Selective Butene Formation in Direct Ethanol-to-C3+-Olefin Valorization over Zn–Y/Beta and Single-Atom Alloy Composite Catalysts Using In Situ-Generated HydrogenClick to copy article linkArticle link copied!
- Michael J. CordonMichael J. CordonManufacturing Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United StatesMore by Michael J. Cordon
- Junyan ZhangJunyan ZhangManufacturing Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United StatesDepartment of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742, United StatesMore by Junyan Zhang
- Stephen C. PurdyStephen C. PurdyDepartment of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, United StatesNeutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United StatesMore by Stephen C. Purdy
- Evan C. WegenerEvan C. WegenerChemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United StatesMore by Evan C. Wegener
- Kinga A. UnocicKinga A. UnocicCenter for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United StatesMore by Kinga A. Unocic
- Lawrence F. AllardLawrence F. AllardMaterial Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United StatesMore by Lawrence F. Allard
- Mingxia ZhouMingxia ZhouMaterials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United StatesMore by Mingxia Zhou
- Rajeev S. AssaryRajeev S. AssaryMaterials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United StatesMore by Rajeev S. Assary
- Jeffrey T. MillerJeffrey T. MillerDepartment of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, United StatesMore by Jeffrey T. Miller
- Theodore R. KrauseTheodore R. KrauseChemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United StatesMore by Theodore R. Krause
- Fan LinFan LinInstitute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United StatesMore by Fan Lin
- Huamin WangHuamin WangInstitute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United StatesMore by Huamin Wang
- A. Jeremy KropfA. Jeremy KropfChemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United StatesMore by A. Jeremy Kropf
- Ce YangCe YangChemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United StatesMore by Ce Yang
- Dongxia LiuDongxia LiuDepartment of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742, United StatesMore by Dongxia Liu
- Zhenglong Li*Zhenglong Li*Email: [email protected]Manufacturing Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United StatesMore by Zhenglong Li
Abstract

The selective production of C3+ olefins from renewable feedstocks, especially via C1 and C2 platform chemicals, is a critical challenge for obtaining economically viable low-carbon middle-distillate transportation fuels (i.e., jet and diesel). Here, we report a multifunctional catalyst system composed of Zn–Y/Beta and “single-atom” alloy (SAA) Pt–Cu/Al2O3, which selectively catalyzes ethanol-to-olefin (C3+, ETO) valorization in the absence of cofed hydrogen, forming butenes as the primary olefin products. Beta zeolites containing predominately isolated Zn and Y metal sites catalyze ethanol upgrading steps (588 K, 3.1 kPa ethanol, ambient pressure) regardless of cofed hydrogen partial pressure (0–98.3 kPa H2), forming butadiene as the primary product (60% selectivity at an 87% conversion). The Zn–Y/Beta catalyst possesses site-isolated Zn and Y Lewis acid sites (at ∼7 wt % Y) and Brønsted acidic Y sites, the latter of which have been previously uncharacterized. A secondary bed of SAA Pt–Cu/Al2O3 selectively hydrogenates butadiene to butene isomers at a consistent reaction temperature using hydrogen generated in situ from ethanol to butadiene (ETB) conversion. This unique hydrogenation reactivity at near-stoichiometric hydrogen and butadiene partial pressures is not observed over monometallic Pt or Cu catalysts, highlighting these operating conditions as a critical SAA catalyst application area for conjugated diene selective hydrogenation at high reaction temperatures (>573 K) and low H2/diene ratios (e.g., 1:1). Single-bed steady-state selective hydrogenation rates, associated apparent hydrogen and butadiene reaction orders, and density functional theory (DFT) calculations of the Horiuti–Polanyi reaction mechanisms indicate that the unique butadiene selective hydrogenation reactivity over SAA Pt–Cu/Al2O3 reflects lower hydrogen scission barriers relative to monometallic Cu surfaces and limited butene binding energies relative to monometallic Pt surfaces. DFT calculations further indicate the preferential desorption of butene isomers over SAA Pt–Cu(111) and Cu(111) surfaces, while Pt(111) surfaces favor subsequent butene hydrogenation reactions to form butane over butene desorption events. Under operating conditions without hydrogen cofeeding, this combination of Zn–Y/Beta and SAA Pt–Cu catalysts can selectively form butenes (65% butenes, 78% C3+ selectivity at 94% conversion) and avoid butane formation using only in situ-generated hydrogen, avoiding costly hydrogen cofeeding requirements that hinder many renewable energy processes.
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