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Title: Single-step Conversion of Methyl Ethyl Ketone to Olefins over Zn xZr yO z Catalysts in Water

Abstract

In this study we investigated the conversion of aqueous methyl-ethyl-ketone (MEK) to olefin fuel precursors over Zn xZr yO z mixed oxide catalysts. Experiments were carried out in water as MEK is intended to be produced from the dehydration of 2,3-butanediol in fermentation broth which is highly diluted in water. We demonstrated that Zn xZr yO z catalysts are highly effective for converting aqueous MEK to C 4-C 5 olefins. High selectivity to olefins equal to 85% was reached at 92% per pass conversion when under H 2 atmosphere. Catalyst stability was demonstrated for 60 hours' time on stream, highlighting the potential for upgrading 2,3-butanediol contained in fermentation broth without the need for energy-intensive water separation. Increased concentration of MEK in the aqueous feed results in increased activity towards olefin production. However, water inhibits catalyst deactivation from coking. A mechanistic investigation revealed the impact of the reaction environment (inert or reducing atmosphere) on the reaction pathways. In an inert environment, the mechanism involves consecutive aldol condensation of MEK and 3-pentanone intermediate. Under reducing conditions two reaction pathways compete with each other as MEK hydrogenation to butenes occurs concurrently with the aldol condensation/decomposition.

Authors:
 [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [2];  [2]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
OSTI Identifier:
1544529
Report Number(s):
NREL/JA-5100-73271
Journal ID: ISSN 1867-3880
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 11; Journal Issue: 15; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; methyl-ethyl-ketone; 2,3-butanediol; olefins; aqueous; bio-fuels

Citation Formats

Dagle, Vanessa L., Dagle, Robert A., Kovarik, Libor, Baddour, Frederick G., Habas, Susan E., and Elander, Richard T. Single-step Conversion of Methyl Ethyl Ketone to Olefins over ZnxZryOz Catalysts in Water. United States: N. p., 2019. Web. doi:10.1002/cctc.201900292.
Dagle, Vanessa L., Dagle, Robert A., Kovarik, Libor, Baddour, Frederick G., Habas, Susan E., & Elander, Richard T. Single-step Conversion of Methyl Ethyl Ketone to Olefins over ZnxZryOz Catalysts in Water. United States. doi:10.1002/cctc.201900292.
Dagle, Vanessa L., Dagle, Robert A., Kovarik, Libor, Baddour, Frederick G., Habas, Susan E., and Elander, Richard T. Wed . "Single-step Conversion of Methyl Ethyl Ketone to Olefins over ZnxZryOz Catalysts in Water". United States. doi:10.1002/cctc.201900292.
@article{osti_1544529,
title = {Single-step Conversion of Methyl Ethyl Ketone to Olefins over ZnxZryOz Catalysts in Water},
author = {Dagle, Vanessa L. and Dagle, Robert A. and Kovarik, Libor and Baddour, Frederick G. and Habas, Susan E. and Elander, Richard T.},
abstractNote = {In this study we investigated the conversion of aqueous methyl-ethyl-ketone (MEK) to olefin fuel precursors over ZnxZryOz mixed oxide catalysts. Experiments were carried out in water as MEK is intended to be produced from the dehydration of 2,3-butanediol in fermentation broth which is highly diluted in water. We demonstrated that ZnxZryOz catalysts are highly effective for converting aqueous MEK to C4-C5 olefins. High selectivity to olefins equal to 85% was reached at 92% per pass conversion when under H2 atmosphere. Catalyst stability was demonstrated for 60 hours' time on stream, highlighting the potential for upgrading 2,3-butanediol contained in fermentation broth without the need for energy-intensive water separation. Increased concentration of MEK in the aqueous feed results in increased activity towards olefin production. However, water inhibits catalyst deactivation from coking. A mechanistic investigation revealed the impact of the reaction environment (inert or reducing atmosphere) on the reaction pathways. In an inert environment, the mechanism involves consecutive aldol condensation of MEK and 3-pentanone intermediate. Under reducing conditions two reaction pathways compete with each other as MEK hydrogenation to butenes occurs concurrently with the aldol condensation/decomposition.},
doi = {10.1002/cctc.201900292},
journal = {ChemCatChem},
number = 15,
volume = 11,
place = {United States},
year = {2019},
month = {5}
}

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