Tailoring olefin distribution via tuning rare earth metals in bifunctional Cu-RE/beta-zeolite catalysts for ethanol upgrading

Meijun Li; Junyan Zhang; Stephen C. Purdy; Fan Lin; Kinga A. Unocic; Michael Cordon; Zili Wu; Huamin Wang; Jacklyn Hall; A. Jeremy Kropf; Theodore R. Krause; Brian Davison; Zhenglong Li; Andrew D. Sutton

doi:10.1016/j.apcatb.2023.123648

Tailoring olefin distribution via tuning rare earth metals in bifunctional Cu-RE/beta-zeolite catalysts for ethanol upgrading

Meijun Li, Junyan Zhang, Stephen C. Purdy, Fan Lin, Kinga A. Unocic, Michael Cordon, Zili Wu, Huamin Wang, Jacklyn Hall, A. Jeremy Kropf, Theodore R. Krause, Brian Davison, Zhenglong Li, Andrew D. Sutton

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

Bioethanol to middle distillate technologies have offered a unique solution to produce renewable aviation fuel for decarbonizing the hard-to-electrify sectors. Here, we have developed the series of bimetallic Cu- and rare earth-containing (RE) Beta zeolite catalysts that yield high C₃₊ alkene selectivity from ethanol upgrading (>80% selectivity at ∼100% conversion, 623 K). The formation rates of butene isomers to C₅₊ alkenes are linearly correlated with the strength of Lewis acidic RE identity, which follows the sequence of Yb₁₂/Beta >Y₇/Beta > Gd₁₂/Beta > Ce₁₀/Beta > La₁₂/Beta. Rate measurements indicate that the RE selection plays the vital role in altering the rate of the key competitive reactions within the ethanol-to-alkenes reaction network, namely C₄ alcohol dehydration and C-C chain growth, which dictate alkene product distributions. These findings indicate a feasible and promising method for tailoring alkene product distributions from ethanol upgrading, which is of notable significance to the generation of renewable middle distillates.

Original language	English
Article number	123648
Journal	Applied Catalysis B: Environmental
Volume	344
DOIs	https://doi.org/10.1016/j.apcatb.2023.123648
State	Published - May 5 2024

Funding

M.L. and A.S. also acknowledges funding from Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (BETO), under contract DE-AC05-00OR22725 (ORNL) with UT-Battle, LLC, and in collaboration with the Chemical Catalysis for Bioenergy (Chem- CatBio) Consortium, a member of the Energy Materials Network. X-ray, electron microscopy and NH 3 -TPD measurements were conducted as part of a user project at the Center for Nanophase Materials Sciences ( CNMS ), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05–00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). Funding provided by the Center for Bioenergy Innovation (CBI), which is a U.S. Department of Energy Bioenergy Research Center supported by the Office of Biological and Environmental Research in the DOE Office of Science. Oak Ridge National Laboratory is managed by UT-Battelle, LLC for the US DOE under Contract Number DE-AC05-00OR22725.

Keywords

Alkenes
Decarbonization
Ethanol
Lewis acid Zeolite catalysts
Rare earth metals

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.apcatb.2023.123648

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Li, M., Zhang, J., Purdy, S. C., Lin, F., Unocic, K. A., Cordon, M., Wu, Z., Wang, H., Hall, J., Kropf, A. J., Krause, T. R., Davison, B., Li, Z., & Sutton, A. D. (2024). Tailoring olefin distribution via tuning rare earth metals in bifunctional Cu-RE/beta-zeolite catalysts for ethanol upgrading. Applied Catalysis B: Environmental, 344, Article 123648. https://doi.org/10.1016/j.apcatb.2023.123648

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abstract = "Bioethanol to middle distillate technologies have offered a unique solution to produce renewable aviation fuel for decarbonizing the hard-to-electrify sectors. Here, we have developed the series of bimetallic Cu- and rare earth-containing (RE) Beta zeolite catalysts that yield high C3+ alkene selectivity from ethanol upgrading (>80% selectivity at ∼100% conversion, 623 K). The formation rates of butene isomers to C5+ alkenes are linearly correlated with the strength of Lewis acidic RE identity, which follows the sequence of Yb12/Beta >Y7/Beta > Gd12/Beta > Ce10/Beta > La12/Beta. Rate measurements indicate that the RE selection plays the vital role in altering the rate of the key competitive reactions within the ethanol-to-alkenes reaction network, namely C4 alcohol dehydration and C-C chain growth, which dictate alkene product distributions. These findings indicate a feasible and promising method for tailoring alkene product distributions from ethanol upgrading, which is of notable significance to the generation of renewable middle distillates.",

