Direct 2,3-Butanediol Conversion to Butene-Rich C3+ Olefins over Copper-Modified 2D Pillared MFI: Consequence of Reduced Diffusion Length
Abstract
2,3-Butanediol (2,3-BDO), a critical C4 platform chemical derived from biomass, syngas, or CO2, can be converted to C3+ olefins, serving as important renewable feedstocks for producing sustainable aviation fuels to decarbonize the hard-to-electrify air transportation sector. Herein, we report a bifunctional Cu-modified diffusion-free 2D pillared MFI catalyst (Cu/PMFI) which can selectively catalyze 2,3-BDO conversion to butene-rich C3+ olefins (95% selectivity at 97% conversion, 523 K). 2,3-BDO conversion to butenes over Cu/PMFI primarily occurs via methyl ethyl ketone intermediate while 2-methyl propanal is also observed as another minor dehydration product that leads to butene formation. In comparison with a control mesoporous Cu/ZSM-5 sample prepared by the postsynthetic approach, Cu/PMFI shows favorable C3+ olefin selectivity (95% over Cu/PMFI vs 80% over Cu/ZSM-5 at ~5.1 h TOS). The coke formation over Cu/PMFI is dramatically suppressed by >50% in contrast to Cu/ZSM-5 in 90 h 2,3-BDO conversion due to the reduced diffusion length. Cu/PMFI also favors butene formation and minimizes nonbutene C3+ olefins by inhibiting the downstream oligomerization and cracking reactions. This study highlights the usefulness of the diffusion-free 2D PMFI materials in catalytic conversion of biomass-derived platform molecules and the significance of diffusion impact on catalyst coke formation and product distributions.
- Authors:
-
[1];
[1];
[1];
[1];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Maryland, College Park, MD (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Maryland, College Park, MD (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
- OSTI Identifier:
- 1844869
- Grant/Contract Number:
- AC05-00OR22725; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Sustainable Chemistry & Engineering
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 2168-0485
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 2,3-butanediol; butane; 2D zeolite; sustainable aviation fuels; diffusion free; decarbonization; hydrocarbons; catalysts; chemical reactions; selectivity; coke
Citation Formats
Adhikari, Shiba, Zhang, Junyan, Unocic, Kinga A., Wegener, Evan C., Kunal, Pranaw, Deka, Dhruba J., Toops, Todd, Majumdar, Sreshtha Sinha, Krause, Theodore R., Liu, Dongxia, and Li, Zhenglong. Direct 2,3-Butanediol Conversion to Butene-Rich C3+ Olefins over Copper-Modified 2D Pillared MFI: Consequence of Reduced Diffusion Length. United States: N. p., 2022.
Web. doi:10.1021/acssuschemeng.1c07670.
Adhikari, Shiba, Zhang, Junyan, Unocic, Kinga A., Wegener, Evan C., Kunal, Pranaw, Deka, Dhruba J., Toops, Todd, Majumdar, Sreshtha Sinha, Krause, Theodore R., Liu, Dongxia, & Li, Zhenglong. Direct 2,3-Butanediol Conversion to Butene-Rich C3+ Olefins over Copper-Modified 2D Pillared MFI: Consequence of Reduced Diffusion Length. United States. https://doi.org/10.1021/acssuschemeng.1c07670
Adhikari, Shiba, Zhang, Junyan, Unocic, Kinga A., Wegener, Evan C., Kunal, Pranaw, Deka, Dhruba J., Toops, Todd, Majumdar, Sreshtha Sinha, Krause, Theodore R., Liu, Dongxia, and Li, Zhenglong. Thu .
"Direct 2,3-Butanediol Conversion to Butene-Rich C3+ Olefins over Copper-Modified 2D Pillared MFI: Consequence of Reduced Diffusion Length". United States. https://doi.org/10.1021/acssuschemeng.1c07670. https://www.osti.gov/servlets/purl/1844869.
@article{osti_1844869,
title = {Direct 2,3-Butanediol Conversion to Butene-Rich C3+ Olefins over Copper-Modified 2D Pillared MFI: Consequence of Reduced Diffusion Length},
author = {Adhikari, Shiba and Zhang, Junyan and Unocic, Kinga A. and Wegener, Evan C. and Kunal, Pranaw and Deka, Dhruba J. and Toops, Todd and Majumdar, Sreshtha Sinha and Krause, Theodore R. and Liu, Dongxia and Li, Zhenglong},
abstractNote = {2,3-Butanediol (2,3-BDO), a critical C4 platform chemical derived from biomass, syngas, or CO2, can be converted to C3+ olefins, serving as important renewable feedstocks for producing sustainable aviation fuels to decarbonize the hard-to-electrify air transportation sector. Herein, we report a bifunctional Cu-modified diffusion-free 2D pillared MFI catalyst (Cu/PMFI) which can selectively catalyze 2,3-BDO conversion to butene-rich C3+ olefins (95% selectivity at 97% conversion, 523 K). 2,3-BDO conversion to butenes over Cu/PMFI primarily occurs via methyl ethyl ketone intermediate while 2-methyl propanal is also observed as another minor dehydration product that leads to butene formation. In comparison with a control mesoporous Cu/ZSM-5 sample prepared by the postsynthetic approach, Cu/PMFI shows favorable C3+ olefin selectivity (95% over Cu/PMFI vs 80% over Cu/ZSM-5 at ~5.1 h TOS). The coke formation over Cu/PMFI is dramatically suppressed by >50% in contrast to Cu/ZSM-5 in 90 h 2,3-BDO conversion due to the reduced diffusion length. Cu/PMFI also favors butene formation and minimizes nonbutene C3+ olefins by inhibiting the downstream oligomerization and cracking reactions. This study highlights the usefulness of the diffusion-free 2D PMFI materials in catalytic conversion of biomass-derived platform molecules and the significance of diffusion impact on catalyst coke formation and product distributions.},
doi = {10.1021/acssuschemeng.1c07670},
journal = {ACS Sustainable Chemistry & Engineering},
number = 4,
volume = 10,
place = {United States},
year = {Thu Jan 20 00:00:00 EST 2022},
month = {Thu Jan 20 00:00:00 EST 2022}
}
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