Ethylenediamine pretreatment changes cellulose allomorph and lignin structure of lignocellulose at ambient pressure

Biotechnology for Biofuels

Lei Qin²  Wen-Chao Li²  Jia-Qing Zhu²  Jing-Nan Liang¹  Bing-Zhi Li²  Ying-Jin Yuan² 

[1] Institute of Microbiology Chinese Academy of Sciences, No.1 West Beichen Road, Chaoyang District, Beijing 100101, People’s Republic of China

[2] SynBio Research Platform, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Weijin Road 92, Nankai District 300072, Tianjin, People’s Republic of China

关键词: Ethylenediamine;    Lignin;    Hydrolysis;    Cellulose;    Pretreatment;    Biomass;   

Others  :  1229672
DOI  :  10.1186/s13068-015-0359-z

 received in 2015-06-08, accepted in 2015-10-14,  发布年份 2015

【 摘 要 】

Background

Pretreatment of lignocellulosic biomass is essential to increase the cellulase accessibility for bioconversion of lignocelluloses by breaking down the biomass recalcitrance. In this work, a novel pretreatment method using ethylenediamine (EDA) was presented as a simple process to achieve high enzymatic digestibility of corn stover (CS) by heating the biomass–EDA mixture with high solid-to-liquid ratio at ambient pressure. The effect of EDA pretreatment on lignocellulose was further studied.

Results

High enzymatic digestibility of CS was achieved at broad pretreatment temperature range (40–180 °C) during EDA pretreatment. Herein, X-ray diffractogram analysis indicated that cellulose I changed to cellulose III and amorphous cellulose after EDA pretreatment, and cellulose III content increased along with the decrease of drying temperature and the increase of EDA loading. Lignin degradation was also affected by drying temperature and EDA loading. Images from scanning electron microscope and transmission electron microscope indicated that lignin coalesced and deposited on the biomass surface during EDA pretreatment, which led to the delamination of cell wall. HSQC NMR analysis showed that ester bonds of p-coumarate and ferulate units in lignin were partially ammonolyzed and ether bonds linking the phenolic monomers were broken during pretreatment. In addition, EDA-pretreated CS exhibited good fermentability for simultaneous saccharification and co-fermentation process.

Conclusions

EDA pretreatment improves the enzymatic digestibility of lignocellulosic biomass significantly, and the improvement was caused by the transformation of cellulose allomorph, lignin degradation and relocalization in EDA pretreatment.

