Ex situ upgrading of pyrolysis vapors over PtTiO 2 : extraction of apparent kinetics via hierarchical transport modeling

Pecha, M. Brennan; Iisa, Kristiina; Griffin, Michael; Mukarakate, Calvin; French, Richard; Adkins, Bruce; Bharadwaj, Vivek S.; Crowley, Meagan; Foust, Thomas D.; Schaidle, Joshua A.; Ciesielski, Peter N.

doi:10.1039/D0RE00339E

Title: Ex situ upgrading of pyrolysis vapors over PtTiO ₂ : extraction of apparent kinetics via hierarchical transport modeling

Journal Article · Tue Jan 05 00:00:00 EST 2021 · Reaction Chemistry & Engineering

DOI:https://doi.org/10.1039/D0RE00339E· OSTI ID:1686196

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National Renewable Energy Laboratory, Golden, USA
Oak Ridge National Laboratory, Oak Ridge, USA

Chemical reaction kinetics enable predictive scaling studies and process sensitivity analyses that can substantially accelerate commercial deployment of new catalytic transformation technologies. The absence of suitable kinetic parameters for catalytic fast pyrolysis (CFP) of biomass feedstocks has precluded such de-risking simulation activities. In this work we consider ex situ CFP using a Pt/TiO₂ catalyst in a packed bed vapor phase upgrading reactor (VPU) with co-fed H₂. We develop a multiscale simulation framework to de-couple apparent kinetics from both intraparticle and reactor-scale transport phenomena. The transport model is integrated with a kinetic scheme that predicts (1) lumped yields of product partially deoxygenated compounds, hydrocarbons, light gases, water, and coke, as well as (2) active site concentration and deactivation of the catalyst. We employ recent advancements in mathematical treatments of cascading reaction systems in the context of an axial-dispersion packed bed reactor model to achieve a rapidly-solving simulation framework that is amenable to iterative regression for kinetic parameter extraction. Results demonstrate accurate predictions of CFP yields within 5% for a variety of conditions, including different reaction times, Pt loadings, and variations in feedstock attributes.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Oak Ridge National Laboratory (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 Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office

Grant/Contract Number:: AC36-08GO28308; AC05-00OR22725

OSTI ID:: 1686196

Alternate ID(s):: OSTI ID: 1710159; OSTI ID: 1775235

Report Number(s):: NREL/JA-2800-77482; RCEEBW

Journal Information:: Reaction Chemistry & Engineering, Journal Name: Reaction Chemistry & Engineering Vol. 6 Journal Issue: 1; ISSN 2058-9883

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Title: Ex situ upgrading of pyrolysis vapors over PtTiO ₂ : extraction of apparent kinetics via hierarchical transport modeling