Single-step Conversion of Methyl Ethyl Ketone to Olefins over ZnxZryOz Catalysts in Water

Dagle, Vanessa L.; Dagle, Robert A.; Kovarik, Libor; Baddour, Frederick G.; Habas, Susan E.; Elander, Richard T.

doi:10.1002/cctc.201900292

Single-step Conversion of Methyl Ethyl Ketone to Olefins over Zn_xZr_yO_z Catalysts in Water

Journal Article · Wed May 08 00:00:00 EDT 2019 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.201900292· OSTI ID:1544529

Dagle, Vanessa L. ^[1]; Dagle, Robert A. ^[1]; Kovarik, Libor ^[1]; ^[2]; ^[2]; Elander, Richard T. ^[2]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

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 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.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; AC36-08GO28308

OSTI ID:: 1544529

Alternate ID(s):: OSTI ID: 1633401

Report Number(s):: NREL/JA--5100-73271

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 15 Vol. 11; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (27)

The dehydration of fermentative 2,3-butanediol into methyl ethyl ketone Tran, Ai V.; Chambers, Robert P. Biotechnology and Bioengineering, Vol. 29, Issue 3 https://doi.org/10.1002/bit.260290308	journal	February 1987
Conversion of 2,3-Butanediol over Phosphate Catalysts Nikitina, Maria A.; Ivanova, Irina I. ChemCatChem, Vol. 8, Issue 7 https://doi.org/10.1002/cctc.201501399	journal	February 2016
Hydrogen-Free Gas-Phase Deoxydehydration of 2,3-Butanediol to Butene on Silica-Supported Vanadium Catalysts Kwok, Kelvin Mingyao; Choong, Catherine Kai Shin; Ong, Daniel Sze Wei ChemCatChem, Vol. 9, Issue 13 https://doi.org/10.1002/cctc.201700301	journal	June 2017
Determination of Integrated Molar Extinction Coefficients for Infrared Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts Emeis, C. A. Journal of Catalysis, Vol. 141, Issue 2 https://doi.org/10.1006/jcat.1993.1145	journal	June 1993
Transformation of 1,2-diols over perfluorinated resinsulfonic acids (Nafion-H) Bucsi, Imre; Molnár, Árpád; Bartók, Mihály Tetrahedron, Vol. 50, Issue 27 https://doi.org/10.1016/S0040-4020(01)85301-1	journal	January 1994
A study of ZnxZryOz mixed oxides for direct conversion of ethanol to isobutene Liu, Changjun; Sun, Junming; Smith, Colin Applied Catalysis A: General, Vol. 467 https://doi.org/10.1016/j.apcata.2013.07.011	journal	October 2013
2,3-Butanediol dehydration catalyzed by silica-supported alkali phosphates Kim, Wooyoung; Shin, Wookyun; Lee, Kyoung Jun Applied Catalysis A: General, Vol. 570 https://doi.org/10.1016/j.apcata.2018.08.015	journal	January 2019
Conversion of methyl ethyl ketone to butenes over bifunctional catalysts Al-Auda, Zahraa; Al-Atabi, Hayder; Li, Xu Applied Catalysis A: General, Vol. 570 https://doi.org/10.1016/j.apcata.2018.09.027	journal	January 2019
Structural identification of ZnxZryOz catalysts for Cascade aldolization and self-deoxygenation reactions Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor Applied Catalysis B: Environmental, Vol. 234 https://doi.org/10.1016/j.apcatb.2018.04.051	journal	October 2018
Microbial 2,3-butanediol production: A state-of-the-art review Ji, Xiao-Jun; Huang, He; Ouyang, Ping-Kai Biotechnology Advances, Vol. 29, Issue 3 https://doi.org/10.1016/j.biotechadv.2011.01.007	journal	May 2011
Conversion of 2,3-butanediol to butenes over bifunctional catalysts in a single reactor Zheng, Quanxing; Wales, Michael D.; Heidlage, Michael G. Journal of Catalysis, Vol. 330 https://doi.org/10.1016/j.jcat.2015.07.004	journal	October 2015
Study of mesoporous catalysts for conversion of 2,3-butanediol to butenes Zheng, Quanxing; Grossardt, Jason; Almkhelfe, Haider Journal of Catalysis, Vol. 354 https://doi.org/10.1016/j.jcat.2017.08.017	journal	October 2017
Mechanistic study of the catalytic conversion of 2,3-butanediol to butenes Zheng, Quanxing; Xu, Jiayi; Liu, Bin Journal of Catalysis, Vol. 360 https://doi.org/10.1016/j.jcat.2018.01.034	journal	April 2018
The ZnxZr1−xO2−y solid solution on m-ZrO2: Creating O vacancies and improving the m-ZrO2 redox properties Silva-Calpa, Leydi del R.; Zonetti, Priscila C.; Rodrigues, Clarissa P. Journal of Molecular Catalysis A: Chemical, Vol. 425 https://doi.org/10.1016/j.molcata.2016.10.008	journal	December 2016