【 授权许可】

   
2015 Qin et al.

【 图 表 】

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【 参考文献 】

• [1]Alvira P, Tomás-Pejó E, Ballesteros M, Negro MJ: Pretreatment technologies for an efficient bioethanol production process based on enzymatic hydrolysis: A review. Bioresour Technol 2010, 101:4851-4861.
• [2]Chundawat SPS, Beckham G, Himmel ME, Dale BE: Deconstruction of lignocellulosic biomass to fuels and chemicals. Annu Rev Chem Biomol Eng 2011, 2:121-145.
• [3]Mosier N, Wyman C, Dale BE, Elander R, Lee YY, Holtzapple M, Ladisch M: Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresour Technol 2005, 96(6):673-686.
• [4]Bali G, Meng X, Deneff JI, Sun Q, Ragauskas AJ: The effect of alkaline pretreatment methods on cellulose structure and accessibility. ChemSusChem 2015, 8(2):275-279.
• [5]Qin L, Liu ZH, Jin MJ, Li BZ, Yuan YJ: High temperature aqueous ammonia pretreatment and post-washing enhance the high solids enzymatic hydrolysis of corn stover. Bioresour Technol 2013, 146:504-511.
• [6]Lau MW, Dale BE: Cellulosic ethanol production from AFEX-treated corn stover using Saccharomyces cerevisiae 424A(LNH-ST). Proc Natl Acad Sci 2009, 106(5):1368-1373.
• [7]Li BZ, Balan V, Yuan YJ, Dale BE: Process optimization to convert forage and sweet sorghum bagasse to ethanol based on ammonia fiber expansion (AFEX) pretreatment. Bioresour Technol 2010, 101:1285-1292.
• [8]Shafiei M, Karimi K, Taherzadeh MJ: Pretreatment of spruce and oak by N-methylmorpholine-N-oxide (NMMO) for efficient conversion of their cellulose to ethanol. Bioresour Technol 2010, 101:4914-4918.
• [9]Tanaka M, Robinson CW, Moo-Young M: Chemical and enzymatic pretreatment of corn stover to produce soluble fermentation substrates. Biotechnol Bioeng 1985, 27(3):362-368.
• [10]Xiao M, Frey MW: The role of salt on cellulose dissolution in ethylene diamine/salt solvent systems. Cellulose 2007, 14:225-234.
• [11]Xiao M, Frey MW: Study of cellulose/ethylene diamine/salt systems. Cellulose 2009, 16:381-391.
• [12]Padmanabhan S, Zaia E, Wu K, Blanch HW, Clark DS, Bell AT, Prausnitz JM: Delignification of Miscanthus by Extraction. Separ Sci Technol. 2012, 47(2):370-376.
• [13]Numata Y, Kono H, Kawano S, Erata T, Takai M: Cross-polarization/magic-angle spinning 13C nuclear magnetic resonance study of cellulose I-ethylenediamine complex. J Biosci Bioeng 2003, 96(5):461-466.
• [14]Sawada D, Nishiyama Y, Petridis L, Parthasarathi R, Gnanakaran S, Forsyth VT, Wada M, Langan P: Structure and dynamics of a complex of cellulose with EDA: insights into the action of amines on cellulose. Cellulose 2013, 20:1563-1571.
• [15]Nishiyama Y, Wada M, Hanson BL, Langan P: Time-resolved X-ray diffraction microprobe studies of the conversion of cellulose I to ethylenediamine-cellulose I. Cellulose 2010, 17:735-745.
• [16]Wada M, Kwon GJ, Nishiyama Y: Structure and thermal behavior of a cellulose I-ethylenediamine complex. Biomacromolecules 2008, 9:2898-2904.
• [17]Wada M, Chanzy H, Nishiyama Y, Langan P: Cellulose III I crystal structure and hydrogen bonding by synchrotron X-ray and neutron fiber diffraction. Macromolecules 2004, 37:8548-8555.
• [18]Wada M: In situ observation of the crystalline transformation from cellulose III I to I β. Macromolecules 2001, 34:3271-3275.
• [19]Chundawat SPS, Bellesia G, Uppugundla N, da Costa Sousa L, Gao D, Cheh AM, Agarwal UP, Bianchetti CM, Phillips GN Jr, Langan P, Balan V, Gnanakaran S, Dale BE: Restructuring the crystalline cellulose hydrogen bond network enhances its depolymerization rate. J Am Chem Soc 2011, 133(29):11163-11174.
• [20]Zhu JY, Pan X, Zalesny RS Jr: Pretreatment of woody biomass for biofuel production: energy efficiency, technologies, and recalcitrance. Appl Microbiol Biotechnol 2010, 87:847-857.
• [21]Zhang J, Wang X, Chu D, He Y, Bao J: Dry pretreatment of lignocellulose with extremely low steam and water usage for bioethanol production. Bioresour Technol 2011, 102:4480-4488.
• [22]Barakat A, Chuetor S, Monlau F, Solhy A, Rouau X: Eco-friendly dry chemo-mechanical pretreatments of lignocellulosic biomass: Impact on energy and yield of the enzymatic hydrolysis. Appl Energ 2014, 113:97-105.
• [23]Mittal A, Katahira R, Himmel ME, Johnson DK: Effects of alkaline or liquid-ammonia treatment on crystalline cellulose: changes in crystalline structure and effects on enzymatic digestibility. Biotechnol Biofuels 2011, 4:41. BioMed Central Full Text
