title: Discerning the Location and Nature of Coke Deposition from Surface to Bulk of Spent Zeolite Catalysts.
abstract: The formation of carbonaceous deposits (coke) in zeolite pores during catalysis leads to temporary deactivation of catalyst, necessitating regeneration steps, affecting throughput, and resulting in partial permanent loss of catalytic efficiency. Yet, even to date, the coke molecule distribution is quite challenging to study with high spatial resolution from surface to bulk of the catalyst particles at a single particle level. To address this challenge we investigated the coke molecules in HZSM-5 catalyst after ethanol conversion treatment by a combination of C K-edge X-ray absorption spectroscopy (XAS),13C Cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR) spectroscopy, and atom probe tomography (APT). XAS and NMR highlighted the aromatic character of coke molecules. APT permitted the imaging of the spatial distribution of hydrocarbon molecules located within the pores of spent HZSM-5 catalyst from surface to bulk at a single particle level.27Al NMR results and APT results indicated association of coke molecules with Al enriched regions within the spent HZSM-5 catalyst particles. The experimental results were additionally validated by a level-set-based APT field evaporation model. These results provide a new approach to investigate catalytic deactivation due to hydrocarbon coking or poisoning of zeolites at an unprecedented spatial resolution.
authors.affiliation: Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory Richland, Washington 99354, USA.
authors.forename: Arun
authors.initials: A
authors.lastname: Devaraj
authors.affiliation: Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA 99354, USA.
authors.forename: Murugesan
authors.initials: M
authors.lastname: Vijayakumar
authors.affiliation: Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA 99354, USA.
authors.forename: Jie
authors.initials: J
authors.lastname: Bao
authors.affiliation: Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA 99354, USA.
authors.forename: Mond F
authors.initials: MF
authors.lastname: Guo
authors.affiliation: Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory Richland, Washington 99354, USA.
authors.forename: Miroslaw A
authors.initials: MA
authors.lastname: Derewinski
authors.affiliation: Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory Richland, Washington 99354, USA.
authors.forename: Zhijie
authors.initials: Z
authors.lastname: Xu
authors.affiliation: Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA 99354, USA.
authors.forename: Michel J
authors.initials: MJ
authors.lastname: Gray
authors.affiliation: Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory Richland, Washington 99354, USA.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Prodinger
authors.affiliation: Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA 99354, USA.
authors.forename: Karthikeyan K
authors.initials: KK
authors.lastname: Ramasamy