Cover Image

Modification of acid on beta zeolite catalysts by ion-exchange method for ethanol dehydration to diethyl ether

Montri Thapplee, Chadaporn Krutpijit, Piyasan Praserthdam, ฺีBunjerd Jongsomjit


The catalytic ethanol dehydration to diethyl ether (DEE) over the synthesized beta zeolite (BEA) with different acidity on catalysts having Na and mixed Na-H forms was studied. The Na form of BEA catalyst was synthesized via the hydrothermal process, including non-calcined (Na-BEA_N) and calcined (Na-BEA_C) catalysts. The Na-BEA_C catalyst was successively used in the synthesis of different mixed Na-H forms under the ion-exchange method using the ammonium nitrate solution at 70°C for 2 h/cycle. In the present study, two different cycles were chosen, including one cycle (M-BEA_1) and four cycles (M-BEA_4) to compare the amount of acidity on catalysts. The results indicated that the M-BEA_1 catalyst exhibited a large surface area and contained the highest moderate acid site, which strongly affected the optimal catalytic activity at low temperature (<250°C) with ethanol conversion of 74.6% and DEE yield of 27.3%. However, the increased number of ion-exchange cycles had not shown remarkable effects on catalytic activity due to low surface area and moderate acidity.

Full Text:



- M. M. Balmaceda, Differentiation, materiality, and power: Towards a political economy of fossil fuels, Energy Research & Social Science, 2018, 39, 130-140.

- J. A. Bolanos, Energy, uncertainty, and entrepreneurship: John D Rockefeller’s sequential approach to transaction costs management in the early oil industry, Energy Research & Social Science, 2019, 55, 26-34.

- J. A. McGee, P. T. Greiner, Renewable energy injustice: The socio-environmental implications of renewable energy consumption, Energy Research & Social Science, 2019, 56, 101214.

- S. Rahmani, M. Rezaei, F. Meshkani, Preparation of highly active nickel catalysts supported on mesoporous nanocrystalline γ-Al2O3 for CO2 methanation, Journal of Industrial and Engineering Chemistry, 2014, 20, 1346-1352.

- F. Ocampo, B. Louis, A.-C. Roger, Methanation of carbon dioxide over nickel-based Ce0.72Zr0.28O2 mixed oxide catalysts prepared by sol-gel method, Applied Catalysis A: General, 2009, 369, 90-96.

- J. W. Akitt, Some observations on the greenhouse effect at the Earth's surface, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2018, 188, 127-134.

- T. R. Anderson, E. Hawkins, P. D. Jones, CO2, the greenhouse effect and global warming: from the pioneering work of Arrhenius and Callendar to today's Earth System Models, Endeavour, 2016, 40, 178-187.

- J. Sun, Y. Wang, Recent Advances in Catalytic Conversion of Ethanol to Chemicals, ACS Catalysis, 2014, 4, 1078-1090.

- G. W. Huber, S. Iborra, A. Corma, Synthesis of Transportation Fuels from Biomass:  Chemistry, Catalysts, and Engineering, Chemical Reviews, 2006, 106, 4044-4098.

- J. Janlamool, B. Jongsomjit, Catalytic Ethanol Dehydration to Ethylene over Nanocrystalline χ- and γ-Al2O3 Catalysts, Journal of Oleo Science, 2017, 66, 1029-1039.

- J. C. Soh, S. L. Chong, S. S. Hossain, C. K. Cheng, Catalytic ethylene production from ethanol dehydration over non-modified and phosphoric acid modified Zeolite H-Y (80) catalysts, Fuel Processing Technology, 2017, 158, 85-95.

- G. Chen, S. Li, F. Jiao, Q. Yuan, Catalytic dehydration of bioethanol to ethylene over TiO2/γ-Al2O3 catalysts in microchannel reactors, Catalysis Today, 2007, 125, 111-119.

- Y. Chen, Y. Wu, L.Tao, B. Dai, M. Yang, Z. Chen, X. Zhu, Dehydration reaction of bio-ethanol to ethylene over modified SAPO catalysts, Journal of Industrial and Engineering Chemistry, 2010, 16, 717-722.

- T. K. Phung, L. Proietti Hernández, A. Lagazzo, G. Busca, Dehydration of ethanol over zeolites, silica alumina and alumina: Lewis acidity, Brønsted acidity, and confinement effects, Applied Catalysis A: General, 2015, 493, 77-89.

- T. K. Phung, G. Busca, Ethanol dehydration on silica-aluminas: Active sites and ethylene/diethyl ether selectivities, Catalysis Communications, 2015, 68, 110-115.

