Center for Molecular Modeling - J. De Ridder

Enthalpy and entropy barriers explain the effects of topology on the kinetics of zeolite-catalyzed reactions

jeroen — Thu, 04 Apr 2013 14:06:37 +0000

J. Van der Mynsbrugge, J. De Ridder, K. Hemelsoet, M. Waroquier, V. Van Speybroeck

Chemistry - A European Journal

19 (35), 11568-11576

2013

Abstract

The methylation of ethene, propene, and trans-2-butene on zeolites H-ZSM-58 (DDR), H-ZSM-22 (TON), and H-ZSM-5 (MFI) is studied to elucidate the particular influence of topology on the kinetics of zeolite-catalyzed reactions. H-ZSM-58 and H-ZSM-22 are found to display overall lower methylation rates compared to H-ZSM-5 and also different trends in methylation rates with increasing alkene size. These variations may be rationalized based on a decomposition of the free-energy barriers into enthalpic and entropic contributions, which reveals that the lower methylation rates on H-ZSM-58 and H-ZSM-22 have virtually opposite reasons. On H-ZSM-58, the lower methylation rates are caused by higher enthalpy barriers, owing to inefficient stabilization of the reaction intermediates in the large cage-like pores. On the other hand, on H-ZSM-22, the methylation rates mostly suffer from higher entropy barriers, because excessive entropy losses are incurred inside the narrow-channel structure. These results show that the kinetics of crucial elementary steps hinge on the balance between proper stabilization of the reaction intermediates inside the zeolite pores and the resulting entropy losses. These fundamental insights into their inner workings are indispensable for ultimately selecting or designing better zeolite catalysts.

DOI

http://dx.doi.org/10.1002/chem.201301272

Private attachment

13_chem_eur_ j_xxx_VanderMynsbrugge.pdf

13_chem_eur_ j_19(35)11568_VanderMynsbrugge.pdf

NCCC-XII

wim — Thu, 07 Feb 2013 13:54:44 +0000

Noordwijkerhout, The Netherlands

Monday, 28 February, 2011 to Wednesday, 2 March, 2011

Participant(s)

K. Hemelsoet, M. Vandichel, T. Bogaerts, J. Van der Mynsbrugge, S. Cottenie, K. De Wispelaere, J. De Ridder, B. De Sterck

Project ref.

FWO mandaat, BOF mandaat

Conference reference

NCCC-XII

Kinetic study on key reaction steps in methanol-to-olefin conversion: influence of catalyst topology

wim — Fri, 09 Mar 2012 11:25:29 +0000

J. Van der Mynsbrugge, J. De Ridder, K. Hemelsoet, M. Waroquier, V. Van Speybroeck

p. 136

Talk

Conference / event / venue

XIIIth Netherlands' Catalysis and Chemistry Conference (NCCC XIII)

Noordwijkerhout, The Netherlands

Monday, 5 March, 2012 to Wednesday, 7 March, 2012

Abstract (private)

2012 NCCC JVDM.pdf

Conference reference

NCCC-XIII

Kinetic study on the effects of zeolite topology on methylation reactions in the methanol-to-olefins process

jeroen — Wed, 29 Feb 2012 09:00:09 +0000

J. Van der Mynsbrugge, J. De Ridder, K. Hemelsoet, M. Waroquier, V. Van Speybroeck

p. 83-84

Poster

Conference / event / venue

ICTAC-14

Vlissingen, The Netherlands

Tuesday, 26 June, 2012 to Saturday, 30 June, 2012

Abstract (private)

2012_ICTAC14_JvdMyns.pdf

Conference reference

ICTAC-14

Effects of zeolite topology on methylation reactions in the MTO process from a theoretical perspective

wim — Mon, 17 Oct 2011 13:12:00 +0000

J. De Ridder, J. Van der Mynsbrugge, B. De Sterck, K. Hemelsoet, M. Waroquier, V. Van Speybroeck

p. 199

Poster

Conference / event / venue

XIIth Netherlands' Catalysis and Chemistry Conference (NCCC XII)

Noordwijkerhout, The Netherlands

Monday, 28 February, 2011 to Wednesday, 2 March, 2011

Abstract

2011_nccc_ridder_v6.pdf

Conference reference

NCCC-XII

Investigation of Confinement Effects on Zeolite-Catalyzed Methylation Reactions

wim — Fri, 26 Aug 2011 12:57:44 +0000

J. Van der Mynsbrugge, K. De Wispelaere, J. De Ridder, K. Hemelsoet, M. Waroquier, V. Van Speybroeck

Abstract OC 059

Talk

Conference / event / venue

Ninth Triennial Congress of the World Association of Theoretical and Computational Chemists (WATOC)

Santiago de Compostela, Spain

Sunday, 17 July, 2011 to Friday, 22 July, 2011

Abstract

2011 WATOC JVDM OC059.pdf

Conference reference

WATOC 2011

Jeroen De Ridder

wim — Thu, 25 Aug 2011 12:21:47 +0000

Ab initio studie naar de invloed van de topologie en samenstelling van een zeolietkatalysator op de kinetiek van methyleringsreacties

wim — Wed, 24 Aug 2011 12:44:18 +0000

J. De Ridder

Master of Science in Chemical Engineering

2011

Supervisors

Prof. Dr. ir. Veronique Van Speybroeck, Prof. Dr. Michel Waroquier

Attachment (public)

MT_jderidder.pdf