Miscanthus x giganteus; Ammonia pretreatment; Formic/acetic acid pretreatment; Lignin chemical structure; Lignin characterisation; Repolymerisation
Abstract :
[en] Miscanthus x giganteus was treated with formic acid/acetic acid/water (30/50/20 v/v) for 3 h at 107 C and 80° C, and soaking in aqueous ammonia (25% w/w) for 6 h at 60 C. The effects of these fractionation processes on chemical structure, physico-chemical properties and antioxidant activity of extracted lignins were investigated. Lignins were characterized by their purity, carbohydrate composition, thermal stability, molecular weight and by Fourier transform infrared (FTIR), 1H and quantitative 13C nuclear magnetic resonance (NMR), adiabatic broadband {13C-1H} 2D heteronuclear (multiplicity edited) single quantum coherence (g-HSQCAD). The radical scavenging activity towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) was also investigated. Formic/acetic acid pretreatment performed in milder conditions (80° C for
3 h) gave a delignification percentage of 44.7% and soaking in aqueous ammonia 36.3%.
Formic/acetic acid pretreatment performed in harsh conditions (107°C for 3 h) was more effective for extensive delignification (86.5%) and delivered the most pure lignin (80%). The three lignin fractions contained carbohydrate in different extent: 3% for the lignin obtained after the formic/acetic acid pretreatment performed at 107 C (FAL-107), 5.8% for the formic/acetic acid performed at 80°C (FAL-80) and 13.7% for the ammonia lignin (AL). The acid pretreatment in harsh conditions (FAL-107) resulted in cleavage of b-O-4' bonds and aromatic C-C. Repolymerisation was thought to originate from formation of new aromatic C-O linkages. Under milder conditions (FAL-80) less b-O-4' linkages were broken and repolymerisation took place to a lesser extent. Ammonia lignin was not degraded to a significant extent and resulted in the highest weight average 3140 g mol -1. Despite the fact of FAL-107 repolymerisation,
significant phenolic hydroxyls remained free, explaining the greater antioxidant activity.
Disciplines :
Life sciences: Multidisciplinary, general & others
Author, co-author :
Vanderghem, Caroline ; Université de Liège - ULiège > Chimie et bio-industries > Chimie biologique industrielle
Richel, Aurore ; Université de Liège - ULiège > Chimie et bio-industries > Chimie biologique industrielle
Jacquet, Nicolas ; Université de Liège - ULiège > Chimie et bio-industries > Chimie biologique industrielle
Blecker, Christophe ; Université de Liège - ULiège > Chimie et bio-industries > Technologie des industries agro-alimentaires
Paquot, Michel ; Université de Liège - ULiège > Chimie et bio-industries > Chimie biologique industrielle
Language :
English
Title :
Impact of formic/acetic acid and ammonia pre-treatments on chemical structure and physico-chemical properties of Miscanthus x giganteus lignins
Publication date :
2011
Journal title :
Polymer Degradation and Stability
ISSN :
0141-3910
eISSN :
1873-2321
Publisher :
Elsevier Science, Oxford, United Kingdom
Volume :
96
Issue :
10
Pages :
1761-1770
Peer reviewed :
Peer Reviewed verified by ORBi
Name of the research project :
TECHNOSE project number 716757
Funders :
DGTRE - Région wallonne. Direction générale des Technologies, de la Recherche et de l'Énergie
D.K. Johnson, E. Chornet, W. Zmierczak, and J. Shabtai Conversion of lignin into a hydrocarbon product for blending with gasoline Fuel Chem Division Preprints 47 1 2002 380 381
A.U. Buranov, and G. Mazza Lignin in straw of herbaceous crops Ind Crops Prod 28 2008 237 259
N.G. Lewis, and E. Yamamoto Lignin: occurrence, biogenesis and biodegradation Annu Rev Plant Mol Biol 41 1990 455 496 (Pubitemid 120024690)
F.S. Chakar, and A.J. Ragauskas Review of current and future softwood kraft lignin process chemistry Ind Crops Prod 20 2004 131 141 (Pubitemid 39301111)
K. Freudenberg, and G. Grion Contribution to the mechanism of formation of lignin and of the lignin-carbohydrate bond Chem Ber 92 1959 1355 1363
K. Freudenberg, and J.M. Harkin Models for the linkages of lignin to carbohydrates Chem Ber 93 1960 2814 2819
B. Kosikova, D. Joniak, and J. Skamla Lignin-carbohydrate bonds in beech wood Cell Chem Technol 6 1972 579 588
R.J.A. Gosselink, E. de Jong, B. Guran, and A. Abächerli Co-ordination network for lignin - standardisation, production and applications adapted to market requirements (EUROLIGNIN) Ind Crops Prod 20 2004 121 129 (Pubitemid 39301110)
J. Zakzeski, P.C.A. Bruijnincx, A.L. Jongerius, and B.M. Weckhuysen The catalytic valorization of lignin for the production of renewable chemicals Chem Rev 110 2010 3552 3599
T. Dizhbite, G. Telysheva, V. Jurkjane, and U. Viesturs Characterization of the radical scavenging activity of lignins-natural antioxidants Bioresour Technol 95 2004 309 317 (Pubitemid 39013372)
H.K. Murnen, V. Balan, S. Chundawat, B. Bals, L. da Costa Sousa, and B.E. Dale Optimization of ammonia fiber expansion (AFEX) pretreatment and enzymatic hydrolysis of Miscanthus x giganteus to fermentable sugars Biotechnol Prog 23 2007 846 850 (Pubitemid 47255069)
R. El Hage, N. Brosse, L. Chrusciel, C. Sanchez, P. Sannigrahi, and A. Ragauskas Characterization of milled wood lignin and ethanol organosolv lignin from miscanthus Polym Degrad Stab 94 10 2009 1632 1638
