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Title: Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors

Abstract

The impact of catalyst acidity on the selectivity of upgraded biomass pyrolysis products was studied by passing pine pyrolysis vapors over five ZSM-5 catalysts of varying acidity at 500 degrees C. The SiO2-to-Al2O3 ratio (SAR) of the ZSM-5 zeolite was varied from 23 to 280 to control the acidity of the catalyst and the composition of upgraded products. The upgraded product stream was analyzed by GCMS. Additionally, catalysts were characterized using temperature programmed desorption, diffuse-reflectance FTIR spectroscopy, N2 physisorption, and X-ray diffraction. The results showed that the biomass pyrolysis vapors were highly deoxygenated to form a slate of aromatic hydrocarbons over all of the tested ZSM-5 catalysts. As the overall acidity of the ZSM-5 increased the selectivity toward alkylated (substituted) aromatics (e.g., xylene, dimethyl-naphthalene, and methyl-anthracene) decreased while the selectivity toward unsubstituted aromatics (e.g., benzene, naphthalene, and anthracene) increased. Additionally, the selectivity toward polycyclic aromatic compounds (2-ring and 3-ring) increased as catalyst acidity increased, corresponding to a decrease in acid site spacing. The increased selectivity toward less substituted polycyclic aromatic compounds with increasing acidity is related to the relative rates of cyclization and alkylation reactions within the zeolite structure. As the acid site concentration increases and sites become closer tomore » each other, the formation of additional cyclization products occurs at a greater rate than alkylated products. The ability to adjust product selectivity within 1-, 2-, and 3-ring aromatic families, as well as the degree of substitution, by varying ZSM-5 acidity could have significant benefits in terms creating a slate of upgraded biomass pyrolysis products to meet specific target market demands.« less

Authors:
 [1];  [2];  [2];  [2];  [2];  [2]
+ Show Author Affiliations
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office; USDOE Office of Science (SC)
OSTI Identifier:
1251593
Alternate Identifier(s):
OSTI ID: 1373341
Report Number(s):
NREL/JA-5900-65796
Journal ID: ISSN 0920-5861
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 269; Journal Issue: C; Journal ID: ISSN 0920-5861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biomass; pyrolysis; vapor phase upgrading; acidity; ZSM-5; zeolite

Citation Formats

Engtrakul, Chaiwat, Mukarakate, Calvin, Starace, Anne K., Magrini, Kimberly A., Rogers, Allyson K., and Yung, Matthew M. Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors. United States: N. p., 2015. Web. doi:10.1016/j.cattod.2015.10.032.
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Engtrakul, Chaiwat, Mukarakate, Calvin, Starace, Anne K., Magrini, Kimberly A., Rogers, Allyson K., & Yung, Matthew M. Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors. United States. https://doi.org/10.1016/j.cattod.2015.10.032
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Engtrakul, Chaiwat, Mukarakate, Calvin, Starace, Anne K., Magrini, Kimberly A., Rogers, Allyson K., and Yung, Matthew M. Sat . "Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors". United States. https://doi.org/10.1016/j.cattod.2015.10.032. https://www.osti.gov/servlets/purl/1251593.
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@article{osti_1251593,
title = {Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors},
author = {Engtrakul, Chaiwat and Mukarakate, Calvin and Starace, Anne K. and Magrini, Kimberly A. and Rogers, Allyson K. and Yung, Matthew M.},
abstractNote = {The impact of catalyst acidity on the selectivity of upgraded biomass pyrolysis products was studied by passing pine pyrolysis vapors over five ZSM-5 catalysts of varying acidity at 500 degrees C. The SiO2-to-Al2O3 ratio (SAR) of the ZSM-5 zeolite was varied from 23 to 280 to control the acidity of the catalyst and the composition of upgraded products. The upgraded product stream was analyzed by GCMS. Additionally, catalysts were characterized using temperature programmed desorption, diffuse-reflectance FTIR spectroscopy, N2 physisorption, and X-ray diffraction. The results showed that the biomass pyrolysis vapors were highly deoxygenated to form a slate of aromatic hydrocarbons over all of the tested ZSM-5 catalysts. As the overall acidity of the ZSM-5 increased the selectivity toward alkylated (substituted) aromatics (e.g., xylene, dimethyl-naphthalene, and methyl-anthracene) decreased while the selectivity toward unsubstituted aromatics (e.g., benzene, naphthalene, and anthracene) increased. Additionally, the selectivity toward polycyclic aromatic compounds (2-ring and 3-ring) increased as catalyst acidity increased, corresponding to a decrease in acid site spacing. The increased selectivity toward less substituted polycyclic aromatic compounds with increasing acidity is related to the relative rates of cyclization and alkylation reactions within the zeolite structure. As the acid site concentration increases and sites become closer to each other, the formation of additional cyclization products occurs at a greater rate than alkylated products. The ability to adjust product selectivity within 1-, 2-, and 3-ring aromatic families, as well as the degree of substitution, by varying ZSM-5 acidity could have significant benefits in terms creating a slate of upgraded biomass pyrolysis products to meet specific target market demands.},
doi = {10.1016/j.cattod.2015.10.032},
journal = {Catalysis Today},
number = C,
volume = 269,
place = {United States},
year = {Sat Nov 14 00:00:00 EST 2015},
month = {Sat Nov 14 00:00:00 EST 2015}
}
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    Works referencing / citing this record:

    Overview of catalytic upgrading of biomass pyrolysis vapors toward the production of fuels and high-value chemicals
    journal, August 2018

    • Iliopoulou, Eleni F.; Triantafyllidis, Kostas S.; Lappas, Angelos A.
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    Thermocatalytic Biomass Processing
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    Sugar ketals as a platform molecule to overcome the limitation of converting biomass into green-hydrocarbons in a typical refinery
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    • Sustainable Energy & Fuels, Vol. 4, Issue 3
    • DOI: 10.1039/c9se00379g
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