Aminated Porous Methacrylate-Based Polymer Monolith as an Anion Exchanger Microreactor for Sustainable Continuous Flow Transesterification of Palm Oil
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Monolithic Polymer, Anion Exchanger Resins, Continuous Transesterification, Biodiesel, Palm Oil
Abstract
The development of regenerable heterogeneous catalysts for sustainable biodiesel production remains a major challenge, particularly for continuous-flow systems. This study aimed to develop a functionalized methacrylate-based monolithic polymer as a catalytic microreactor for the continuous transesterification of palm oil. The novelty of this work lies in (i) the use of diethylamine (DEA) as an amination agent for poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (PGMEGD) monoliths, (ii) the systematic optimization of the alkalization process to produce an anion-exchange resin, and (iii) the demonstration of catalyst regeneration through an effective sequential washing procedure. PGMEGD monoliths were synthesized in situ using a ternary porogenic system consisting of 1-propanol, 1,4-butanediol, and water, followed by functionalization with DEA at concentrations ranging from 5 to 25% and subsequent alkalization with NaOH. FTIR and SEM analyses confirmed successful chemical modification while preserving the interconnected three-dimensional porous structure of the monolith. The highest amine density of 3.43 mmol g−1 was obtained at a DEA concentration of 20%, whereas an optimum OH− exchange capacity of 3.28 mmol g−1, corresponding to 96% of the amine density, was achieved after alkalization with 1.0 M NaOH. In the continuous transesterification of palm oil with methanol, the catalyst achieved an optimum biodiesel yield of 86.28% at a methanol-to-oil molar ratio of 9:1 and a flow rate of 0.05 mL min−1. The catalyst maintained a biodiesel yield above 80% for four consecutive cycles, while regeneration using sequential citric acid-NaOH-ethanol washing restored more than 99% of its catalytic activity and exhibited a consistent recovery pattern over two regeneration cycles. These findings demonstrate that the PGMEGD-NH2-OH monolithic resin is a promising catalytic microreactor for sustainable biodiesel production under continuous-flow conditions.
References
Abdulla Yusuf, H., S. M. Z. Hossain, S. Aloraibi, N. J. Alzaabi, M. A. Alfayhani, and H. J. Almedfaie (2022). Fabrication of Novel Microreactors in-House and Their Performance Analysis Via Continuous Production of Biodiesel. Chemical Engineering and Processing - Process Intensification, 172; 108792
Abiev, R. S. (2022). Chemical and Biochemical Reactors for Controlled Synthesis of Organic and Inorganic Compounds. Russian Journal of Applied Chemistry, 95(11); 1339–1364
Aghel, B., M. Mohadesi, and S. Sahraei (2016). New Heterogeneous Process for Continuous Biodiesel Production in Microreactors. The Canadian Journal of Chemical Engineering, 95(7); 1280–1287
Aljaafari, A., I. M. R. Fattah, M. I. Jahirul, Y. Gu, T. M. I. Mahlia, M. A. Islam, and M. S. Islam (2022). Biodiesel Emissions: A State-of-the-Art Review on Health and Environmental Impacts. Energies, 15(18); 6854
Amalia, S., S. C. Angga, E. D. Iftitah, D. Septiana, B. O. D. Anggraeny, Warsito, A. N. Hasanah, and A. Sabarudin (2021). Immobilization of Trypsin onto Porous Methacrylate-Based Monolith for Flow-Through Protein Digestion and Its Potential Application to Chiral Separation Using Liquid Chromatography. Heliyon, 7(8); e07707
Amalia, S., N. A. Rafika, S. A. Hardiyanti, A. D. Ashari, B.W. Khabibi, E. D. Iftitah, W. Warsito, A. N. Hasanah, and A. Sabarudin (2022). Cobalt (II)-Mediated Molecularly Imprinted Polymer as a Monolithic Stationary Phase for Separation of Racemic Citronellal by Liquid Chromatography. The Scientific World Journal, 2022; 7891525
Chen,W., Z.Wu, Z.Wang, C. Chen, and Z. Zhang (2022). Preparation of a Reusable and Pore Size Controllable Porous Polymer Monolith and Its Catalysis of Biodiesel Synthesis. RSC Advances, 12(20); 12363–12370
Chueluecha, N., A. Kaewchada, and A. Jaree (2017). Biodiesel Synthesis Using Heterogeneous Catalyst in a Packed-Microchannel. Energy Conversion and Management, 141; 145–154
Costa, L. C., R. C. Monteiro, H. M. A. Castro, and T. S. Ribeiro (2020). Glycidyl Methacrylate-ethylene Glycol Dimethacrylate Copolymers with Varied Pore Structures Prepared with Different Reaction Parameters. Materials Research, 23(3)
Deora, P. S., Y. Verma, R. A. Muhal, C. Goswami, T. Singh, et al. (2022). Biofuels: An Alternative to Conventional Fuel and Energy Source. Materials Today: Proceedings, 48; 1178–1184
Erwanto, E., W. Warsito, A. Sabarudin, and D. Mardiana (2026). Immobilized L-Arginine on Methacrylate Polymer As Reusable Heterogeneous Catalyst for Crude Palm Oil Transesterification. The International Journal of Renewable Energy Development, 16(3); 522–531
