Sodium tungstate-promoted CaMnO3 as an effective, phase-transition redox catalyst for redox oxidative cracking of cyclohexane

Hao, Fang; Gao, Yunfei; Neal, Luke; Dudek, Ryan B.; Li, Wenyuan; Chung, Chingchang; Guan, Bo; Liu, Pingle; Liu, Xingbo; Li, Fanxing

doi:10.1016/j.jcat.2020.03.022

Sodium tungstate-promoted CaMnO₃ as an effective, phase-transition redox catalyst for redox oxidative cracking of cyclohexane

Journal Article · Fri Apr 03 00:00:00 EDT 2020 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2020.03.022· OSTI ID:1803997

Hao, Fang ^[1]; Gao, Yunfei ^[2]; Neal, Luke ^[2]; Dudek, Ryan B. ^[2]; Li, Wenyuan ^[3]; Chung, Chingchang ^[2]; Guan, Bo ^[3]; Liu, Pingle ^[4]; Liu, Xingbo ^[3]; Li, Fanxing ^[2]

North Carolina State Univ., Raleigh, NC (United States); Xiangtan Univ. (China); OSTI
North Carolina State Univ., Raleigh, NC (United States)
West Virginia Univ., Morgantown, WV (United States)
Xiangtan Univ. (China)

Oxidative cracking, which combines catalytic oxidation and cracking reactions, represents a promising approach to reduce the energy and carbon intensities for light olefin production from naphtha. The need to co-feed gaseous oxygen with hydrocarbons, however, leads to significant CO_x formation and safety concerns. The cost and energy consumption associated with air separation also affects its economic attractiveness. In this study, we investigated a redox oxidative cracking (ROC) scheme and evaluated perovskites (La_0.8Sr_0.2FeO₃ and CaMnO₃) and Na₂WO₄-promoted perovskite (La_0.8Sr_0.2FeO₃@Na₂WO₄ and CaMnO₃@Na₂WO₄) as the redox catalysts for ROC. CaMnO₃@Na₂WO₄ redox catalyst shows high activity, selectivity, and stability for light olefin production from cyclohexane. Operated under a redox oxidative cracking (ROC) scheme, CaMnO₃@Na₂WO₄ enhances the catalytic cracking of cyclohexane, while showing high selectivity towards hydrogen combustion with its built-in, active lattice oxygen. Over three-fold increase in olefin yield compared to thermal cracking and 35% yield increase compared to conventional O₂-cofeed oxidative cracking were achieved. Low energy ion scattering (LEIS), X-ray photoelectric spectroscopy (XPS), and differential scanning calorimetry (DSC) indicated a core-shell structure, where a molten Na₂WO₄ layer covers the CaMnO₃ core. Na₂WO₄ modifies the oxygen donation behavior of CaMnO₃ and provides a catalytically active surface for cyclohexane activation. In-situ XRD revealed that CaMnO₃@Na₂WO₄ exhibited excellent structural stability and regenerability. The transformation of Mn⁴⁺ ↔ Mn³⁺ ↔ Mn²⁺ in CaMnO₃, facilitated by reversible phase transition to (Ca/Mn)O solid solution, is responsible for the lattice oxygen donation and uptake during redox cycles. Electrochemical impedance spectroscopy (EIS) measurements further confirmed that the oxygen species were transported through the molten Na₂WO₄ layer to participate in ROC. These findings offer mechanistic insights to design effective redox catalysts for hydrocarbon valorization using the chemical looping strategy.

View Accepted Manuscript (DOE)

Research Organization:: American Institute of Chemical Engineers (AIChE), New York, NY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0007888

OSTI ID:: 1803997

Alternate ID(s):: OSTI ID: 1608349

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 385; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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