Multiscale Catalytic Fast Pyrolysis of Grindelia Reveals Opportunities for Generating Low Oxygen Content Bio-Oils from Drought Tolerant Biomass
Abstract
Grindelia squarrosa (curlycup gumweed) biomass possesses unique biochemistry, cell wall composition, and leaf architecture tailored for prolific growth in arid and semiarid climates. Most notably, this plant has developed high levels of extractable resins that have high effective H/Ceff ratios ((mol H - 2 x mol O)/mol C), which is hypothesized to lead to low coke formation during catalytic fast pyrolysis (CFP) over the ZSM-5 catalyst. In microscale experiments with high ZSM-5 loadings (biomass-to-catalyst mass ratio (B/C) ~ 0.1), in situ CFP generated high yields of aromatic hydrocarbons (30% carbon yield) while ex situ CFP favored aliphatic hydrocarbons (25% carbon yield). The difference between the two configurations was attributed to the constant catalyst temperature during ex situ CFP. Deactivation leading to partially deoxygenated vapor products occurred rapidly until B/C ≤ 0.5 by the adsorption of organic species blocking access to acid sites inside the micropores of the catalyst. This was followed by more gradual deactivation leading to primary vapor breakthrough, which we attribute to coke formation on acid sites on the external surface of ZSM-5 crystallites. Noncatalytic fast pyrolysis of Grindelia in a bench scale reactor produced oils with oxygen content (18 wt % on dry basis) and carbon yieldmore »
- Authors:
-
[2];
[2];
[2];
[2];
[1];
[2]
- Auburn Univ., AL (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Univ. of Nevada, Reno, NV (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), Transportation Office. Bioenergy Technologies Office
- OSTI Identifier:
- 1827893
- Report Number(s):
- NREL/JA-5100-80515
Journal ID: ISSN 0887-0624; MainId:43717;UUID:28e9bd8d-ec7e-41a6-b049-6cad2a32bb59;MainAdminID:63206
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy and Fuels
- Additional Journal Information:
- Journal Volume: 36; Journal Issue: 1; Journal ID: ISSN 0887-0624
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- BIOMASS FUELS; biofuels; catalytic fast pyrolysis; chemicals; drought tolerant feedstocks; gumweed; ZSM-5
Citation Formats
Cross, Phillip, Iisa, Kristiina, To, Anh, Nimlos, Mark, Carpenter, Daniel, Mayer, Jesse A., Crushman, John C., Neupane, Bishnu, Miller, Glenn C., Adhikari, Sushil, and Mukarakate, Calvin. Multiscale Catalytic Fast Pyrolysis of Grindelia Reveals Opportunities for Generating Low Oxygen Content Bio-Oils from Drought Tolerant Biomass. United States: N. p., 2021.
Web. doi:10.1021/acs.energyfuels.1c02403.
Cross, Phillip, Iisa, Kristiina, To, Anh, Nimlos, Mark, Carpenter, Daniel, Mayer, Jesse A., Crushman, John C., Neupane, Bishnu, Miller, Glenn C., Adhikari, Sushil, & Mukarakate, Calvin. Multiscale Catalytic Fast Pyrolysis of Grindelia Reveals Opportunities for Generating Low Oxygen Content Bio-Oils from Drought Tolerant Biomass. United States. https://doi.org/10.1021/acs.energyfuels.1c02403
Cross, Phillip, Iisa, Kristiina, To, Anh, Nimlos, Mark, Carpenter, Daniel, Mayer, Jesse A., Crushman, John C., Neupane, Bishnu, Miller, Glenn C., Adhikari, Sushil, and Mukarakate, Calvin. Tue .
"Multiscale Catalytic Fast Pyrolysis of Grindelia Reveals Opportunities for Generating Low Oxygen Content Bio-Oils from Drought Tolerant Biomass". United States. https://doi.org/10.1021/acs.energyfuels.1c02403. https://www.osti.gov/servlets/purl/1827893.