Fadarina, F., T. O. Fiyansah, J. Bin, M. Nasir, R. Junaidi, M. Zamhari, C. Ramayanti, and T. Mawarni (2022). Synthesis and Characterization of CaOCatalyst from Snakehead Fishbone Impregnated on Fly Ash for Palm Oil Transesterification. 9; 392–399
Farobie, O. and E. Hartulistiyoso (2022). Palm Oil Biodiesel as a Renewable Energy Resource in Indonesia: Current Status and Challenges. BioEnergy Research, 15(1); 93–111
Hadi, B., E. Parandi, M. Nouri, B. Aghel, and A. Gouran (2023). Optimization of Microreactor-Assisted Transesterification for Biodiesel Production Using Bimetal Zirconium-Titanium Oxide Doped Magnetic Graphene Oxide Heterogeneous Nanocatalyst. Chemical Engineering and Processing - Process Intensification, 191; 109479
He, Z., M. Wai, Z. Shan, R. Dai, F. Cheng, and H. Chen (2022). Preparation and Characterization of Crosslinked Starch Films Pretreated with Sodium Hydroxide / Amide / Water Solvent System. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 650; 129544
Hermansyah, H. (2023). Ion Exchange Resin and Entrapped Candida Rugosa Lipase for Biodiesel Synthesis in the Recirculating Packed-Bed Reactor: A Performance Comparison of Heterogeneous Catalysts. Energies, 16(12); 4765
Kibar, M. E., L. Hilal, B. Tuna Çapa, B. Bahçıvanlar, and B. Ben Abdeljelil (2023). Assessment of Homogeneous and Heterogeneous Catalysts in Transesterification Reaction: A Mini Review. ChemBioEng Reviews, 10(4); 412–422
Lin, C.-Y. and S.-L. Tseng (2024). Investigation into the Fuel Characteristics of Biodiesel Synthesized through the Transesterification of Palm Oil Using a TiO2/CH3ONa Nanocatalyst. Catalysts, 14(9); 623
Maleki, F., R. Torkaman, M. Torab-mostaedi, and M. Asadollahzadeh (2022). Optimization of Grafted Fibrous Polymer Preparation Procedure As a New Solid Basic Catalyst for Biodiesel Fuel Production from Palm Oil. Fuel, 329; 125015
Minaria, M. and R. Mohadi (2016). Preparation and Characterization of Calcium Oxide from Crab Shells (Portunus pelagicus) and Its Application in Biodiesel Synthesis ofWaste Cooking Oil, Palm and Coconut Oil. Science and Technology Indonesia, 1(1); 1–7
Nasef, M. M., S. S. Alinezhad, R. Mat, R. Yusof, M. Zakeri, and H. Farag (2016). Preparation of Alkaline Polymer Catalyst by Radiation Induced Grafting for Transesterification of Triacetin under Neural Network Optimized Conditions. Journal of Macromolecular Science, Part A, 53(9); 570–579
Priya, P. S. Deora, Y. Verma, R. A. Muhal, C. Goswami, and T. Singh (2021). Biofuels: An Alternative to Conventional Fuel and Energy Source. Materials Today: Proceedings, 48; 1178–1184
Sabarudin, A., S. Shu, K. Yamamoto, and T. Umemura (2021). Preparation of Metal-Immobilized Methacrylate-Based Monolithic Columns for Flow-Through Cross-Coupling Reactions. Molecules, 26(23); 7346
Sitompul, S. O. C. and R. Mohadi (2017). Preparation of CalciumOxide from Cattle Bones as Catalyst for Conversion of Waste Cooking Oil to Biodiesel. Science and Technology Indonesia, 2(3); 76–79
Sulaiman, N. F., A. R. Yacob, and S. L. Lee (2020). Transesterification Reaction from Rice Bran Oil to Biodiesel over Heterogeneous Base Calcium Oxide Nanoparticles Catalyst. Science and Technology Indonesia, 5(3); 62–69
Sumari, S., S. Arni, A. Santoso, L. Putri, M. Roy, and A. Budianto (2024). Contribution of Malang Quartzite-Based Silica in K2O / Zeolite Y Catalyst forMethyl Ester Synthesis of off Grade Crude Palm Oil. Heliyon, 10(13); e33563
Szkudlarek, Ł., K. Cha, W. Maniukiewicz, M. Nowosielska, J. Albi, and I. Szynkowska-Jóźwiak (2024). Cao Catalysts Supported on Zsm-5 Zeolite for Biodiesel Production Via Transesterification of Rapeseed Oil. Applied Catalysis O: Open, 194; 206999
Ueki, Y., T. Umemura, J. Li, T. Odake, and K. I. Tsunoda (2004). Preparation and Application of Methacrylate-Based Cation-Exchange Monolithic Columns for Capillary Ion Chromatography. Analytical Chemistry, 76(23); 7007–7012
United States Department of Agriculture (2022). Oilseeds and Products Update. Technical report
Wang, T., X. Ma, N. Bingwa, H. Yu, Y.Wang, G. Li, M. Guo, Q. Xiao, S. Li, X. Zhao, and H. Li (2024). A Novel Bimetallic Cafe-Mof Derivative for Transesterification: Catalytic Performance, Characterization, and Stability. Energy, 292; 130544
Zhao, G., J. A. Moulijn, F. Kapteijn, F. M. Dautzenberg, and Y. Lu (2024). Monolithic Fiber / Foam-Structured Catalysts: Beyond Honeycombs and Micro-Channels. Catalysis Reviews, 66(5); 1870–1950
Zu, Y., T. Yie, H. Tan, N. M. Mubarak, B. Lai, F. Chin, and R. Rao (2024). Kinetic and Thermodynamic Studies of Transesterification Catalysed by Black Pepper Seed - Potassium Hydroxide Catalyst. Topics in Catalysis, 67(9); 810–827
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