Dimethyl ether (DME) is considered as a significant fuel alternative with a critical manufacturing process. Only a few authors have presented the kinetic analysis of attractive and alternative catalysts to Al 2 O 3 and/or zeolite in DME production, despite the fact that there is a large library of kinetic studies for these commercial catalysts. The purpose of this research was to contribute to this direction by conducting a catalytic test to determine kinetic parameters for methanol dehydration over sulfonic acid catalysts (resin). However, due to the relevance of the mathematical description of this process in the industry was also studied, a study of kinetics parameters and mathematical modeling of methanol dehydration in an atmospheric gas phase in a fixed bed reactor with a temperature range (90° C - 120 ° C) was examined. The Langmuir-Hinshelwood (L-H) model provides the best fit to experimental data, with an excellent R 2 = 0.9997, and the experimental results were compared to those predicted by these models with very small deviations. The kinetic parameters were found to be in good agreement with the Arrhenius equation, with acceptable straight-line graphs. The activation energy E was computed and found to be 27.66 kJ/mole, with an av erage variation of 0.32 percent between the predicted and calculated results . Simple mathematical continuum models (plug flow reactor PFR) showed an acceptable agreement with the experimental data.
KeywordsCatalystDimethyl EtherFixed Bed ReactorDehydrationModelling
Fleisch, T.H., Basu, A., Gradassi, M.J. and Masin, J.G. (1997) Dimethyl Ether: A Fuel for the 21st Century. Studies in Surface Science and Catalysis, 107, 117-125. https://doi.org/10.1016/S0167-2991(97)80323-0
Ardy, A., Pohan, R.D.A., Rizkiana, J., Laniwati, M. and Susanto, H. (2019) Dehydration of Methanol to Dimethyl Ether (DME): Performance of Three Types of Catalyst at Atmospheric Pressure. AIP Conference Proceedings, 2085, Article ID: 020064. https://doi.org/10.1063/1.5095042
An, X., Zuo, Y.Z., Zhang, Q., Wang, D.Z. and Wang, J.F. (2008) Dimethyl Ether Synthesis from CO2 Hydrogenation on a CuO-ZnO-Al2O3-ZrO2/HZSM-5 Bifunctional Catalyst. Industrial & Engineering Chemistry Research, 47, 6547-6554. https://doi.org/10.1021/ie800777t
Barbarossa, V., Viscardi, R., Maestri, G., Maggi, R., Mirabile Gattia, D. and Paris, E. (2019) Sulfonated Catalysts for Methanol Dehydration to Dimethyl Ether (DME). Materials Research Bulletin, 113, 64-69. https://doi.org/10.1016/j.materresbull.2019.01.018
Barbarossa, V., Viscardi, R., Di Nardo, A. and Santagata, A. (2020) Kinetic Parameter Estimation for Methanol Dehydration to Dimethyl Ether over Sulfonic and Polymeric Acid Catalysts. Journal of Chemical Technology & Biotechnology, 95, 1739-1747. https://doi.org/10.1002/jctb.6372
Jiang, S., Hwang, J.S., Jin, T., Cai, T., Cho, W., Baek, Y.S. and Park, S.E. (2004) Dehydration of Methanol to Dimethyl Ether over ZSM-5 Zeolite. Bulletin of the Korean Chemical Society, 25, 185-189. https://doi.org/10.5012/bkcs.2004.25.2.185
Berčič, G. and Levee, J. (1992) Intrinsic and Global Reaction Rate of Methanol Dehydration over γ-Al2O3 Pellets. Industrial & Engineering Chemistry Research, 31, 1035-1040. https://doi.org/10.1021/ie00004a010
Sierra, I., Ereña, J., Aguayo, A.T., Ateka, A. and Bilbao, J. (2013) Kinetic Modelling for the Dehydration of Methanol to Dimethyl Ether over γ-Al2O3. Chemical Engineering Transactions, 32, 613-618.
Spivey, J.J. (1991) Review: Dehydration Catalysts for the Methanol/Dimethyl Ether Reaction. Chemical Engineering Communications, 110, 123-142. https://doi.org/10.1080/00986449108939946
Gates, B.C. and Johanson, L.N. (1971) Langmuir-Hinshelwood Kinetics of the Dehydration of Methanol Catalyzed by Cation Exchange Resin. AIChE Journal, 17, 981-983. https://doi.org/10.1002/aic.690170435
van der Vaart, D. (1988) Catalytic Dehydration of Methanol. EPA Research Report.
An, W., Chuang, K.T. and Sanger, A.R. (2004) Dehydration of Methanol to Dimethyl Ether by Catalytic Distillation. The Canadian Journal of Chemical Engineering, 82, 948-955. https://doi.org/10.1002/cjce.5450820510
Zablouka, M.A., Kaseera, N.W., Hadi, G.J. and Hadi, A.J. (2011) Comparison the Performance of Four Catalyst Types in the Calytic Dehaydration of Ethanol. Journal of Advanced Science and Engineering Research, 1, 137-149.
