Unraveling the structural characteristics of lignin in hydrothermal pretreated fibers and manufactured binderless boards from Eucalyptus grandis

Sustainable Chemical Processes

Ling-Ping Xiao²  Zhi Lin¹  Wan-Xi Peng¹  Tong-Qi Yuan²  Feng Xu²  Nian-Chun Li¹  Qing-Song Tao⁴  Hang Xiang³  Run-Cang Sun⁵ 

[1] School of Materials and Engineering, Central South University of Forestry and Technology, Changsha 410004, China

[2] Beijng Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China

[3] Hunan Yuanhang Biotechnology Co., Ltd., Wangcheng 410200, China

[4] Jiangxi JooMuTang Bamboo Flooring Co., Ltd., Nanchang 330052, China

[5] State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China

关键词: Self-bonding;    Binderless board;    Cellulolytic enzyme lignin;    Hot pressing;    Hydrothermal pretreatment;   

Others  :  789160
DOI  :  10.1186/2043-7129-2-9

 received in 2013-12-17, accepted in 2014-04-04,  发布年份 2014

【 摘 要 】

Background

Eucalyptus grandis is one of the most abundant biomass from plantation in many parts of the world. The binderless board were manufactured from hydrothermal pretreated fibers of Eucalyptus wood and characterized for the chemical analyses and mechanical strengths in order to assess the mechanism of self-bonding. To make clear the self-bonding mechanism of these binderless boards, the structural characteristics of cellulolytic enzyme lignin (CEL) isolated from Eucalyptus wood, its hydrothermal pretreated fibers, and binderless boards were thoroughly investigated by chemical and spectroscopic methods.

Results

The result revealed that hydrothermal pretreatment and hot pressing process could change cellulose crystalline structures by disrupting inter/intra hydrogen bonding of cellulose chains. During the hydrothermal pretreatment of Eucalyptus wood, acid-catalyzed cleavage of β-O-4′ linkages and ester bonds were the major mechanisms of lignin cleavage. This degradation pathway led to a more condensed lignin which has a high average molecular weight and more phenolic hydroxyl groups than the control. The hot pressing process resulted in the binderless boards with reduced lignin contents and decreased the glass transition temperature, thus making the lignin more accessible to the fiber surface. CEL isolated from the binderless boards showed an increased syringyl to guaiacyl propane (S/G) ratio but a lower molecular weight than those of the untreated Eucalyptus wood and the hydrothermal pretreated fibers.

Conclusions

Based on the finding of this study, it is suggested that the combination of hydrothermal pretreatment and hot pressing process is a good way for conditioning hardwood sawdust for the production of binderless boards. The thermal softening of lignin, rich in phenolic hydroxyl groups, and increased condensed lignin structure contributed to the self-bonding formation of lignocellulosic materials.