@article{osti_1827893,
title = {Multiscale Catalytic Fast Pyrolysis of Grindelia Reveals Opportunities for Generating Low Oxygen Content Bio-Oils from Drought Tolerant Biomass},
author = {Cross, Phillip and Iisa, Kristiina and To, Anh and Nimlos, Mark and Carpenter, Daniel and Mayer, Jesse A. and Crushman, John C. and Neupane, Bishnu and Miller, Glenn C. and Adhikari, Sushil and Mukarakate, Calvin},
abstractNote = {Grindelia squarrosa (curlycup gumweed) biomass possesses unique biochemistry, cell wall composition, and leaf architecture tailored for prolific growth in arid and semiarid climates. Most notably, this plant has developed high levels of extractable resins that have high effective H/Ceff ratios ((mol H - 2 x mol O)/mol C), which is hypothesized to lead to low coke formation during catalytic fast pyrolysis (CFP) over the ZSM-5 catalyst. In microscale experiments with high ZSM-5 loadings (biomass-to-catalyst mass ratio (B/C) ~ 0.1), in situ CFP generated high yields of aromatic hydrocarbons (30% carbon yield) while ex situ CFP favored aliphatic hydrocarbons (25% carbon yield). The difference between the two configurations was attributed to the constant catalyst temperature during ex situ CFP. Deactivation leading to partially deoxygenated vapor products occurred rapidly until B/C ≤ 0.5 by the adsorption of organic species blocking access to acid sites inside the micropores of the catalyst. This was followed by more gradual deactivation leading to primary vapor breakthrough, which we attribute to coke formation on acid sites on the external surface of ZSM-5 crystallites. Noncatalytic fast pyrolysis of Grindelia in a bench scale reactor produced oils with oxygen content (18 wt % on dry basis) and carbon yield (33%) comparable to those of CFP of woody biomass. The CFP of Grindelia further reduced the oxygen content to 7 wt % for in situ CFP and 4 wt % for ex situ CFP at B/C of 2-3. The good deoxygenation was attributed to a combination of a high H/Ceff ratio and overall better quality of the pyrolysis vapors that were passed over the ZSM-5 catalyst. The high inorganic content of the Grindelia likely catalyzed pyrolysis to remove oxygenated coke precursors. This integrated CFP study demonstrated that Grindelia could be an important feedstock for generating stabilized noncatalytic and CFP oils for downstream processing into fuels and/or extraction of high-value chemicals. The preprocessing of this feedstock will be required to remove inorganics, which cause an irreversible deactivation of ZSM-5.},
doi = {10.1021/acs.energyfuels.1c02403},
journal = {Energy and Fuels},
number = 1,
volume = 36,
place = {United States},
year = {Tue Oct 19 00:00:00 EDT 2021},
month = {Tue Oct 19 00:00:00 EDT 2021}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Increasing drought under global warming in observations and models
journal, August 2012
- Dai, Aiguo
- Nature Climate Change, Vol. 3, Issue 1
Fast Pyrolysis of Opuntia ficus-indica (Prickly Pear) and Grindelia squarrosa (Gumweed)
journal, February 2018
- Cross, Phillip; Mukarakate, Calvin; Nimlos, Mark
- Energy & Fuels, Vol. 32, Issue 3
Development and use of bioenergy feedstocks for semi-arid and arid lands
journal, April 2015
- Cushman, John C.; Davis, Sarah C.; Yang, Xiaohan
- Journal of Experimental Botany, Vol. 66, Issue 14
A roadmap for research on crassulacean acid metabolism (CAM) to enhance sustainable food and bioenergy production in a hotter, drier world
journal, July 2015
- Yang, Xiaohan; Cushman, John C.; Borland, Anne M.
- New Phytologist, Vol. 207, Issue 3
Review of fast pyrolysis of biomass and product upgrading
journal, March 2012
- Bridgwater, A. V.
- Biomass and Bioenergy, Vol. 38, p. 68-94
Pyrolysis of Wood/Biomass for Bio-oil: A Critical Review
journal, May 2006
- Mohan, Dinesh; Pittman,, Charles U.; Steele, Philip H.
- Energy & Fuels, Vol. 20, Issue 3, p. 848-889
Comparison of in-situ and ex-situ catalytic pyrolysis in a micro-reactor system
journal, December 2014
- Wang, Kaige; Johnston, Patrick A.; Brown, Robert C.
- Bioresource Technology, Vol. 173
Investigation of in situ and ex situ catalytic pyrolysis of miscanthus × giganteus using a PyGC–MS microsystem and comparison with a bench-scale spouted-bed reactor
journal, September 2015
- Gamliel, David P.; Du, Shoucheng; Bollas, George M.
- Bioresource Technology, Vol. 191
Survey of biocrude-producing plants from the southwest
journal, July 1982
- McLaughlin, Steven P.; Hoffmann, Joseph J.
- Economic Botany, Vol. 36, Issue 3
Biocrude production in arid lands
journal, April 1983
- McLaughlin, Steven P.; Kingsolver, Barbara E.; Hoffmann, Joseph J.
- Economic Botany, Vol. 37, Issue 2
Grindelia squarrosa: A Potential Arid Lands Biofuel Plant
journal, November 2016
- Neupane, Bishnu P.; Shintani, David; Lin, Hongfei
- ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 1
Grindelia camporum: Potential cash crop for the arid southwest
journal, April 1986
- Hoffmann, Joseph J.; Mclaughlin, Steven P.
- Economic Botany, Vol. 40, Issue 2
Catalytic conversion of biomass-derived feedstocks into olefins and aromatics with ZSM-5: the hydrogen to carbon effective ratio
journal, January 2011
- Zhang, Huiyan; Cheng, Yu-Ting; Vispute, Tushar P.
- Energy & Environmental Science, Vol. 4, Issue 6, p. 2297-2307
Real-time monitoring of the deactivation of HZSM-5 during upgrading of pine pyrolysis vapors
journal, January 2014
- Mukarakate, Calvin; Zhang, Xiaodong; Stanton, Alexander R.
