. (2022). Zeolites in adsorption processes: State of the art and future prospects. Chemical Reviews, 122(24), 17647-17695.
Wei, L., Yang, H., Ren, P., Yang, Y., Li, Y. W., Li, R., and Jiao, H. (2022). Distribution of multiple Al substitution in HY zeolite and Brønsted acid strength-A periodic DFT study. Microporous and Mesoporous Materials, 344, 112184.
Xiong, G., Feng, M., Liu, J., Meng, Q., Liu, L., and Guo, H. (2019). The synthesis of hierarchical high-silica beta zeolites in NaF media. RSC Advances, 9(7), 3653-3660.
Khaleque, A., Alam, M. M., Hoque, M., Mondal, S., Haider, J. B., Xu, B., and Moni, M. A. (2020). Zeolite synthesis from low-cost materials and environmental applications: A review. Environmental Advances, 2, 100019.
Corma, A., Martinez, A., Martinezsoria, V., and Monton, J. B. (1995). Hydrocracking of vacuum gasoil on the novel mesoporous MCM-41 aluminosilicate catalyst. Journal of Catalysis, 153(1), 25-31.
Katkar, S., Mohite, P., Gadekar, L., Arbad, B., and Lande, M. (2010). ZnO-beta zeolite mediated simple and efficient method for the one-pot synthesis of quinoxaline derivatives at room temperature. Open Chemistry, 8(2), 320-325.
Mekki, A., Benmaati, A., Mokhtar, A., Hachemaoui, M., Zaoui, F., Habib Zahmani, H., and Boukoussa, B. (2020). Michael addition of 1, 3-dicarbonyl derivatives in the presence of zeolite Y as an heterogeneous catalyst. Journal of Inorganic and Organometallic Polymers and Materials, 30(7), 2323-2334.
Zween, A. F., Shakor, Z. M., and Sherhan, B. Y. (2024). Coke Decomposition Kinetic Model of Spent Hydrodesulfurization catalysts. Journal of Applied Science Nanotechnology, 4, 29-46.
Yan, J., Jiang, X., Han, X., and Liu, J. (2013). A TG–FTIR investigation to the catalytic effect of mineral matrix in oil shale on the pyrolysis and combustion of kerogen. Fuel, 104, 307-317.
Al-Iessa, M. S., Al-Zaidi, B. Y., Almukhtar, R. S., Shakor, Z. M., and Hamawand, I. (2023). Optimization of polypropylene waste recycling products as alternative fuels through non-catalytic thermal and catalytic hydrocracking using fresh and spent Pt/Al2O3 and NiMo/Al2O3 catalysts. Energies, 16(13), 4871.
Cowley, M., de Klerk, A., and Nel, R. J. (2005). Amylation of toluene by solid acid catalysis. Industrial & Engineering Chemistry Research, 44(15), 5535-5541.
Al-Kinany, M. C., Al-Megren, H. A., Al-Ghilan, E. A., Edwards, P. P., Xiao, T., Al-Shammari, A. S., and Al-Drees, S. A. (2012). Selective zeolite catalyst for alkylation of benzene with ethylene to produce ethylbenzene. Applied Petrochemical Research, 2(3), 73-83.
Ahmed, R., Sinnathambi, C. M., and Subbarao, D. (2011). Kinetics of de-coking of spent reforming catalyst. Journal of Applied Sciences, 11(7), 1225-1230.
DOI: https://doi.org/10.17509/ajse.v6i2.90148
Refbacks
- There are currently no refbacks.
Copyright (c) 2025 Universitas Pendidikan Indonesia
This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.