Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels-Alder Products

Ryan E. Patet, Nima Nikbin, C. Luke Williams, Sara K. Green, Chun Chih Chang, Wei Fan, Stavros Caratzoulas, Paul J Dauenhauer, Dionisios G. Vlachos

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

Renewable production of p-xylene from [4 + 2] Diels-Alder cycloaddition of 2,5-dimethylfuran (DMF) and ethylene with H-Y zeolite catalyst in n-heptane solvent is investigated. Experimental studies varying the solid acid catalyst concentration reveal two kinetic regimes for the p-xylene production rate: (i) a linear regime at low acid site concentrations with activation energy Ea = 10.8 kcal/mol and (ii) a catalyst-independent kinetic regime at high acid site concentrations with activation energy Ea = 20.1 kcal/mol. We carry out hybrid QM/MM calculations with a three-layer embedded cluster ONIOM model to compute the energetics along the main reaction pathway, and a microkinetic model is constructed for the interpretation of the experimental kinetic data. At high solid acid concentrations, p-xylene production is limited by the homogeneous Diels-Alder reaction, whereas at low acid concentrations, the overall rate is limited by the heterogeneously catalyzed dehydration of the Diels-Alder cycloadduct of DMF and ethylene because of an insufficient number of acid sites, despite the dehydration reaction requiring significantly less activation energy. A reduced kinetic model reveals that the production of p-xylene follows the general kinetics of tandem reactions in which the first step is uncatalyzed and the second step is heterogeneously catalyzed. Reaction orders and apparent activation energies of quantum mechanical and microkinetic simulations are in agreement with experimental values. (Chemical Presented).

Original languageEnglish (US)
Pages (from-to)2367-2375
Number of pages9
JournalACS Catalysis
Volume5
Issue number4
DOIs
StatePublished - Apr 3 2015

Fingerprint

Aromatization
Xylene
Kinetics
Acids
Activation energy
Dehydration
Catalysts
Ethylene
Zeolites
Cycloaddition
Heptane
furan
4-xylene

Keywords

  • 2,5-Dimethylfuran (DMF)
  • Dehydration
  • Diels-Alder
  • Ethylene
  • Faujasite
  • Microkinetic model
  • p-xylene

Cite this

Patet, R. E., Nikbin, N., Williams, C. L., Green, S. K., Chang, C. C., Fan, W., ... Vlachos, D. G. (2015). Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels-Alder Products. ACS Catalysis, 5(4), 2367-2375. https://doi.org/10.1021/cs5020783

Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels-Alder Products. / Patet, Ryan E.; Nikbin, Nima; Williams, C. Luke; Green, Sara K.; Chang, Chun Chih; Fan, Wei; Caratzoulas, Stavros; Dauenhauer, Paul J; Vlachos, Dionisios G.

In: ACS Catalysis, Vol. 5, No. 4, 03.04.2015, p. 2367-2375.

Research output: Contribution to journalArticle

Patet, RE, Nikbin, N, Williams, CL, Green, SK, Chang, CC, Fan, W, Caratzoulas, S, Dauenhauer, PJ & Vlachos, DG 2015, 'Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels-Alder Products', ACS Catalysis, vol. 5, no. 4, pp. 2367-2375. https://doi.org/10.1021/cs5020783
Patet RE, Nikbin N, Williams CL, Green SK, Chang CC, Fan W et al. Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels-Alder Products. ACS Catalysis. 2015 Apr 3;5(4):2367-2375. https://doi.org/10.1021/cs5020783
Patet, Ryan E. ; Nikbin, Nima ; Williams, C. Luke ; Green, Sara K. ; Chang, Chun Chih ; Fan, Wei ; Caratzoulas, Stavros ; Dauenhauer, Paul J ; Vlachos, Dionisios G. / Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels-Alder Products. In: ACS Catalysis. 2015 ; Vol. 5, No. 4. pp. 2367-2375.
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AU - Chang, Chun Chih

AU - Fan, Wei

AU - Caratzoulas, Stavros

AU - Dauenhauer, Paul J

AU - Vlachos, Dionisios G.

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N2 - Renewable production of p-xylene from [4 + 2] Diels-Alder cycloaddition of 2,5-dimethylfuran (DMF) and ethylene with H-Y zeolite catalyst in n-heptane solvent is investigated. Experimental studies varying the solid acid catalyst concentration reveal two kinetic regimes for the p-xylene production rate: (i) a linear regime at low acid site concentrations with activation energy Ea = 10.8 kcal/mol and (ii) a catalyst-independent kinetic regime at high acid site concentrations with activation energy Ea = 20.1 kcal/mol. We carry out hybrid QM/MM calculations with a three-layer embedded cluster ONIOM model to compute the energetics along the main reaction pathway, and a microkinetic model is constructed for the interpretation of the experimental kinetic data. At high solid acid concentrations, p-xylene production is limited by the homogeneous Diels-Alder reaction, whereas at low acid concentrations, the overall rate is limited by the heterogeneously catalyzed dehydration of the Diels-Alder cycloadduct of DMF and ethylene because of an insufficient number of acid sites, despite the dehydration reaction requiring significantly less activation energy. A reduced kinetic model reveals that the production of p-xylene follows the general kinetics of tandem reactions in which the first step is uncatalyzed and the second step is heterogeneously catalyzed. Reaction orders and apparent activation energies of quantum mechanical and microkinetic simulations are in agreement with experimental values. (Chemical Presented).

AB - Renewable production of p-xylene from [4 + 2] Diels-Alder cycloaddition of 2,5-dimethylfuran (DMF) and ethylene with H-Y zeolite catalyst in n-heptane solvent is investigated. Experimental studies varying the solid acid catalyst concentration reveal two kinetic regimes for the p-xylene production rate: (i) a linear regime at low acid site concentrations with activation energy Ea = 10.8 kcal/mol and (ii) a catalyst-independent kinetic regime at high acid site concentrations with activation energy Ea = 20.1 kcal/mol. We carry out hybrid QM/MM calculations with a three-layer embedded cluster ONIOM model to compute the energetics along the main reaction pathway, and a microkinetic model is constructed for the interpretation of the experimental kinetic data. At high solid acid concentrations, p-xylene production is limited by the homogeneous Diels-Alder reaction, whereas at low acid concentrations, the overall rate is limited by the heterogeneously catalyzed dehydration of the Diels-Alder cycloadduct of DMF and ethylene because of an insufficient number of acid sites, despite the dehydration reaction requiring significantly less activation energy. A reduced kinetic model reveals that the production of p-xylene follows the general kinetics of tandem reactions in which the first step is uncatalyzed and the second step is heterogeneously catalyzed. Reaction orders and apparent activation energies of quantum mechanical and microkinetic simulations are in agreement with experimental values. (Chemical Presented).

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