Title: Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels–Alder Products

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 E_a = 10.8 kcal/mol and (ii) a catalyst-independent kinetic regime at high acid site concentrations with activation energy E_a = 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 apparentmore » activation energies of quantum mechanical and microkinetic simulations are in agreement with experimental values.« less

Authors:

Patet, Ryan E. ^[1]; Nikbin, Nima ^[1]; Williams, C. Luke ^[2]; Green, Sara K. ^[2]; Chang, Chun-Chih ^[2]; Fan, Wei ^[2]; Caratzoulas, Stavros ^[1]; Dauenhauer, Paul J. ^[3]; Vlachos, Dionisios G. ^[1]

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+ Show Author Affiliations

1. Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, United States, Catalysis Center for Energy Innovation (CCEI), University of Delaware, Newark, Delaware 19716, United States,
2. Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003, United States, Catalysis Center for Energy Innovation (CCEI), University of Delaware, Newark, Delaware 19716, United States,
3. Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455, United States, Catalysis Center for Energy Innovation (CCEI), University of Delaware, Newark, Delaware 19716, United States,

Publication Date:

Thu Mar 05 00:00:00 EST 2015

Research Org.:

Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

OSTI Identifier:

1174229

Alternate Identifier(s):

OSTI ID: 1385384

Grant/Contract Number:  

SC0001004; AC02-05CH11231

Resource Type:

Published Article

Journal Name:

ACS Catalysis

Additional Journal Information:

Journal Name: ACS Catalysis Journal Volume: 5 Journal Issue: 4; Journal ID: ISSN 2155-5435

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); biofuels (including algae and biomass); bio-inspired; hydrogen and fuel cells; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); p-xylene; 2,5-dimethylfuran (DMF); ethylene; Diels−Alder; dehydration; faujasite; microkinetic model