【 授权许可】

   
2014 Xiao et al.; licensee Chemistry Central Ltd.

【 图 表 】

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【 参考文献 】

• [1]Widsten P, Kandelbauer A: Adhesion improvement of lignocellulosic products by enzymatic pre-treatment. Biotechnol Adv 2008, 26:379-386.
• [2]Fahmy TYA, Mobarak F: Advanced binderless board-like green nanocomposites from undebarked cotton stalks and mechanism of self-bonding. Cellulose 2013, 20:1453-1457.
• [3]Fahmy TYA, Mobarak F, Fahmy Y, Fadl MH, El-Sakhawy M: Nanocomposites from natural cellulose fibers incorporated with sucrose. Wood Sci Technol 2006, 40:77-86.
• [4]Fahmy TYA, Mobarak F: Nanocomposites from natural cellulose fibers filled with kaolin in presence of sucrose. Carbohydr Polym 2008, 72:751-755.
• [5]Fahmy TYA, Mobarak F: Vaccination of biological cellulose fibers with glucose: a gateway to novel nanocomposites. Int J Biol Macromol 2008, 42:52-54.
• [6]Xiao LP, Shi ZJ, Xu F, Sun RC: Hydrothermal treatment and enzymatic hydrolysis of Tamarix ramosissima: evaluation of the process as a conversion method in a biorefinery concept. Bioresour Technol 2013, 135:73-81.
• [7]Pelaez-Samaniego MR, Yadama V, Lowell E, Espinoza-Herrera R: A review of wood thermal pretreatments to improve wood composite properties. Wood Sci Technol 2013, 7:1321-1322.
• [8]Saito Y, Ishii M, Sato M: The suitable harvesting season and the part of moso bamboo (Phyllostachys pubescens) for producing binderless boards. Wood Sci Technol 2013, 47:1071-1081.
• [9]Donohoe BS, Decker SR, Tucker MP, Himmel ME, Vinzant TB: Visualizing lignin coalescence and migration through maize cell walls following thermochemical pretreatment. Biotechnol Bioeng 2008, 101:913-925.
• [10]Anglès MN, Ferrando F, Farriol X, Salvadó J: Suitability of steam exploded residual softwood for the production of binderless panels: effect of the pre-treatment severity and lignin addition. Biomass Bioenergy 2001, 21:211-224.
• [11]Xiao LP, Sun ZJ, Shi ZJ, Xu F, Sun RC: Impact of hot compressed water pretreatment on the structural changes of woody biomass for bioethanol production. BioResources 2011, 6:1576-1598.
• [12]Selig MJ, Viamajala S, Decker SR, Tucker MP, Himmel ME, Vinzant TB: Deposition of lignin droplets produced during dilute acid pretreatment of maize stems retards enzymatic hydrolysis of cellulose. Biotechnol Progr 2007, 23:1333-1339.
• [13]Hsu W, Schwald W, Schwald MJ, Shields MJ: Chemical and physical changes required for producing dimensionally stable wood-based composites. Wood Sci Technol 1988, 22:281-289.
• [14]Boonstra MJ, Pizzi A, Ohlmeyer M, Paul W: The effects of a two stage heat treatment process on the properties of particleboard. Holz Roh Werkst 2006, 64:157-164.
• [15]Okuda N, Hori K, Sato M: Chemical changes of kenaf core binderless boards during hot pressing (I): influence of the pressing temperature condition. J Wood Sci 2006, 52:244-248.
• [16]Hashim R, Nadhari WNAW, Sulaiman O, Kawamura F, Hiziroglu S, Sato M, Sugimoto T, Seng TG, Tanaka R: Characterization of raw materials and manufactured binderless particleboard from oil palm biomass. Mater Design 2011, 32:246-254.
• [17]Mancera C, Ferrando F, Salvado J: Cynara cardunculus as raw material for the production of binderless fiberboards: optimization of pretreatment and pressing conditions. J Wood Chem Technol 2008, 28:207-226.
• [18]Okuda N, Hori K, Sato M: Chemical changes of kenaf core binderless boards during hot pressing (II): effects on the binderless board properties. J Wood Sci 2006, 52:249-254.
• [19]Björkman A: Studies on finely divided wood: part 1: extraction of lignin with neutral solvents. Sven Papperstidn 1956, 59:477-485.
• [20]Ikeda T, Holtman K, Kadla JF, Chang H-m, Jameel H: Studies on the effect of ball milling on lignin structure using a modified DFRC method. J Agric Food Chem 2001, 50:129-135.
