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Title: General Acid-Type Catalysis in the Dehydrative Aromatization of Furans to Aromatics in H-[Al]-BEA, H-[Fe]-BEA, H-[Ga]-BEA, and H-[B]-BEA Zeolites

Abstract

Al, Ga, Fe, and B metal substituents have been examined for their ability to change the Brønsted acid strength of BEA zeolite and inhibit undesired hydrolysis in the production of aromatics from furan, 2-methylfuran, and 2,5-dimethylfuran. We employed electronic structure calculations to examine this series of furans in H-[Al]-, H-[Fe]-, H-[Ga]-, and H-[B]-BEA zeolites. These calculations were used to parametrize a microkinetic model to make direct comparisons to experiments run with furan and DMF in the weakest and strongest acid zeolites, H-[B]-BEA and H-[Al]-BEA, respectively. Electronic structure calculations revealed that the Diels–Alder reaction remains unaffected by changes to the Brønsted acid strength of the zeolite, whereas the dehydration and hydrolysis reactions are affected in a fashion reminiscent of general acid catalysis. Interestingly, despite its significantly lower acid strength, H-[B]-BEA was experimentally shown to have an activity similar to that of H-[Al]-BEA for the production of both benzene and p-xylene from furan and 2,5-dimethylfuran, respectively. Analysis with the microkinetic model revealed that, even with this weaker heterogeneous acid site, the dehydration reaction is sufficiently catalyzed, activating the aromatic production pathway. Finally, the use of a weaker, heterogeneous Brønsted-acidic zeolite did not have a significant effect on the product selectivity, however, indicatingmore » that the same reaction pathways are active with both catalysts.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1]
  1. Univ. of Delaware, Newark, DE (United States). Dept. of Chemical and Biomolecular Engineering and Catalysis Center for Energy Innovation (CCEI)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1480470
Grant/Contract Number:  
SC0001004; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 25; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Patet, Ryan E., Koehle, Maura, Lobo, Raul F., Caratzoulas, Stavros, and Vlachos, Dionisios G. General Acid-Type Catalysis in the Dehydrative Aromatization of Furans to Aromatics in H-[Al]-BEA, H-[Fe]-BEA, H-[Ga]-BEA, and H-[B]-BEA Zeolites. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b02344.
Patet, Ryan E., Koehle, Maura, Lobo, Raul F., Caratzoulas, Stavros, & Vlachos, Dionisios G. General Acid-Type Catalysis in the Dehydrative Aromatization of Furans to Aromatics in H-[Al]-BEA, H-[Fe]-BEA, H-[Ga]-BEA, and H-[B]-BEA Zeolites. United States. doi:10.1021/acs.jpcc.7b02344.
Patet, Ryan E., Koehle, Maura, Lobo, Raul F., Caratzoulas, Stavros, and Vlachos, Dionisios G. Wed . "General Acid-Type Catalysis in the Dehydrative Aromatization of Furans to Aromatics in H-[Al]-BEA, H-[Fe]-BEA, H-[Ga]-BEA, and H-[B]-BEA Zeolites". United States. doi:10.1021/acs.jpcc.7b02344. https://www.osti.gov/servlets/purl/1480470.
@article{osti_1480470,
title = {General Acid-Type Catalysis in the Dehydrative Aromatization of Furans to Aromatics in H-[Al]-BEA, H-[Fe]-BEA, H-[Ga]-BEA, and H-[B]-BEA Zeolites},
author = {Patet, Ryan E. and Koehle, Maura and Lobo, Raul F. and Caratzoulas, Stavros and Vlachos, Dionisios G.},
abstractNote = {Al, Ga, Fe, and B metal substituents have been examined for their ability to change the Brønsted acid strength of BEA zeolite and inhibit undesired hydrolysis in the production of aromatics from furan, 2-methylfuran, and 2,5-dimethylfuran. We employed electronic structure calculations to examine this series of furans in H-[Al]-, H-[Fe]-, H-[Ga]-, and H-[B]-BEA zeolites. These calculations were used to parametrize a microkinetic model to make direct comparisons to experiments run with furan and DMF in the weakest and strongest acid zeolites, H-[B]-BEA and H-[Al]-BEA, respectively. Electronic structure calculations revealed that the Diels–Alder reaction remains unaffected by changes to the Brønsted acid strength of the zeolite, whereas the dehydration and hydrolysis reactions are affected in a fashion reminiscent of general acid catalysis. Interestingly, despite its significantly lower acid strength, H-[B]-BEA was experimentally shown to have an activity similar to that of H-[Al]-BEA for the production of both benzene and p-xylene from furan and 2,5-dimethylfuran, respectively. Analysis with the microkinetic model revealed that, even with this weaker heterogeneous acid site, the dehydration reaction is sufficiently catalyzed, activating the aromatic production pathway. Finally, the use of a weaker, heterogeneous Brønsted-acidic zeolite did not have a significant effect on the product selectivity, however, indicating that the same reaction pathways are active with both catalysts.},
doi = {10.1021/acs.jpcc.7b02344},
journal = {Journal of Physical Chemistry. C},
number = 25,
volume = 121,
place = {United States},
year = {2017},
month = {5}
}

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