Pyrolysis mechanism study of minimally damaged hemicellulose polymers isolated from agricultural waste straw samples.

The pyrolysis mechanism of hemicellulose has been investigated using two minimally damaged hemicellulose polymers isolated from two agricultural straw samples. The obtained hemicelluloses have been characterized by multiple methods, and the results showed that they were mainly composed of l-arabino-4-O-methyl-d-glucurono-d-xylan. Their O-acetyl groups and high degrees of polymerization and branching were well preserved. Their pyrolyses were subsequently investigated by TG-FTIR and Py-GC/MS. The evolutions of four typical volatile components and the distributions of eight product species were scrutinized. A DG-DAEM kinetic model was applied to quantify the contributions of two major pyrolytic routes for devolatilization during hemicellulose pyrolysis. A mean activation energy of 150kJ/mol for the formation of volatiles was derived. The thermal stability of each bond in four typical fragments of hemicellulose was assessed by DFT study, and the deduced decomposition pathways were in agreement with experimental analysis.

[1]  J. Bilbao,et al.  Transformation of Oxygenate Components of Biomass Pyrolysis Oil on a HZSM-5 Zeolite. II. Aldehydes, Ketones, and Acids , 2004 .

[2]  N. Blumenkrantz,et al.  New method for quantitative determination of uronic acids. , 1973, Analytical biochemistry.

[3]  P. E. Sánchez-Jiménez,et al.  Comparison of thermal behavior of natural and hot-washed sisal fibers based on their main components: Cellulose, xylan and lignin. TG-FTIR analysis of volatile products , 2014 .

[4]  Jenny M. Jones,et al.  Phosphorus catalysis in the pyrolysis behaviour of biomass , 2008 .

[5]  D. Resasco,et al.  Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion , 2013 .

[6]  D. T. Liang,et al.  In-Depth Investigation of Biomass Pyrolysis Based on Three Major Components: Hemicellulose, Cellulose and Lignin , 2006 .

[7]  Jun Li,et al.  Formation mechanism of levoglucosan and formaldehyde during cellulose pyrolysis , 2011 .

[8]  J. Bellan,et al.  A Generalized Biomass Pyrolysis Model Based on Superimposed Cellulose, Hemicelluloseand Liqnin Kinetics , 1997 .

[9]  Sai Gu,et al.  Study on the pyrolytic behaviour of xylan-based hemicellulose using TG–FTIR and Py–GC–FTIR , 2010 .

[10]  K. Pandey.  A study of chemical structure of soft and hardwood and wood polymers by FTIR spectroscopy , 1999 .

[11]  Zhong-yang Luo,et al.  Comparison of the pyrolysis behavior of pyrolytic lignin and milled wood lignin by using TG–FTIR analysis , 2014 .

[12]  B. Shanks,et al.  Product distribution from the fast pyrolysis of hemicellulose. , 2011, ChemSusChem.

[13]  K. Pihlaja,et al.  Characterisation of lake-aquatic humic matter isolated with two different sorbing solid techniques: tetramethylammonium hydroxide treatment and pyrolysis-gas chromatography/mass spectrometry , 2000 .

[14]  I. Pitkänen,et al.  Formation of the main degradation compounds from arabinose, xylose, mannose and arabinitol during pyrolysis , 2003 .

[15]  Bin Ru,et al.  Degradation mechanism of monosaccharides and xylan under pyrolytic conditions with theoretic modeling on the energy profiles. , 2013, Bioresource technology.

[16]  R. Sun,et al.  Isolation and characterization of hemicelluloses extracted by hydrothermal pretreatment. , 2012, Bioresource technology.

[17]  D. Mohan,et al.  Pyrolysis of Wood/Biomass for Bio-oil: A Critical Review , 2006 .

[18]  T. Carlson,et al.  Green gasoline by catalytic fast pyrolysis of solid biomass derived compounds. , 2008, ChemSusChem.

[19]  R. Sun,et al.  Fractional and structural characterization of wheat straw hemicelluloses , 1996 .

[20]  B. Saake,et al.  Specificity of an Aspergillus Niger Esterase Deacetylating Cellulose Acetate , 2003 .

[21]  Van Soest.  Use of Detergents in the Analysis of Fibrous Feeds. II. A Rapid Method for the Determination of Fiber and Lignin , 1963 .

[22]  C. Geantet,et al.  Impact of Oxygenated Compounds from Lignocellulosic Biomass Pyrolysis Oils on Gas Oil Hydrotreatment , 2009 .

[23]  Minhua Zhang,et al.  Density Functional Theory (DFT) Study on the Dehydration of Cellulose , 2011 .

[24]  István Mayer,et al.  Charge, bond order and valence in the AB initio SCF theory , 1983 .

[25]  Zhong-yang Luo,et al.  Pyrolysis mechanism of hemicellulose monosaccharides in different catalytic processes , 2014, Chemical Research in Chinese Universities.

[26]  A. Broido,et al.  Char yield on pyrolysis of cellulose , 1975 .

[27]  Bin Ru,et al.  Pyrolysis behaviors of four lignin polymers isolated from the same pine wood. , 2015, Bioresource technology.

[28]  S. Kong,et al.  Assessment of devolatilization schemes in predicting product yields of biomass fast pyrolysis , 2014 .

[29]  G. Huber,et al.  A distributed activation energy model for the pyrolysis of lignocellulosic biomass , 2013 .

[30]  Q. Beg,et al.  Microbial xylanases and their industrial applications: a review , 2001, Applied Microbiology and Biotechnology.

[31]  Shubin Wu,et al.  Analytical pyrolysis studies of corn stalk and its three main components by TG-MS and Py-GC/MS , 2012 .

[32]  William E. Michener,et al.  Efficient extraction of xylan from delignified corn stover using dimethyl sulfoxide , 2013, 3 Biotech.

[33]  Chao Liu,et al.  Theoretical studies on pyrolysis mechanism of xylopyranose , 2012 .

[34]  Wei-min Li,et al.  Molecular dynamic simulation study on pyrolytic behaviour of xylan , 2013 .

[35]  R. Sun,et al.  Fractional purification and bioconversion of hemicelluloses. , 2012, Biotechnology advances.