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Title: Catalytic fast pyrolysis with metal-modified ZSM-5 catalysts in inert and hydrogen atmospheres

Abstract

The objective of this work was to determine the impact of hydrogen-activating metals on catalytic fast pyrolysis over ZSM-5 with and without hydrogen addition. Ga-, Ni-, Cu-, Co-, and Pt-modified ZSM-5 catalysts with metal-to-aluminum molar ratios of 2 were prepared by incipient wetness method. The catalysts were evaluated for hydrocarbon and oxygenate yields and for deactivation by analytical pyrolysis (Py-GC-MS), and post-reaction catalysts for characterization were prepared in a larger fixed-bed reactor. In inert atmosphere, there was a linear correlation between both the hydrocarbon yield and coke formation and density of strong acid sites, and the main impact of the metals was occlusion of active sites in ZSM-5, leading to proportional reductions in hydrocarbon and coke yields. With the addition of hydrogen, several metals (Pt, Ni, Cu, Co) activated hydrogen and further reduced coke formation, leading to improvements in the ratio of hydrocarbons to coke. No metal-modified catalyst out-performed fresh unmodified ZSM-5 in terms of hydrocarbon yield; however, Ni/ZSM-5 and Cu/ZSM-5 in hydrogen produced comparable hydrocarbon yields to ZSM-5 while reducing coke formation.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [2]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado State Univ., Fort Collins, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1475116
Report Number(s):
NREL/JA-5100-72331
Journal ID: ISSN 0165-2370
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Analytical and Applied Pyrolysis
Additional Journal Information:
Journal Volume: 135; Journal Issue: C; Journal ID: ISSN 0165-2370
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; catalytic pyrolysis; ZSM-5; metal; hydrogen; deactivation; pine

Citation Formats

Iisa, Maarit K., Stanton, Alexander R., Yung, Matthew M., and Magrini, Kimberly A. Catalytic fast pyrolysis with metal-modified ZSM-5 catalysts in inert and hydrogen atmospheres. United States: N. p., 2018. Web. doi:10.1016/j.jaap.2018.09.002.
Iisa, Maarit K., Stanton, Alexander R., Yung, Matthew M., & Magrini, Kimberly A. Catalytic fast pyrolysis with metal-modified ZSM-5 catalysts in inert and hydrogen atmospheres. United States. doi:10.1016/j.jaap.2018.09.002.
Iisa, Maarit K., Stanton, Alexander R., Yung, Matthew M., and Magrini, Kimberly A. Wed . "Catalytic fast pyrolysis with metal-modified ZSM-5 catalysts in inert and hydrogen atmospheres". United States. doi:10.1016/j.jaap.2018.09.002. https://www.osti.gov/servlets/purl/1475116.
@article{osti_1475116,
title = {Catalytic fast pyrolysis with metal-modified ZSM-5 catalysts in inert and hydrogen atmospheres},
author = {Iisa, Maarit K. and Stanton, Alexander R. and Yung, Matthew M. and Magrini, Kimberly A.},
abstractNote = {The objective of this work was to determine the impact of hydrogen-activating metals on catalytic fast pyrolysis over ZSM-5 with and without hydrogen addition. Ga-, Ni-, Cu-, Co-, and Pt-modified ZSM-5 catalysts with metal-to-aluminum molar ratios of 2 were prepared by incipient wetness method. The catalysts were evaluated for hydrocarbon and oxygenate yields and for deactivation by analytical pyrolysis (Py-GC-MS), and post-reaction catalysts for characterization were prepared in a larger fixed-bed reactor. In inert atmosphere, there was a linear correlation between both the hydrocarbon yield and coke formation and density of strong acid sites, and the main impact of the metals was occlusion of active sites in ZSM-5, leading to proportional reductions in hydrocarbon and coke yields. With the addition of hydrogen, several metals (Pt, Ni, Cu, Co) activated hydrogen and further reduced coke formation, leading to improvements in the ratio of hydrocarbons to coke. No metal-modified catalyst out-performed fresh unmodified ZSM-5 in terms of hydrocarbon yield; however, Ni/ZSM-5 and Cu/ZSM-5 in hydrogen produced comparable hydrocarbon yields to ZSM-5 while reducing coke formation.},
doi = {10.1016/j.jaap.2018.09.002},
journal = {Journal of Analytical and Applied Pyrolysis},
number = C,
volume = 135,
place = {United States},
year = {2018},
month = {9}
}

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