Ethanol Conversion to C4+ Olefins over Bimetallic Copper- And Lanthanum-Containing Beta Zeolite Catalysts

Cordon, Michael J.; Zhang, Junyan; Samad, Nohor River; Harris, James W.; Unocic, Kinga A.; Li, Meijun; Liu, Dongxia; Li, Zhenglong

doi:10.1021/acssuschemeng.1c07442

Title: Ethanol Conversion to C₄₊ Olefins over Bimetallic Copper- And Lanthanum-Containing Beta Zeolite Catalysts

Journal Article · Fri Apr 22 00:00:00 EDT 2022 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.1c07442· OSTI ID:1883667

Cordon, Michael J. ^[1]; Zhang, Junyan ^[2]; Samad, Nohor River ^[3]; Harris, James W. ^[3]; Unocic, Kinga A. ^[1];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); University of Maryland, College Park, MD (United States)
University of Alabama, Tuscaloosa, AL (United States)
University of Maryland, College Park, MD (United States)

We report ethanol conversion to C₄₊ olefins remains a critical yet nonselective process for producing renewable middle distillates. Here, Cu–La/Beta catalysts composed of copper and lanthanum incorporated onto a dealuminated Beta support are reported for ethanol conversion to C₄₊ olefins (73% selectivity, ~98% ethanol conversion, 623 K,<4% C₁–C₃ hydrocarbons) which particularly favors C₅₊ olefin formation (43% selectivity) as a distinction from the benchmarking Cu–Y/Beta catalyst. Monometallic Cu/Beta or La/Beta samples are insufficient to catalyze the C₄₊ olefin formation and primarily form dehydration products (e.g., ethylene and diethyl ether), indicating the necessity of both Cu and La species for butene and C₅₊ olefin formation. Increasing the bulk La loading at a fixed Cu content yields higher C₅₊ olefins until the La/Cu molar ratio reaches 3.6. These findings indicate Cu–La/Beta as an effective ethanol conversion catalyst that facilitates multiple C–C bond formation events required for synthesizing C₅₊ olefins (i.e., hexenes and octenes).

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1883667

Journal Information:: ACS Sustainable Chemistry & Engineering, Vol. 10, Issue 18; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (26)