- T. K. R. de Oliveira, M. Rosset, O. W. Perez-Lopez, Ethanol dehydration to diethyl ether over Cu-Fe/ZSM-5 catalysts, Catalysis Communications, 2018, 104, 32-36.

- D. Zhang, R. Wang, X. Yang, Effect of P Content on the Catalytic Performance of P-modified HZSM-5 Catalysts in Dehydration of Ethanol to Ethylene, Catalysis Letters, 2008, 124, 3, 384-391.

- W. Choopun, S. Jitkarnka, Catalytic activity, and stability of HZSM-5 zeolite and hierarchical uniform mesoporous MSU-SZSM-5 during bio-ethanol dehydration, Journal of Cleaner Production, 2016, 368-378.

- C. Yen Wu, H. Shing Wu, Ethylene Formation from Ethanol Dehydration Using ZSM-5 Catalyst, ACS Omega, 2017, 2, 4287-4296

- A. E.-A. A. Said, M. M. M. Abd El-Wahab, M. M. Abdelhak, The role of Brønsted acid site strength on the catalytic performance of phosphotungstic acid supported on nano γ-alumina catalysts for the dehydration of ethanol to diethyl ether, Reaction Kinetics, Mechanisms and Catalysis, 2017, 122, 433-449.

- H. G. Karge, Post-synthesis modification of microporous materials by solid-state reactions, Surface Science and Catalysis, Elsevier, 1997, 105, 1901-1948.

- R. P. Townsend, E. N. Coker, Chapter 11 Ion exchange in zeolites, Studies in Surface Science and Catalysis, Elsevier, 2001, 137, 467-524.

- M. A. Camblor, J. Perez-Pariente, Chapter 31-BEA Zeolite Beta Si(93), Al(7), Verified Syntheses of Zeolitic Materials, Elsevier, 2001, 115-117.

- T. Kamsuwan, P. Praserthdam, B. Jongsomjit, Diethyl Ether Production during Catalytic Dehydration of Ethanol over Ru- and Pt- modified H-beta Zeolite Catalysts, Journal of Oleo Science, 2017, 66, 199-207.

- G. Ye, Y. Sun, Z. Guo, K. Zhu, H. Liu, X. Zhou, M.O. Coppens, Effects of zeolite particle size and internal grain boundaries on Pt/Beta catalyzed isomerization of n-pentane, Journal of Catalysis, 2018, 360, 152-159.

- A. Vimont, F. Thibault-Starzyk, J. C. Lavalley, Infrared Spectroscopic Study of the Acidobasic Properties of Beta Zeolite, The Journal of Physical Chemistry B, 2000, 104, 286-291.

- S. T. F. Grecco, E. A, Urquieta-González, P. Reyes, M. Oportus, M. d. C. Rangel, Influence of Temperature and Time of Seed Aging on the Properties of Beta Zeolite/MCM-41 Materials, Chem. Soc., 2014, 25, 2444-2454.

- A. Sher, Characterization of Beta Zeolites by X-Ray Diffraction, Scanning Electron Microscope, and Refractive Index Techniques, J. Chem. Soc. Pak., 2010, 32, 592-598.

- F. Lónyi, J. Valyon, On the interpretation of the NH3-TPD patterns of H-ZSM-5 and

H-mordenite, Microporous and Mesoporous Materials, 2001, 47, 2, 293-301.

- L. Martins, D. Cardoso, P. Hammer, T. Garetto, S. H. Pulcinelli, C. V. Santilli, Efficiency of ethanol conversion induced by controlled modification of pore structure and acidic properties of alumina catalysts, Applied Catalysis A: General, 2011, 398, 59-65.

- J. Weitkamp, Zeolites and catalysis, Solid State Ionics, 2000, 131, 175-188.

- K. Chalupka, R. Sadek, L. Valentin, Y. Millot, C. Calers, M. Nowosielska, J. Rynkowski, S. Dzwigaj, Dealuminated Beta Zeolite Modified by Alkaline Earth Metals, Journal of Chemistry, 2018, 2018, 1-11.

- A. Lima, A. J De Assis, C. Hori, M. Reis, A. E. Da Hora Machado, Thermodynamic Analysis of Ethanol Dehydration to Ethylene through Equilibrium Constant Method Using Classic Thermodynamics and Quantum Chemistry, International Review of Chemical Engineering, 2012, 4, 466-473.


Copyright (c) 2020 Mediterranean Journal of Chemistry