Abstract
This PhD thesis deeply analyzes the mechanistic and kinetic behavior of methanol and dimethyl ether (DME) in the industrially relevant Methanol-To-Hydrocarbons (MTH) reaction, which employs zeolitic materials as catalysts. Industrial MTH processes use methanol, DME or combined methanol/DME feeds over zeolitic catalysts. Methanol and its dehydration product, DME, are conventionally attributed an analogous behavior in MTH; however, a thorough investigation on the theme was missing even though the MTH reaction has been studied for 40 years already. By means of mechanistic and kinetic studies, methanol has been found to negatively impact catalyst stability as compared to DME. This is rationalized based on the ability of methanol to form formaldehyde, a molecule that can act as coke promoter. Furthermore, the work presented in this PhD thesis suggest different strategies to reduce the impact of methanol on catalyst deactivation, thereby optimizing the lifetime of the catalyst during MTH operation.
List of papers
I. Benzene co-reaction with methanol and dimethyl ether over zeolite and zeotype catalysts: Evidence of parallel reaction paths to toluene and diphenylmethane. J. S. Martínez-Espín, K. De Wispelaere, M. Westgård Erichsen, S. Svelle, T. V. W. Janssens, V. Van Speybroeck, P. Beato, U. Olsbye. Journal of Catalysis, 349, 2017, 136-148. The article is not available in DUO due to publisher restrictions. The published version is available at: https://doi.org/10.1016/j.jcat.2017.03.007 |
II. New insights in catalyst deactivation and product distribution of zeolites in the Methanol-To-Hydrocarbons (MTH) reaction with methanol and dimethyl ether feeds. J. S. Martínez-Espín, M. Mortén, T. V. W. Janssens, S. Svelle, P. Beato, U. Olsbye. Catalysis Science & Technology, 2017 (published). The article is not available in DUO due to publisher restrictions. The published version is available at: https://doi.org/10.1039/c7cy00129k |
III. Hydrogen transfer versus methylation: on the genesis of aromatics formation in the Methanol-To-Hydrocarbons reaction over H-ZSM-5. J. S. Martínez-Espín, K. De Wispelaere, T. V. W. Janssens, S. Svelle, K. P. Lillerud, V. Van Speybroeck, P. Beato, U. Olsbye. ACS Catalysis, 2017 (submitted). The article is not available in DUO due to publisher restrictions. The published version is available at: https://doi.org/10.1021/acscatal.7b01643 |
IV. Syngas to liquids via oxygenates. M. Westgård Erichsen, J. S. Martínez-Espín, P. del Campo, K. P.Lillerud, S. Svelle, P. Beato, U. Olsbye. Book chapter in “Small-Scale Gas to Liquid Fuel Synthesis”, CRC Press, 2015, 431-463.The article is not available in DUO due to publisher restrictions. |
V. Fossil Fuels: The Effect of Zeolite Catalyst Particle Morphology on Catalyst Performance in the Conversion of Methanol to Hydrocarbons. K. A. Lukaszuk, P. del Campo, A. Molino, M. Nielsen, D. Rojo-Gama, J. S. Martínez-Espín, K. P. Lillerud, U. Olsbye, S. Bordiga, P. Beato, S. Svelle. Book chapter in “Nanotechnology for Energy Sustainability”, Wiley-VCH Verlag GmbH & Co. KGaA, 2017, 1-40.The article is not available in DUO due to publisher restrictions. |
VI. Phosphorous modified ZSM-5 zeolites: impact on methanol conversion into olefins. P. Losch, G.Laugel, J. S. Martínez-Espín, S. Chavan, U. Olsbye, B. Louis. Topics in Catalysis, 58, 2015, 826-832. The article is not available in DUO due to publisher restrictions. The published version is available at: https://doi.org/10.1007/s11244-015-0449-y |
VII. On the formation and special role of formaldehyde in the conversion of methanol into hydrocarbons. K. De Wispelaere, J. S. Martínez-Espín, S. Svelle, P. Beato, U. Olsbye, V. Van Speybroeck (in preparation). The paper is not available in DUO awaiting publishing. |