keywords = "Alkenes, Decarbonization, Ethanol, Lewis acid Zeolite catalysts, Rare earth metals",

author = "Meijun Li and Junyan Zhang and Purdy, {Stephen C.} and Fan Lin and Unocic, {Kinga A.} and Michael Cordon and Zili Wu and Huamin Wang and Jacklyn Hall and Kropf, {A. Jeremy} and Krause, {Theodore R.} and Brian Davison and Zhenglong Li and Sutton, {Andrew D.}",

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doi = "10.1016/j.apcatb.2023.123648",

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Li, M, Zhang, J, Purdy, SC, Lin, F, Unocic, KA, Cordon, M, Wu, Z, Wang, H, Hall, J, Kropf, AJ, Krause, TR, Davison, B, Li, Z & Sutton, AD 2024, 'Tailoring olefin distribution via tuning rare earth metals in bifunctional Cu-RE/beta-zeolite catalysts for ethanol upgrading', Applied Catalysis B: Environmental, vol. 344, 123648. https://doi.org/10.1016/j.apcatb.2023.123648

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T1 - Tailoring olefin distribution via tuning rare earth metals in bifunctional Cu-RE/beta-zeolite catalysts for ethanol upgrading

AU - Li, Meijun

AU - Zhang, Junyan

AU - Purdy, Stephen C.

AU - Lin, Fan

AU - Unocic, Kinga A.

AU - Cordon, Michael

AU - Wu, Zili

AU - Wang, Huamin

AU - Hall, Jacklyn

AU - Kropf, A. Jeremy

AU - Krause, Theodore R.

AU - Davison, Brian

AU - Li, Zhenglong

AU - Sutton, Andrew D.

PY - 2024/5/5

Y1 - 2024/5/5

N2 - Bioethanol to middle distillate technologies have offered a unique solution to produce renewable aviation fuel for decarbonizing the hard-to-electrify sectors. Here, we have developed the series of bimetallic Cu- and rare earth-containing (RE) Beta zeolite catalysts that yield high C3+ alkene selectivity from ethanol upgrading (>80% selectivity at ∼100% conversion, 623 K). The formation rates of butene isomers to C5+ alkenes are linearly correlated with the strength of Lewis acidic RE identity, which follows the sequence of Yb12/Beta >Y7/Beta > Gd12/Beta > Ce10/Beta > La12/Beta. Rate measurements indicate that the RE selection plays the vital role in altering the rate of the key competitive reactions within the ethanol-to-alkenes reaction network, namely C4 alcohol dehydration and C-C chain growth, which dictate alkene product distributions. These findings indicate a feasible and promising method for tailoring alkene product distributions from ethanol upgrading, which is of notable significance to the generation of renewable middle distillates.

AB - Bioethanol to middle distillate technologies have offered a unique solution to produce renewable aviation fuel for decarbonizing the hard-to-electrify sectors. Here, we have developed the series of bimetallic Cu- and rare earth-containing (RE) Beta zeolite catalysts that yield high C3+ alkene selectivity from ethanol upgrading (>80% selectivity at ∼100% conversion, 623 K). The formation rates of butene isomers to C5+ alkenes are linearly correlated with the strength of Lewis acidic RE identity, which follows the sequence of Yb12/Beta >Y7/Beta > Gd12/Beta > Ce10/Beta > La12/Beta. Rate measurements indicate that the RE selection plays the vital role in altering the rate of the key competitive reactions within the ethanol-to-alkenes reaction network, namely C4 alcohol dehydration and C-C chain growth, which dictate alkene product distributions. These findings indicate a feasible and promising method for tailoring alkene product distributions from ethanol upgrading, which is of notable significance to the generation of renewable middle distillates.

KW - Alkenes

KW - Decarbonization

KW - Ethanol

KW - Lewis acid Zeolite catalysts

KW - Rare earth metals

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ER -

Tailoring olefin distribution via tuning rare earth metals in bifunctional Cu-RE/beta-zeolite catalysts for ethanol upgrading

Abstract

Funding

Keywords

UN SDGs

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