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Title: Insights into the effect of dilute acid, hot water or alkaline pretreatment on cellulose accessible surface area and the overall porosity of Populus

Abstract

Pretreatment is known to render biomass more reactive to cellulase by altering the chemical compositions as well as physical structures of biomass. Simons stain technique along with mercury porosimetry were applied on the acid, neutral, and alkaline pretreated materials to measure the accessible surface area of cellulose and pore size distribution of Populus. Results indicated that acid pretreatment is much more effective than water and alkaline pretreatment in terms of cellulose accessibility increase. Further investigation suggests that lignin does not dictate cellulose accessibility to the extent that hemicellulose does, but it does restrict xylan accessibility which in turn controls the access of cellulase to cellulose. The most interesting finding is that severe acid pretreatment significantly decreases the average pore size, i.e., 90% average size decrease could be observed after 60 min dilute acid pretreatment at 160 °C; moreover, the nano-pore space formed between coated microfibrils is increased after pretreatment, especially for the acid pretreatment, suggesting this particular type of biomass porosity is probably the most fundamental barrier to effective enzymatic hydrolysis.

Authors:
 [1];  [2];  [2];  [2];  [3]
  1. Georgia Inst. of Technology, Atlanta, GA (United States). Bioenergy Science Center
  2. Georgia Inst. of Technology, Atlanta, GA (United States). Renewable Bioproducts Institute
  3. Univ. of Tennessee, Knoxville, TN (United States). Bioenergy Science Center, Dept. of Chemical and Biomolecular Engineering, and Dept. of Forestry, Wildlife, and Fisheries
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1237144
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 17; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; populus; pretreatment; accessibility

Citation Formats

Meng, Xianzhi, Wells, Tyrone, Sun, Qining, Huang, Fang, and Ragauskas, Arthur J. Insights into the effect of dilute acid, hot water or alkaline pretreatment on cellulose accessible surface area and the overall porosity of Populus. United States: N. p., 2015. Web. doi:10.1039/C5GC00689A.
Meng, Xianzhi, Wells, Tyrone, Sun, Qining, Huang, Fang, & Ragauskas, Arthur J. Insights into the effect of dilute acid, hot water or alkaline pretreatment on cellulose accessible surface area and the overall porosity of Populus. United States. doi:10.1039/C5GC00689A.
Meng, Xianzhi, Wells, Tyrone, Sun, Qining, Huang, Fang, and Ragauskas, Arthur J. Fri . "Insights into the effect of dilute acid, hot water or alkaline pretreatment on cellulose accessible surface area and the overall porosity of Populus". United States. doi:10.1039/C5GC00689A. https://www.osti.gov/servlets/purl/1237144.
@article{osti_1237144,
title = {Insights into the effect of dilute acid, hot water or alkaline pretreatment on cellulose accessible surface area and the overall porosity of Populus},
author = {Meng, Xianzhi and Wells, Tyrone and Sun, Qining and Huang, Fang and Ragauskas, Arthur J.},
abstractNote = {Pretreatment is known to render biomass more reactive to cellulase by altering the chemical compositions as well as physical structures of biomass. Simons stain technique along with mercury porosimetry were applied on the acid, neutral, and alkaline pretreated materials to measure the accessible surface area of cellulose and pore size distribution of Populus. Results indicated that acid pretreatment is much more effective than water and alkaline pretreatment in terms of cellulose accessibility increase. Further investigation suggests that lignin does not dictate cellulose accessibility to the extent that hemicellulose does, but it does restrict xylan accessibility which in turn controls the access of cellulase to cellulose. The most interesting finding is that severe acid pretreatment significantly decreases the average pore size, i.e., 90% average size decrease could be observed after 60 min dilute acid pretreatment at 160 °C; moreover, the nano-pore space formed between coated microfibrils is increased after pretreatment, especially for the acid pretreatment, suggesting this particular type of biomass porosity is probably the most fundamental barrier to effective enzymatic hydrolysis.},
doi = {10.1039/C5GC00689A},
journal = {Green Chemistry},
number = ,
volume = 17,
place = {United States},
year = {Fri Jun 19 00:00:00 EDT 2015},
month = {Fri Jun 19 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 26works
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  • Consolidated bioprocessing (CBP) by anaerobes, such as Clostridium thermocellum, which combine enzyme production, hydrolysis, and fermentation are promising alternatives to historical economic challenges of using fungal enzymes for biological conversion of lignocellulosic biomass. However, limited research has integrated CBP with real pretreated biomass, and understanding how pretreatment impacts subsequent deconstruction by CBP vs. fungal enzymes can provide valuable insights into CBP and suggest other novel biomass deconstruction strategies. This study focused on determining the effect of pretreatment by dilute sulfuric acid alone (DA) and with tetrahydrofuran (THF) addition via co-solvent-enhanced lignocellulosic fractionation (CELF) on deconstruction of corn stover and Populusmore » with much different recalcitrance by C. thermocellum vs. fungal enzymes and changes in pretreated biomass related to these differences.« less
  • Obtaining a better understanding of the complex mechanisms occurring during lignocellulosic deconstruction is critical to the continued growth of renewable biofuel production. A key step in bioethanol production is thermochemical pretreatment to reduce plant cell wall recalcitrance for downstream processes. Previous studies of dilute acid pretreatment (DAP) have shown significant changes in cellulose ultrastructure that occur during pretreatment, but there is still a substantial knowledge gap with respect to the influence of lignin on these cellulose ultrastructural changes. This study was designed to assess how the presence of lignin influences DAP-induced changes in cellulose ultrastructure, which might ultimately have largemore » implications with respect to enzymatic deconstruction efforts. Native, untreated hybrid poplar (Populus trichocarpa x Populus deltoids) samples and a partially delignified poplar sample (facilitated by acidic sodium chlorite pulping) were separately pretreated with dilute sulfuric acid (0.10 M) at 160°C for 15 minutes and 35 minutes, respectively . Following extensive characterization, the partially delignified biomass displayed more significant changes in cellulose ultrastructure following DAP than the native untreated biomass. With respect to the native untreated poplar, delignified poplar after DAP (in which approximately 40% lignin removal occurred) experienced: increased cellulose accessibility indicated by increased Simons’ stain (orange dye) adsorption from 21.8 to 72.5 mg/g, decreased cellulose weight-average degree of polymerization (DP w) from 3087 to 294 units, and increased cellulose crystallite size from 2.9 to 4.2 nm. These changes following DAP ultimately increased enzymatic sugar yield from 10 to 80%. We conclude that, overall, the results indicate a strong influence of lignin content on cellulose ultrastructural changes occurring during DAP. With the reduction of lignin content during DAP, the enlargement of cellulose microfibril dimensions and crystallite size becomes more apparent. Further, this enlargement of cellulose microfibril dimensions is attributed to specific processes, including the co-crystallization of crystalline cellulose driven by irreversible inter-chain hydrogen bonding (similar to hornification) and/or cellulose annealing that converts amorphous cellulose to paracrystalline and crystalline cellulose. Essentially, lignin acts as a barrier to prevent cellulose crystallinity increase and cellulose fibril coalescence during DAP.« less