- Green Chem., Vol. 16, Issue 3
Catalytic Hydroprocessing of Fast Pyrolysis Bio-oil from Pine Sawdust
journal, May 2012
- Elliott, Douglas C.; Hart, Todd R.; Neuenschwander, Gary G.
- Energy & Fuels, Vol. 26, Issue 6
Integration of catalytic fast pyrolysis and hydroprocessing: a pathway to refinery intermediates and “drop-in” fuels from biomass
journal, January 2016
- Mante, Ofei D.; Dayton, David C.; Gabrielsen, Jostein
- Green Chemistry, Vol. 18, Issue 22
Tuning the selectivity of methanol-to-hydrocarbons conversion on H-ZSM-5 by co-processing olefin or aromatic compounds
journal, June 2012
- Ilias, Samia; Bhan, Aditya
- Journal of Catalysis, Vol. 290
Influence of Crystal Allomorph and Crystallinity on the Products and Behavior of Cellulose during Fast Pyrolysis
journal, July 2016
- Mukarakate, Calvin; Mittal, Ashutosh; Ciesielski, Peter N.
- ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 9
Heat and Mass Transfer Effects in a Furnace-Based Micropyrolyzer
journal, August 2016
- Proano-Aviles, Juan; Lindstrom, Jake K.; Johnston, Patrick A.
- Energy Technology, Vol. 5, Issue 1
Catalytic Pyrolysis of Pine Over HZSM-5 with Different Binders
journal, October 2015
- Iisa, Kristiina; French, Richard J.; Orton, Kellene A.
- Topics in Catalysis, Vol. 59, Issue 1
Deactivation of Multilayered MFI Nanosheet Zeolite during Upgrading of Biomass Pyrolysis Vapors
journal, May 2017
- Xu, Mengze; Mukarakate, Calvin; Iisa, Kristiina
- ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 6
Chemical composition of seed essential oils from AlgerianNigella sativa extracted by microwave and hydrodistillation
journal, January 2007
- Benkaci–Ali, Farid; Baaliouamer, Aoumeur; Meklati, Brahim Y.
- Flavour and Fragrance Journal, Vol. 22, Issue 2
Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass
journal, January 2016
- Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar
- Green Chemistry, Vol. 18, Issue 20
Catalytic fast pyrolysis of biomass: the reactions of water and aromatic intermediates produces phenols
journal, January 2015
- Mukarakate, Calvin; McBrayer, Josefine D.; Evans, Tabitha J.
- Green Chemistry, Vol. 17, Issue 8
Upgrading biomass pyrolysis vapors over β-zeolites: role of silica-to-alumina ratio
journal, January 2014
- Mukarakate, Calvin; Watson, Michael J.; ten Dam, Jeroen
- Green Chem., Vol. 16, Issue 12
In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System
journal, December 2015
- Iisa, Kristiina; French, Richard J.; Orton, Kellene A.
- Energy & Fuels, Vol. 30, Issue 3
Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration
journal, January 2018
- Griffin, Michael B.; Iisa, Kristiina; Wang, Huamin
- Energy & Environmental Science, Vol. 11, Issue 10
Mechanistic Insights from Isotopic Studies of Glucose Conversion to Aromatics Over ZSM-5
journal, August 2009
- Carlson, Torren R.; Jae, Jungho; Huber, George W.
- ChemCatChem, Vol. 1, Issue 1
Role of Biopolymers in the Deactivation of ZSM-5 during Catalytic Fast Pyrolysis of Biomass
journal, June 2018
- Stanton, Alexander R.; Iisa, Kristiina; Mukarakate, Calvin
- ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 8
A review on ex situ catalytic fast pyrolysis of biomass
journal, August 2014
- Wan, Shaolong; Wang, Yong
- Frontiers of Chemical Science and Engineering, Vol. 8, Issue 3
Detailed Oil Compositional Analysis Enables Evaluation of Impact of Temperature and Biomass-to-Catalyst Ratio on ex Situ Catalytic Fast Pyrolysis of Pine Vapors over ZSM-5
journal, January 2020
- Patel, Himanshu; Hao, Naijia; Iisa, Kristiina
- ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 4
Evaluating the effect of potassium on cellulose pyrolysis reaction kinetics
journal, March 2015
- Trendewicz, Anna; Evans, Robert; Dutta, Abhijit
- Biomass and Bioenergy, Vol. 74
Production of low-oxygen bio-oil via ex situ catalytic fast pyrolysis and hydrotreating
journal, November 2017
- Iisa, Kristiina; French, Richard J.; Orton, Kellene A.
- Fuel, Vol. 207
Influence of inorganic salts on the primary pyrolysis products of cellulose
journal, June 2010
- Patwardhan, Pushkaraj R.; Satrio, Justinus A.; Brown, Robert C.
- Bioresource Technology, Vol. 101, Issue 12
Understanding the Fast Pyrolysis of Lignin
journal, September 2011
- Patwardhan, Pushkaraj R.; Brown, Robert C.; Shanks, Brent H.
- ChemSusChem, Vol. 4, Issue 11