• [21]Whiting P, Goring D: The morphological origin of milled wood lignin. Sven Papperstidn 1981, 84:120-122.
• [22]Whiting P, Goring D: Chemical characterization of tissue fractions from the middle lamella and secondary wall of black spruce tracheids. Wood Sci Technol 1982, 16:261-267.
• [23]Chang H, Cowling EB, Brown W: Comparative studies on cellulolytic enzyme lignin and milled wood lignin of sweetgum and spruce. Holzforschung 1975, 29:153-159.
• [24]Hu Z, Yeh T-F, Chang H-m, Matsumoto Y, Kadla JF: Elucidation of the structure of cellulolytic enzyme lignin. Holzforschung 2006, 60:389-397.
• [25]Prinsen P, Gutiérrez A, Rencoret J, Nieto L, Jiménez-Barbero J, Burnet A, Petit-Conil M, Colodette JL, Martínez ÁT, del Río JC: Morphological characteristics and composition of lipophilic extractives and lignin in Brazilian woods from different eucalypt hybrids. Ind Crops Prod 2012, 36:572-583.
• [26]JIS – A 5908: Particleboards. Tokyo, Japan: Japanese Industrial Standard (JIS). Japanese Standards Association; 2003:1-24.
• [27]GB/T 11718–2009: Medium density fibreboard. Beijing, China: China National Standard. Standardization Administration of the People’s Republic of China; 2009:1-32.
• [28]Nadhari WNAW, Hashim R, Sulaiman O, Sato M, Sugimoto T, Selamat ME: Utilization of oil palm trunk waste for manufacturing of binderless particleboard: optimization study. BioResources 2013, 8:1675-1696.
• [29]Oh SY, Yoo DI, Shin Y, Seo G: FTIR analysis of cellulose treated with sodium hydroxide and carbon dioxide. Carbohydr Res 2005, 340:417-428.
• [30]Poletto M, Pistor V, Santana RMC, Zattera AJ: Materials produced from plant biomass: part II: evaluation of crystallinity and degradation kinetics of cellulose. Mater Res 2012, 15:421-427.
• [31]Ninomiya K, Kamide K, Takahashi K, Shimizu N: Enhanced enzymatic saccharification of kenaf powder after ultrasonic pretreatment in ionic liquids at room temperature. Bioresour Technol 2012, 103:259-265.
• [32]Cao S, Aita GM: Enzymatic hydrolysis and ethanol yields of combined surfactant and dilute ammonia treated sugarcane bagasse. Bioresour Technol 2013, 131:357-364.
• [33]Silva MR, Machado GO, Brito JO, Calil Junior C: Strength and stiffness of thermally rectified eucalyptus wood under compression. Mat Res 2013, 16:1077-1083.
• [34]Kumar R, Mago G, Balan V, Wyman CE: Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies. Bioresour Technol 2009, 100:3948-3962.
• [35]Faix O: Classification of lignins from different botanical origins by FT-IR spectroscopy. Holzforschung 1991, 45:21-28.
• [36]Ibarra D, Chávez MI, Rencoret J, del Río JC, Gutiérrez A, Romero J, Camarero S, Martínez MJ, Jiménez-Barbero J, Martínez ÁT: Structural modification of eucalypt pulp lignin in a totally chlorine-free bleaching sequence including a laccase-mediator stage. Holzforschung 2007, 61:634-646.
• [37]Xiao LP, Shi ZJ, Xu F, Sun RC: Characterization of MWLs from Tamarix ramosissima isolated before and after hydrothermal treatment by spectroscopical and wet chemical methods. Holzforschung 2012, 66:295-302.
• [38]Villaverde JJ, Li J, Ek M, Ligero P, de Vega A: Native lignin structure of Miscanthus x giganteus and its changes during acetic and formic acid fractionation. J Agric Food Chem 2009, 57:6262-6270.
• [39]Yelle DJ, Ralph J, Frihart CR: Characterization of nonderivatized plant cell walls using high‒resolution solution‒state NMR spectroscopy. Magn Reson Chem 2008, 46:508-517.
• [40]Kim H, Ralph J: Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d6/pyridine-d5. Org Biomol Chem 2010, 8:576-591.
• [41]Rencoret J, Gutiérrez A, Nieto L, Jiménez-Barbero J, Faulds CB, Kim H, Ralph J, Martínez ÁT, José C: Lignin composition and structure in young versus adult Eucalyptus globulus plants. Plant Physiol 2011, 155:667-682.