Hadi, G.J. (2021) Dehydration of Methanol in Catalytic Fixed Bed Reactor. IOP Conference Series: Materials Science and Engineering, 1076, Article ID: 012024. https://doi.org/10.1088/1757-899X/1076/1/012024
Jain, J.R. and Pillai, C.N. (1967) Catalytic Dehydration of Alcohols over Alumina. Mechanism of Ether Formation. Journal of Catalysis, 9, 322-330. https://doi.org/10.1016/0021-9517(67)90260-6
Štich, I., Gale, J.D., Terakura, K. and Payne, M.C. (1999) Role of the Zeolitic Environment in Catalytic Activation of Methanol. Journal of the American Chemical Society, 121, 3292-3302. https://doi.org/10.1021/ja983470q
Gates, B.C. and Johanson, L.N. (1969) The Dehydration of Methanol and Ethanol Catalyzed by Polystyrene Sulfonate Resins. Journal of Catalysis, 14, 69-76. https://doi.org/10.1016/0021-9517(69)90357-1
Kiviranta-Pääkkönen, P.K., Struckmann née Rihko, L.K., Linnekoski, J.A. and Krause, A.O.I. (1998) Dehydration of the Alcohol in the Etherification of Isoamylenes with Methanol and Ethanol. Industrial & Engineering Chemistry Research, 37, 18-24. https://doi.org/10.1021/ie970454d
Devika, P.D., Dinesh, P.A., Padmavathi, G. and Prasad, R.K. (2012) Numerical Methods for Mathematical Models of Heterogeneous Catalytic Fixed Bed Chemical Reactors. Mapana Journal of Sciences, 11, 49-64. https://doi.org/10.12723/mjs.20.4
Agrawal, A.K., Devika, K. and Manabe, T. (2001) Simulation of Hydrolytic Polymerization of Nylon-6 in Industrial Reactors: Part I. Mono-Acid-Stabilized Systems in VK Tube Reactors. Industrial & Engineering Chemistry Research, 40, 2563-2572. https://doi.org/10.1021/ie0002576
Rudraiah, N. and Dinesh, P.A. (2004) Nonlinear Flow between Permeable Disks Using Computer-Extended Series Method. Studies in Applied Mathematics, 113, 163-182. https://doi.org/10.1111/j.1467-9590.2004.01528.x
Levenspiel, O. (1962) Chemical Reaction Engineering. John Wiley & Sons, New York.
Migliori, M., Aloise, A., Catizzone, E. and Giordano, G. (2014) Kinetic Analysis of Methanol to Dimethyl Ether Reaction over H-MFI Catalyst. Industrial & Engineering Chemistry Research, 53, 14885-14891.
Eisenman, G. (1983) The Molecular Basis of Ionic Selectivity in Macroscopic Systems. In: Liberti, L. and Helfferich, F.G., Eds., Mass Transfer and Kinetics of Ion Exchange, Springer, Dordrecht, 121-155. https://doi.org/10.1021/ie502775u
Kabel, R.L. and Johanson, L.N. (1962) Reaction Kinetics and Adsorption Equilibria in the Vapor-Phase Dehydration of Ethanol. AIChE Journal, 8, 621-628. https://doi.org/10.1002/aic.690080512
Hosseininejad, S., Afacan, A. and Hayes, R.E. (2012) Catalytic and Kinetic Study of Methanol Dehydration to Dimethyl Ether. Chemical Engineering Research and Design, 90, 825-833. https://doi.org/10.1016/j.cherd.2011.10.007
Linnekoski, J.A., Krause, A.O. and Rihko, L.K. (1997) Kinetics of the Heterogeneously Catalyzed Formation of tert-Amyl Ethyl Ether. Industrial & Engineering Chemistry Research, 36, 310-316.
Zhang, T., Jensen, K., Kitchaiya, P., Phillips, C. and Datta, R. (1997) Liquid-Phase Synthesis of Ethanol-Derived Mixed Tertiary Alkyl Ethyl Ethers in an Isothermal Integral Packed-Bed Reactor. Industrial & Engineering Chemistry Research, 36, 4586-4594. https://doi.org/10.1021/ie970099r
Lee, H.H. (1989) Gas-Liquid-Solid Fluidization Engineering (Butterworth’s Series in Chemical Engineering). Butterworth, Boston.
Olaofe, O. (1984) Kinetics of Dehydration of 1-Butanol over Zeolites. Collection of Czechoslovak Chemical Communications, 50, 1784-1800. https://doi.org/10.1135/cccc19851784 http://cccc.uochb.cas.cz/50/8/1784/
Ertl, G., Knozinger, H., Schuth, F. and Weitkamp, J. (2007) Handbook of Heterogeneous Catalysis Vol. 1. Wiley-VCH, Weinheim.
Gates, B.C., Wisnouskas, J.S. and Heath, H.W. (1972) The Dehydration of t-Butyl Alcohol Catalyzed by Sulfonic Acid Resin. Journal of Catalysis, 24, 320-327. https://doi.org/10.1016/0021-9517(72)90076-0
Osman, A.I. and Abu-Dahrieh, J.K. (2018) Kinetic Investigation of Η-Al2O3 Catalyst for Dimethyl Ether Production. Catalysis Letters, 148, 1236-1245. https://doi.org/10.1007/s10562-018-2319-2
Bird, R.B., Stewart, W.E. and Lightfoot, E.N. (2006) Transport Phenomena. 2nd Edition, John Wiley & Sons, New York.
Berčič, G. and Levec, J. (1993) Catalytic Dehydration of Methanol to Dimethyl Ether. Kinetic Investigation and Reactor Simulation. Industrial & Engineering Chemistry Research, 32, 2478-2484. https://doi.org/10.1021/ie00023a006
Froment, G.F. and Bischoff, K.B. (1991) Chemical Reactor Analysis and Design. Wiley, New York.
Rase, H.F. (1977) Chemical Reactor Design for Process Plants. Volume 2: Case Studies and Design Data. John Wiley & Sons, New York, 123-132.