R. El Hage, N. Brosse, P. Sannigrahi, and A. Ragauskas Effects of process severity on the chemical structure of Miscanthus ethanol organosolv lignin Polym Degrad Stab 95 6 2010 997 1003
T. Le Ngoc Huyen, C. Rémond, R.M. Dheilly, and B. Chabbert Effect of harvesting date on the composition and the saccharification of Miscanthus x giganteus Bioresour Technol 101 2010 8224 8231
J.J. Villaverde, J. Li, M. Ek, P. Ligero, and A. de Vega Native lignin structure of Miscanthus x giganteus and its changes during acetic and formic acid fractionation J Agric Food Chem 57 2009 6262 6270
H.Q. Lam, Y. Le Bigot, M. Delmas, and G. Avignon A new procedure for the destructuring of vegetable matter at atmospheric pressure by a catalyst/solvent system of formic acid/ acetic acid. Applied to the pulping of triticale straw Ind Crop Prod 4 2001 139 144 (Pubitemid 32812208)
A. Sluiter, B. Hames, R. Ruiz, C. Scarlata, J. Sluiter, and D. Templeton Determination of structural carbohydrates and lignin in biomass 2008 National Renewable Energy Laboratory Golden, CO., USA Laboratory Analytical Procedure
A.B. Blakeney, P.J. Harris, R.J. Henry, and B.A. Stone A simple and rapid preparation of alditol acetates for monosaccharides analysis Carbohydr Res 113 1983 291 299
S.S. Abdullah, S. Yusup, M.M. Ahmad, A. Ramli, and L. Ismal Thermogravimetry study on pyrolysis of various lignocellulosic biomass for potential hydrogen production Int J Chem Biol Eng 3 3 2010 137 141
Y. Wu, Z. Zhao, H. Li, and F. He Low temperature pyrolysis characteristics of major components of biomass J Fuel Chem Technol 37 4 2009 427 432
A. Uslu, A.P.C. Faaij, and P.C.A. Bergman Pre-treatment technologies and their effect on international bioenergy supply chain logistics. Techno-economic evaluation of torrefaction, fast pyrolysis and pelletisation Energy 33 2008 1206 1223
L. Serrano, I. Egües, M. González Alriols, R. Llano-Ponte, and J. Labidi Miscanthus sinensis fractionation by different reagents Chem Eng J 156 1 2010 49 55
R.C. Sun, J. Tomkinson, and J. Bolton Effects of precipitation pH on the physico-chemical properties of the lignins isolated from the black liquor of oil palm empty fruit bunch fibre pulping Polym Deg Stab 63 2 1999 195 200
S.A. Ralph, J. Ralph, and L.L. Landucci NMR Database of Lignin and Cell Wall Model Compounds 2004 Available at http://ars.usda.gov/Services/docs.htm? docid=10491
E.A. Capanema, M.Y. Balakshin, and J.F. Kadla A comprehensive approach for quantitative lignin characterization by NMR spectroscopy J Agric Food Chem 52 2004 1850 1860
A. Toledano, L. Serrano, A. Garcia, I. Mondragon, and J. Labidi Comparative study of lignin fractionation by ultrafiltration and selective precipitation Chem Eng J 157 1 2010 93 99
Z. Xia, L.G. Akim, and D.S. Argyropoulos Quantitative 13C NMR analyses of lignins with internal standards J Agric Food Chem 49 2001 3573 3578 (Pubitemid 32822660)
C.L. Chen N. Lewis, S. Sarkanen, Characterization of milled wood lignins and dehydrogenative polymerizates from monolignols by carbon-13 NMR spectroscopy, Lignin and Lignan Biosynthesis 1998 American Chemical Society Washington DC 255 275 ACS Symposium Series 697
X.J. Pan, D. Xie, R.W. Yu, D. Lam, and J.N. Saddler Pre-treatment of Iodgepole pine killed by mountain pine beetle using the ethanol organosolv process: fractionation and process optimization Ind Eng Chem Res 46 8 2007 2609 2617 (Pubitemid 46652798)
J. Li, G. Henriksson, and G. Gellerstedt Lignin depolymerization/ repolymerisation and its critical role for delignification of aspen wood by steam explosion Bioresour Technol 98 2007 3061 3068 (Pubitemid 46603259)
J.H. Grabber How do lignin composition, structure, and cross-linking affect degradability? A review of cell wall model studies Crop Sci 45 2005 820 831 (Pubitemid 40670262)
T.J. McDonough The chemistry of organosolv delignification Tappi J 76 1993 186 193
A. Garcia, A. Toledano, M.A. Andrés, and J. Labidi Study of the antioxidant capacity of Miscanthus sinensis lignins Proc Biochem 45 2010 935 940
Similar publications
Sorry the service is unavailable at the moment. Please try again later.
This website uses cookies to improve user experience. Read more
Save & Close
Accept all
Decline all
Show detailsHide details
Cookie declaration
About cookies
Strictly necessary
Performance
Strictly necessary cookies allow core website functionality such as user login and account management. The website cannot be used properly without strictly necessary cookies.
This cookie is used by Cookie-Script.com service to remember visitor cookie consent preferences. It is necessary for Cookie-Script.com cookie banner to work properly.
Performance cookies are used to see how visitors use the website, eg. analytics cookies. Those cookies cannot be used to directly identify a certain visitor.
Used to store the attribution information, the referrer initially used to visit the website
Cookies are small text files that are placed on your computer by websites that you visit. Websites use cookies to help users navigate efficiently and perform certain functions. Cookies that are required for the website to operate properly are allowed to be set without your permission. All other cookies need to be approved before they can be set in the browser.
You can change your consent to cookie usage at any time on our Privacy Policy page.