• [42]Samuel R, Foston M, Jaing N, Cao S, Allison L, Studer M, Wyman C, Ragauskas AJ: HSQC (heteronuclear single quantum coherence) 13C–1H correlation spectra of whole biomass in perdeuterated pyridinium chloride–DMSO system: an effective tool for evaluating pretreatment. Fuel 2011, 90:2836-2842.
• [43]Li J, Henriksson G, Gellerstedt G: Lignin depolymerization/repolymerization and its critical role for delignification of aspen wood by steam explosion. Bioresour Technol 2007, 98:3061-3068.
• [44]Xiao LP, Shi ZJ, Xu F, Sun RC: Characterization of lignins isolated with alkaline ethanol from the hydrothermal pretreated Tamarix ramosissima. Bioenerg Res 2013, 6:519-532.
• [45]Rencoret J, Marques G, Gutiérrez A, Nieto L, Santos JI, Jiménez-Barbero J, Martínez ÁT, del Río JC: HSQC-NMR analysis of lignin in woody (Eucalyptus globulus and Picea abies) and non-woody (Agave sisalana) ball-milled plant materials at the gel state. Holzforschung 2009, 63:691-698.
• [46]Çetinkol ÖP, Smith-Moritz AM, Cheng G, Lao J, George A, Hong K, Henry R, Simmons BA, Heazlewood JL, Holmes BM: Structural and chemical characterization of hardwood from tree species with applications as bioenergy feedstocks. PLoS One 2012, 7:e52820.
• [47]Kawai S, Nakagawa M, Ohashi H: Degradation mechanisms of a nonphenolic β-O-4 lignin model dimer by Trametes versicolor laccase in the presence of 1-hydroxybenzotriazole. Enzyme Microb Technol 2002, 30:482-489.
• [48]Gutiérrez A, Rencoret J, Cadena EM, Rico A, Barth D, del Río JC, Martínez ÁT: Demonstration of laccase-based removal of lignin from wood and non-wood plant feedstocks. Bioresour Technol 2012, 119:114-122.
• [49]Muheim A, Fiechter A, Harvey PJ, Schoemaker HE: On the mechanism of oxidation of non-phenolic lignin model compounds by the laccase-ABTS couple. Holzforschung 1992, 46:121-126.
• [50]Granata A, Argyropoulos DS: 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, a reagent for the accurate determination of the uncondensed and condensed phenolic moieties in lignins. J Agric Food Chem 1995, 43:1538-1544.
• [51]Chandra R, Bura R, Mabee W, Berlin A, Pan X, Saddler J: Substrate pretreatment: the key to effective enzymatic hydrolysis of lignocellulosics? Biofuels 2007, 108:67-93.
• [52]El Hage R, Brosse N, Sannigrahi P, Ragauskas A: Effects of process severity on the chemical structure of Miscanthus ethanol organosolv lignin. Polym Degrad Stab 2010, 95:997-1003.
• [53]Ramos LP: The chemistry involved in the steam treatment of lignocellulosic materials. Quim Nova 2003, 26:863-871.
• [54]GB/T 17657–1999: Test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels. China National Standard. Beijing, China: Standardization Administration of the People’s Republic of China; 1999:393-451.
• [55]Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker D: Determination of structural carbohydrates and lignin in biomass. Golden, CO, USA: National Renewable Energy Laboratory analytical procedure. NREL/TP-510-42618; 2008.
• [56]Bai YY, Xiao LP, Shi ZJ, Sun RC: Structural variation of bamboo lignin before and after ethanol organosolv pretreatment. Int J Mol Sci 2013, 14:21394-21413.
• [57]Hallac BB, Sannigrahi P, Pu Y, Ray M, Murphy RJ, Ragauskas AJ: Biomass characterization of Buddleja davidii: a potential feedstock for biofuel production. J Agric Food Chem 2009, 57:1275-1281.
• [58]Cateto CA, Barreiro MF, Rodrigues AE, Brochier-Salon MC, Thielemans W, Belgacem MN: Lignins as macromonomers for polyurethane synthesis: a comparative study on hydroxyl group determination. J Appl Polym Sci 2008, 109:3008-3017.
• [59]Monteil-Rivera F, Huang GH, Paquet L, Deschamps S, Beaulieu C, Hawari J: Microwave-assisted extraction of lignin from triticale straw: optimization and microwave effects. Bioresour Technol 2012, 104:775-782.