• [24]Lee JM, Jameel H, Venditti RA: A comparison of the autohydrolysis and ammonia fiber explosion (AFEX) pretreatments on the subsequent enzymatic hydrolysis of coastal Bermuda grass. Bioresour Technol 2010, 101:5449-5458.
• [25]Chundawat SPS, Donohoe BS, daCostaSousa L, Elder T, Agarwal UP, Lu F, Ralph J, Himmel ME, Balan V, Dale BE: Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment. Energ Environ Sci 2011, 4:973.
• [26]Donohoe S, Decker SR, Tucker MP, Himmel ME, Vinzant TB: Visualizing lignin coalescence and migration through maize cell walls following thermochemical pretreatment. Biotechnol Bioeng 2008, 101(5):913-925.
• [27]Boukari I, Putaux JL, Cathala B, Barakat A, Saake B, Rémond C, O’Donohue M, Chabber B: In vitro model assemblies to study the impact of lignin-carbohydrate interactions on the enzymatic conversion of xylan. Biomacromolecules 2009, 10:2489-2498.
• [28]Donohoe S, Vinzant TB, Elander RT, Pallapolu VR, Lee YY, Garlock RJ, Balan V, Dale BE, Kim Y, Mosier NS, Ladisch MR, Falls M, Holtzapple MT, Sierra-Ramirez R, Shi J, Ebrik MA, Redmond T, Yang B, Wyman CE, Hames B, Thomas S, Warner RE: Surface and ultrastructural characterization of raw and pretreated switchgrass. Bioresour Technol 2011, 102:11097-11104.
• [29]Zeng J, Tong Z, Wang L, Zhu JY, Ingram L: Isolation and structural characterization of sugarcane bagasse lignin after dilute phosphoric acid plus steam explosion pretreatment and its effect on cellulose hydrolysis. Bioresour Technol 2014, 154:274-281.
• [30]Zeng J, Helms GL, Gao X, Chen S: Quantification of wheat straw lignin structure by comprehensive NMR analysis. J Agric Food Chem 2013, 61:10848-10857.
• [31]Rencoret J, Prinsen P, Gutierrez A, Martinez AT, Del Rio JC: Isolation and structural characterization of the milled wood lignin, dioxane lignin, and cellulolytic lignin preparations from brewer’s spent grain. J Agri Food Chem 2015.
• [32]Wen JL, Sun SL, Yuan TQ, Xu F, Sun RC: Structural elucidation of lignin polymers of Eucalyptus chips during organosolv pretreatment and extended delignification. J Agri Food Chem 2013, 61(46):11067-11075.
• [33]Huang X, Korányi TI, Boot MD, Hensen EJ: Catalytic depolymerization of lignin in supercritical ethanol. ChemSusChem 2014, 7(8):2276-2288.
• [34]Cui T, Li J, Yan Z, Yu M, Li S: The correlation between the enzymatic saccharification and the multidimensional structure of cellulose changed by different pretreatments. Biotechnol Biofuels 2014, 7:134. BioMed Central Full Text
• [35]Liu ZH, Qin L, Li BZ, Yuan YJ: Physical and chemical characterizations of corn stover from leading pretreatment methods and effects on enzymatic hydrolysis. ACS Sustain Chem Eng 2015, 3:140-146.
• [36]Yu Z, Gwak KS, Treasure T, Jameel H, Chang HM, Park S: Effect of lignin chemistry on the enzymatic hydrolysis of woody biomass. ChemSusChem 2014, 7:1942-1950.
• [37]Chundawat SPS, Vismeh R, Sharma LN, Humpula JF, da Costa Sousa L, Chambliss CK, Jones AD, Balan V, Dale BE: Multifaceted characterization of cell wall decomposition products formed during ammonia fiber expansion (AFEX) and dilute acid based pretreatments. Bioresour Technol 2010, 101:8429-8438.
• [38]Sewalt VJH, Glasser WG, Beauchemin KA: Lignin impact on fiber degradation. 3. Reversal of inhibition of enzymatic hydrolysis by chemical modification of lignin and by additives. J Agri Food Chem 1997, 45(5):1823-1828.
• [39]Zhong C, Lau MW, Balan V, Dale BE, Yuan YJ: Optimization of enzymatic hydrolysis and ethanol fermentation from AFEX-treated rice straw. Appl Microbiol Biotechnol 2009, 84:667-676.
• [40]Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK: Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 2010, 3:10. BioMed Central Full Text
• [41]Ciolacu D, Gorgieva S, Tampu D, Kokol V: Enzymatic hydrolysis of different allomorphic forms of microcrystalline cellulose. Cellulose 2011, 18:1527-1541.
• [42]Donohoe BS, Selig MJ, Viamajala S, Vinzant TB, Adney WS, Himmel ME: Detecting cellulase penetration into corn stover cell walls by immuno-electron microscopy. Biotechnol Bioeng 2009, 103(3):480-489.
• [43]Zha J, Shen MH, Hu ML, Song H, Yuan YJ: Enhanced expression of genes involved in initial xylose metabolism and the oxidative pentose phosphate pathway in the improved xylose-utilizing Saccharomyces cerevisiae through evolutionary engineering. J Ind Microbiol Biotechnol 2013, 41:27-39.