Kinetic Model Development for Dehydration of 2,3-Butanediol to 1,3-Butadiene and Methyl Ethyl Ketone over an Amorphous Calcium Phosphate Catalyst Song, Daesung Industrial & Engineering Chemistry Research, Vol. 55, Issue 45 https://doi.org/10.1021/acs.iecr.6b02930	journal	November 2016
Conceptual Design of Methyl Ethyl Ketone Production via 2,3-Butanediol for Fuels and Chemicals Penner, Daniel; Redepenning, Christian; Mitsos, Alexander Industrial & Engineering Chemistry Research, Vol. 56, Issue 14 https://doi.org/10.1021/acs.iecr.6b03678	journal	March 2017
Low-Temperature Dehydrogenation of Ethanol on Atomically Dispersed Gold Supported on ZnZrO _x Wang, Chongyang; Garbarino, Gabriella; Allard, Lawrence F. ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b01593	journal	December 2015
Recent Advances in Catalytic Conversion of Ethanol to Chemicals Sun, Junming; Wang, Yong ACS Catalysis, Vol. 4, Issue 4 https://doi.org/10.1021/cs4011343	journal	March 2014
Cascade Reactions for the Continuous and Selective Production of Isobutene from Bioderived Acetic Acid Over Zinc-Zirconia Catalysts Crisci, Anthony J.; Dou, Herui; Prasomsri, Teerawit ACS Catalysis, Vol. 4, Issue 11 https://doi.org/10.1021/cs501018k	journal	October 2014
Kinetics of dehydration of aqueous 2,3-butanediol to methyl ethyl ketone Emerson, Richard R.; Flickinger, Michael C.; Tsao, George T. Industrial & Engineering Chemistry Product Research and Development, Vol. 21, Issue 3 https://doi.org/10.1021/i300007a025	journal	September 1982
Direct Conversion of Bio-ethanol to Isobutene on Nanosized Zn _x Zr _y O _z Mixed Oxides with Balanced Acid–Base Sites Sun, Junming; Zhu, Kake; Gao, Feng Journal of the American Chemical Society, Vol. 133, Issue 29 https://doi.org/10.1021/ja204235v	journal	July 2011
Key Roles of Lewis Acid–Base Pairs on Zn _x Zr _y O _z in Direct Ethanol/Acetone to Isobutene Conversion Sun, Junming; Baylon, Rebecca A. L.; Liu, Changjun Journal of the American Chemical Society, Vol. 138, Issue 2 https://doi.org/10.1021/jacs.5b07401	journal	December 2015
Beyond ketonization: selective conversion of carboxylic acids to olefins over balanced Lewis acid–base pairs Baylon, Rebecca A. L.; Sun, Junming; Martin, Kevin J. Chemical Communications, Vol. 52, Issue 28 https://doi.org/10.1039/C5CC10528E	journal	January 2016
Conversion of syngas-derived C₂+ mixed oxygenates to C₃–C₅ olefins over Zn_xZr_yO_z mixed oxide catalysts Smith, Colin; Dagle, Vanessa Lebarbier; Flake, Matthew Catalysis Science & Technology, Vol. 6, Issue 7, p. 2325-2336 https://doi.org/10.1039/C5CY01261A	journal	January 2016
Catalytic dehydration of 2,3-butanediol over P/HZSM-5: effect of catalyst, reaction temperature and reactant configuration on rearrangement products Zhao, Jinbo; Yu, Dinghua; Zhang, Wengui RSC Advances, Vol. 6, Issue 21 https://doi.org/10.1039/C5RA23251A	journal	January 2016
Efficient dehydration of bio-based 2,3-butanediol to butanone over boric acid modified HZSM-5 zeolites Zhang, Wengui; Yu, Dinghua; Ji, Xiaojun Green Chemistry, Vol. 14, Issue 12 https://doi.org/10.1039/c2gc36324k	journal	January 2012
Influence of crystal structure of nanosized ZrO2 on photocatalytic degradation of methyl orange Basahel, Sulaiman N.; Ali, Tarek T.; Mokhtar, Mohamed Nanoscale Research Letters, Vol. 10, Issue 1 https://doi.org/10.1186/s11671-015-0780-z	journal	February 2015

Cited By (1)

Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C3–C5 Olefins over ZnxZryOz Catalyst Davidson, Stephen D.; Lopez-Ruiz, Juan A.; Flake, Matthew Catalysts, Vol. 9, Issue 11 https://doi.org/10.3390/catal9110923	journal	November 2019

Similar Records

Production and catalytic upgrading of 2,3-butanediol fermentation broth into sustainable aviation fuel blendstock and fuel properties measurement

Journal Article · Mon Oct 17 00:00:00 EDT 2022 · Fuel · OSTI ID:1897938

Production and Catalytic Upgrading of 2,3-Butanediol Fermentation Broth into Sustainable Aviation Fuel Blendstock and Fuel Properties Measurement

Journal Article · Mon Oct 17 00:00:00 EDT 2022 · Fuel · OSTI ID:1900017

Related Subjects

09 BIOMASS FUELS
2
3-butanediol
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
aqueous
bio-fuels
methyl-ethyl-ketone
olefins