1-Hexene: a renewable C6 platform for full-performance jet and diesel fuels Harvey, Benjamin G.; Meylemans, Heather A. Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC41554F	journal	January 2014
Dehydrated Lanthanum-exchanged Type Y Zeolite Smith, J. V.; Bennett, J. M.; Flanigen, E. M. Nature, Vol. 215, Issue 5098 https://doi.org/10.1038/215241a0	journal	July 1967
Tandem mass spectrometric analysis of rare earth(III) complexes: evaluation of the relative strength of their Lewis acidity Tsuruta, Hideyuki; Yamaguchi, Kentaro; Imamoto, Tsuneo Tetrahedron, Vol. 59, Issue 52 https://doi.org/10.1016/j.tet.2003.06.006	journal	December 2003
Unraveling the Homologation Reaction Sequence of the Zeolite‐Catalyzed Ethanol‐to‐Hydrocarbons Process Chowdhury, Abhishek Dutta; Lucini Paioni, Alessandra; Whiting, Gareth T. Angewandte Chemie International Edition, Vol. 58, Issue 12 https://doi.org/10.1002/anie.201814268	journal	March 2019
Selective conversion of bio-derived ethanol to renewable BTX over Ga-ZSM-5 Li, Zhenglong; Lepore, Andrew W.; Salazar, Mariam F. Green Chemistry, Vol. 19, Issue 18 https://doi.org/10.1039/C7GC01188A	journal	January 2017
Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces Li, Fengwang; Li, Yuguang C.; Wang, Ziyun Nature Catalysis, Vol. 3, Issue 1 https://doi.org/10.1038/s41929-019-0383-7	journal	December 2019
Comparison of conventional and solid-state ion exchange procedures for the incorporation of lanthanum in H-beta zeolite Jia, Chunjuan; Beaunier, Patricia; Massiani, Pascale Microporous and Mesoporous Materials, Vol. 24, Issue 1-3 https://doi.org/10.1016/S1387-1811(98)00144-9	journal	October 1998
Influence of rare earth elements on the acid and metal sites of Pt/HBEA catalyst for short chain n-alkane hydroisomerization Martins, A.; Silva, J. M.; Ribeiro, M. F. Applied Catalysis A: General, Vol. 466 https://doi.org/10.1016/j.apcata.2013.06.043	journal	September 2013
Ethanol Conversion to Butadiene over Isolated Zinc and Yttrium Sites Grafted onto Dealuminated Beta Zeolite Qi, Liang; Zhang, Yanfei; Conrad, Matthew A. Journal of the American Chemical Society, Vol. 142, Issue 34 https://doi.org/10.1021/jacs.0c06906	journal	July 2020
Disproportionation of hydrogen peroxide into singlet oxygen catalyzed by lanthanum-exchanged zeolites Wahlen, J.; Dehertogh, S.; Devos, D. Journal of Catalysis, Vol. 233, Issue 2 https://doi.org/10.1016/j.jcat.2005.05.013	journal	July 2005
Selective Butene Formation in Direct Ethanol-to-C ₃₊ -Olefin Valorization over Zn–Y/Beta and Single-Atom Alloy Composite Catalysts Using In Situ-Generated Hydrogen Cordon, Michael J.; Zhang, Junyan; Purdy, Stephen C. ACS Catalysis, Vol. 11, Issue 12 https://doi.org/10.1021/acscatal.1c01136	journal	June 2021
Role of Rare Earth Ions in the Prevention of Dealumination of Zeolite Y for Fluid Cracking Catalysts Louwen, Jaap N.; Simko, Stanislav; Stanciakova, Katarina The Journal of Physical Chemistry C, Vol. 124, Issue 8 https://doi.org/10.1021/acs.jpcc.9b11956	journal	February 2020
Integrated Catalytic Conversion of γ-Valerolactone to Liquid Alkenes for Transportation Fuels Bond, J. Q.; Alonso, D. M.; Wang, D. Science, Vol. 327, Issue 5969, p. 1110-1114 https://doi.org/10.1126/science.1184362	journal	February 2010
Nature and Location of Cationic Lanthanum Species in High Alumina Containing Faujasite Type Zeolites Schüßler, Florian; Pidko, Evgeny A.; Kolvenbach, Robin The Journal of Physical Chemistry C, Vol. 115, Issue 44 https://doi.org/10.1021/jp205771e	journal	October 2011
Single-Step Conversion of Ethanol to n -Butene over Ag-ZrO ₂ /SiO ₂ Catalysts Dagle, Vanessa Lebarbier; Winkelman, Austin D.; Jaegers, Nicholas R. ACS Catalysis, Vol. 10, Issue 18 https://doi.org/10.1021/acscatal.0c02235	journal	July 2020
Concentration and acid strength of hydroxyl groups in zeolites La,Na-X and La,Na-Y with different lanthanum exchange degrees studied by solid-state NMR spectroscopy Huang, Jun; Jiang, Yijiao; Reddy Marthala, V. R. Microporous and Mesoporous Materials, Vol. 104, Issue 1-3 https://doi.org/10.1016/j.micromeso.2007.01.016	journal	August 2007
Conversion of ethanol to propylene over HZSM-5(Ga) co-modified with lanthanum and phosphorous Furumoto, Yoshiyasu; Tsunoji, Nao; Ide, Yusuke Applied Catalysis A: General, Vol. 417-418 https://doi.org/10.1016/j.apcata.2011.12.034	journal	February 2012
Oligomerization of ethanol-derived propene and isobutene mixtures to transportation fuels: catalyst and process considerations Saavedra Lopez, Johnny; Dagle, Robert A.; Dagle, Vanessa Lebarbier Catalysis Science & Technology, Vol. 9, Issue 5 https://doi.org/10.1039/C8CY02297F	journal	January 2019
Modified zeolites as catalysts in the Friedel-Crafts acylation Gaare, Kristin; Akporiaye, Duncan Journal of Molecular Catalysis A: Chemical, Vol. 109, Issue 2 https://doi.org/10.1016/1381-1169(96)00023-4	journal	June 1996
Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C ₃₊ Olefin Formation from Ethanol Zhang, Junyan; Wegener, Evan C.; Samad, Nohor River ACS Catalysis, Vol. 11, Issue 15 https://doi.org/10.1021/acscatal.1c02177	journal	July 2021
Chemistries and processes for the conversion of ethanol into middle-distillate fuels Eagan, Nathaniel M.; Kumbhalkar, Mrunmayi D.; Buchanan, J. Scott Nature Reviews Chemistry, Vol. 3, Issue 4 https://doi.org/10.1038/s41570-019-0084-4	journal	March 2019
Ag-Promoted ZrBEA Zeolites Obtained by Post-Synthetic Modification for Conversion of Ethanol to Butadiene Sushkevich, Vitaly L.; Ivanova, Irina I. ChemSusChem, Vol. 9, Issue 16 https://doi.org/10.1002/cssc.201600572	journal	July 2016
On the formation of the acid sites in lanthanum exchanged X zeolites used for isobutane/cis-2-butene alkylation Guzman, Alexander; Zuazo, Iker; Feller, Andreas Microporous and Mesoporous Materials, Vol. 83, Issue 1-3 https://doi.org/10.1016/j.micromeso.2005.04.024	journal	September 2005
Synthesis of renewable jet and diesel fuels from 2-ethyl-1-hexene Harvey, Benjamin G.; Quintana, Roxanne L. Energy & Environmental Science, Vol. 3, Issue 3 https://doi.org/10.1039/b924004g	journal	January 2010
A hybrid pathway to biojet fuel via 2,3-butanediol Adhikari, Shiba P.; Zhang, Junyan; Guo, Qianying Sustainable Energy & Fuels, Vol. 4, Issue 8 https://doi.org/10.1039/D0SE00480D	journal	January 2020
Stabilizing copper species using zeolite for ethanol catalytic dehydrogenation to acetaldehyde Yu, Dongni; Dai, Weili; Wu, Guangjun Chinese Journal of Catalysis, Vol. 40, Issue 9 https://doi.org/10.1016/S1872-2067(19)63378-4	journal	September 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ethanol
lanthanum
copper
beta zeolite
catalysis
olefins

Title: Ethanol Conversion to C4+ Olefins over Bimetallic Copper- And Lanthanum-Containing Beta Zeolite Catalysts

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Title: Ethanol Conversion to C₄₊ Olefins over Bimetallic Copper- And Lanthanum-Containing Beta Zeolite Catalysts