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Title: Influence of crystal allomorph and crystallinity on the products and behavior of cellulose during fast pyrolysis

Abstract

Here, cellulose is the primary biopolymer responsible for maintaining the structural and mechanical integrity of cell walls and, during the fast pyrolysis of biomass, may be restricting cell wall expansion and inhibiting phase transitions that would otherwise facilitate efficient escape of pyrolysis products. Here, we test whether modifications in two physical properties of cellulose, its crystalline allomorph and degree of crystallinity, alter its performance during fast pyrolysis. We show that both crystal allomorph and relative crystallinity of cellulose impact the slate of primary products produced by fast pyrolysis. For both cellulose-I and cellulose-II, changes in crystallinity dramatically impact the fast pyrolysis product portfolio. In both cases, only the most highly crystalline samples produced vapors dominated by levoglucosan. Cellulose-III, on the other hand, produces largely the same slate of products regardless of its relative crystallinity and produced as much or more levoglucosan at all crystallinity levels compared to cellulose-I or II. In addition to changes in products, the different cellulose allomorphs affected the viscoelastic properties of cellulose during rapid heating. Real-time hot-stage pyrolysis was used to visualize the transition of the solid material through a molten phase and particle shrinkage. SEM analysis of the chars revealed additional differences in viscoelastic propertiesmore » and molten phase behavior impacted by cellulose crystallinity and allomorph. Regardless of relative crystallinity, the cellulose-III samples displayed the most obvious evidence of having transitioned through a molten phase.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1324229
Report Number(s):
NREL/JA-5100-66920
Journal ID: ISSN 2168-0485
Grant/Contract Number:  
AC36-08GO28308; SC000997
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 4; Journal Issue: 9; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; allomorph; biochar; biomass conversion; cellulose; crystallinity; pyrolysis

Citation Formats

Mukarakate, Calvin, Mittal, Ashutosh, Ciesielski, Peter N., Budhi, Sridhar, Thompson, Logan, Iisa, Kristiina, Nimlos, Mark R., and Donohoe, Bryon S.. Influence of crystal allomorph and crystallinity on the products and behavior of cellulose during fast pyrolysis. United States: N. p., 2016. Web. https://doi.org/10.1021/acssuschemeng.6b00812.
Mukarakate, Calvin, Mittal, Ashutosh, Ciesielski, Peter N., Budhi, Sridhar, Thompson, Logan, Iisa, Kristiina, Nimlos, Mark R., & Donohoe, Bryon S.. Influence of crystal allomorph and crystallinity on the products and behavior of cellulose during fast pyrolysis. United States. https://doi.org/10.1021/acssuschemeng.6b00812
Mukarakate, Calvin, Mittal, Ashutosh, Ciesielski, Peter N., Budhi, Sridhar, Thompson, Logan, Iisa, Kristiina, Nimlos, Mark R., and Donohoe, Bryon S.. Tue . "Influence of crystal allomorph and crystallinity on the products and behavior of cellulose during fast pyrolysis". United States. https://doi.org/10.1021/acssuschemeng.6b00812. https://www.osti.gov/servlets/purl/1324229.
@article{osti_1324229,
title = {Influence of crystal allomorph and crystallinity on the products and behavior of cellulose during fast pyrolysis},
author = {Mukarakate, Calvin and Mittal, Ashutosh and Ciesielski, Peter N. and Budhi, Sridhar and Thompson, Logan and Iisa, Kristiina and Nimlos, Mark R. and Donohoe, Bryon S.},
abstractNote = {Here, cellulose is the primary biopolymer responsible for maintaining the structural and mechanical integrity of cell walls and, during the fast pyrolysis of biomass, may be restricting cell wall expansion and inhibiting phase transitions that would otherwise facilitate efficient escape of pyrolysis products. Here, we test whether modifications in two physical properties of cellulose, its crystalline allomorph and degree of crystallinity, alter its performance during fast pyrolysis. We show that both crystal allomorph and relative crystallinity of cellulose impact the slate of primary products produced by fast pyrolysis. For both cellulose-I and cellulose-II, changes in crystallinity dramatically impact the fast pyrolysis product portfolio. In both cases, only the most highly crystalline samples produced vapors dominated by levoglucosan. Cellulose-III, on the other hand, produces largely the same slate of products regardless of its relative crystallinity and produced as much or more levoglucosan at all crystallinity levels compared to cellulose-I or II. In addition to changes in products, the different cellulose allomorphs affected the viscoelastic properties of cellulose during rapid heating. Real-time hot-stage pyrolysis was used to visualize the transition of the solid material through a molten phase and particle shrinkage. SEM analysis of the chars revealed additional differences in viscoelastic properties and molten phase behavior impacted by cellulose crystallinity and allomorph. Regardless of relative crystallinity, the cellulose-III samples displayed the most obvious evidence of having transitioned through a molten phase.},
doi = {10.1021/acssuschemeng.6b00812},
journal = {ACS Sustainable Chemistry & Engineering},
number = 9,
volume = 4,
place = {United States},
year = {2016},
month = {7}
}

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