Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5
Abstract
Metal-impregnated (Ni or Ga) ZSM-5 catalysts were studied for biomass pyrolysis vapor upgrading to produce hydrocarbons using three reactors constituting a 100 000x change in the amount of catalyst used in experiments. Catalysts were screened for pyrolysis vapor phase upgrading activity in two small-scale reactors: (i) a Pyroprobe with a 10 mg catalyst in a fixed bed and (ii) a fixed-bed reactor with 500 mg of catalyst. The best performing catalysts were then validated with a larger scale fluidized-bed reactor (using ~1 kg of catalyst) that produced measurable quantities of bio-oil for analysis and evaluation of mass balances. Despite some inherent differences across the reactor systems (such as residence time, reactor type, analytical techniques, mode of catalyst and biomass feed) there was good agreement of reaction results for production of aromatic hydrocarbons, light gases, and coke deposition. Relative to ZSM-5, Ni or Ga addition to ZSM-5 increased production of fully deoxygenated aromatic hydrocarbons and light gases. In the fluidized bed reactor, Ga/ZSM-5 slightly enhanced carbon efficiency to condensed oil, which includes oxygenates in addition to aromatic hydrocarbons, and reduced oil oxygen content compared to ZSM-5. Ni/ZSM-5, while giving the highest yield of fully deoxygenated aromatic hydrocarbons, gave lower overall carbonmore »
- Authors:
-
- National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1333411
- Report Number(s):
- NREL/JA-5100-67397
Journal ID: ISSN 0887-0624
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy and Fuels
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 11; Journal ID: ISSN 0887-0624
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; biomass; catalysts; pyrolysis vapors; hydrocarbons
Citation Formats
Yung, Matthew M., Stanton, Alexander R., Iisa, Kristiina, French, Richard J., Orton, Kellene A., and Magrini, Kimberly A. Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5. United States: N. p., 2016.
Web. doi:10.1021/acs.energyfuels.6b01866.
Yung, Matthew M., Stanton, Alexander R., Iisa, Kristiina, French, Richard J., Orton, Kellene A., & Magrini, Kimberly A. Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5. United States. https://doi.org/10.1021/acs.energyfuels.6b01866
Yung, Matthew M., Stanton, Alexander R., Iisa, Kristiina, French, Richard J., Orton, Kellene A., and Magrini, Kimberly A. Fri .
"Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5". United States. https://doi.org/10.1021/acs.energyfuels.6b01866. https://www.osti.gov/servlets/purl/1333411.
@article{osti_1333411,
title = {Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5},
author = {Yung, Matthew M. and Stanton, Alexander R. and Iisa, Kristiina and French, Richard J. and Orton, Kellene A. and Magrini, Kimberly A.},
abstractNote = {Metal-impregnated (Ni or Ga) ZSM-5 catalysts were studied for biomass pyrolysis vapor upgrading to produce hydrocarbons using three reactors constituting a 100 000x change in the amount of catalyst used in experiments. Catalysts were screened for pyrolysis vapor phase upgrading activity in two small-scale reactors: (i) a Pyroprobe with a 10 mg catalyst in a fixed bed and (ii) a fixed-bed reactor with 500 mg of catalyst. The best performing catalysts were then validated with a larger scale fluidized-bed reactor (using ~1 kg of catalyst) that produced measurable quantities of bio-oil for analysis and evaluation of mass balances. Despite some inherent differences across the reactor systems (such as residence time, reactor type, analytical techniques, mode of catalyst and biomass feed) there was good agreement of reaction results for production of aromatic hydrocarbons, light gases, and coke deposition. Relative to ZSM-5, Ni or Ga addition to ZSM-5 increased production of fully deoxygenated aromatic hydrocarbons and light gases. In the fluidized bed reactor, Ga/ZSM-5 slightly enhanced carbon efficiency to condensed oil, which includes oxygenates in addition to aromatic hydrocarbons, and reduced oil oxygen content compared to ZSM-5. Ni/ZSM-5, while giving the highest yield of fully deoxygenated aromatic hydrocarbons, gave lower overall carbon efficiency to oil but with the lowest oxygen content. Reaction product analysis coupled with fresh and spent catalyst characterization indicated that the improved performance of Ni/ZSM-5 is related to decreasing deactivation by coking, which keeps the active acid sites accessible for the deoxygenation and aromatization reactions that produce fully deoxygenated aromatic hydrocarbons. The addition of Ga enhances the dehydrogenation activity of the catalyst, which leads to enhanced olefin formation and higher fully deoxygenated aromatic hydrocarbon yields compared to unmodified ZSM-5. Catalyst characterization by ammonia temperature programmed desorption, surface area measurements, and postreaction temperature-programmed oxidation (TPO) also showed that the metal-modified zeolites retained a greater percentage of their initial acidity and surface area, which was consistent between the reactor scales. These results demonstrate that the trends observed with smaller (milligram to gram) catalyst reactors are applicable to larger, more industrially relevant (kg) scales to help guide catalyst research toward application.},
doi = {10.1021/acs.energyfuels.6b01866},
journal = {Energy and Fuels},
number = 11,
volume = 30,
place = {United States},
year = {Fri Oct 07 00:00:00 EDT 2016},
month = {Fri Oct 07 00:00:00 EDT 2016}
}
Web of Science
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