Abstract
In the present study, deep eutectic solvent (DES) was employed for an effective pretreatment of recalcitrant corn stover (CS) to improve the efficiency of the subsequent saccharification process. Accordingly, the molar ratios of lactic acid (LA)/choline chloride (ChCl), temperature, and time were studied via response surface methodology to optimize pretreatment conditions. While the best cellulose and hemicelluloses digestibility (94.85%) and delignification (29.27%) efficiency were achieved using the LA/ChCl molar ratio of 1 at 140 °C after 4 h. Overall, this efficiency was nearly seven-fold higher when compared to the untreated CS. Besides, at higher temperatures (> 140 °C), the humins were generated in the pretreatment process, which might have wrapped around the surface of the pretreated CS and resulted in an impeded enzymatic accessibility. The pretreatment efficiency was also fully maintained after three repeated cycles. This study provides an insight into the comprehensive utilization of the LA/ChCl type of DES for robust lignocellulosic biomass pretreatment.
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Lin X, Liu Y, Zheng X, Qureshi N (2021) High-efficient cellulosic butanol production from deep eutectic solvent pretreated corn stover without detoxification. Ind Crops Prod 162:113258
Suopajärvi T, Ricci P, Karvonen V, Ottolina G, Liimatainen H (2020) Acidic and alkaline deep eutectic solvents in delignification and nanofibrillation of corn stalk, wheat straw, and rapeseed stem residues. Ind Crops Prod 145:111956
Khan MFS, Akbar M, Xu Z, Wang H (2021) A review on the role of pretreatment technologies in the hydrolysis of lignocellulosic biomass of corn stover. Biomass Bioenerg 155:106276
Liu Y, Zheng X, Tao S, Hu L, Zhang X, Lin X (2021) Process optimization for deep eutectic solvent pretreatment and enzymatic hydrolysis of sugar cane bagasse for cellulosic ethanol fermentation. Renewable Energy 177:259–267
Liang X, Zhu Y, Qi B, Li S, Luo J, Wan Y (2021) Structure-property-performance relationships of lactic acid-based deep eutectic solvents with different hydrogen bond acceptors for corn stover pretreatment. Bioresour Technol 336:125312
Yang X, Li H, Chang C, Chen J, Ma X (2017) The integrated process of microbial ensiling and hot-washing pretreatment of dry corn stover for ethanol production. Waste Biomass Valorization 9:2031–2040
Okuofu SI, Gerrano AS, Singh S, Pillai S (2020) Deep eutectic solvent pretreatment of Bambara groundnut haulm for enhanced saccharification and bioethanol production. Biomass Conver Bioref. https://doi.org/10.1007/s13399-020-01053-w
Anastas P, Eghbali N (2010) Green chemistry: principles and practice. Chem Soc Rev 39:301–312
Bhagwat P, Amobonye A, Singh S, Pillai S (2021) Deep eutectic solvents in the pretreatment of feedstock for efficient fractionation of polysaccharides: current status and future prospects. Biomass Conver Bioref. https://doi.org/10.1007/s13399-021-01745-x
Isci A, Kaltschmitt M (2021) Recovery and recycling of deep eutectic solvents in biomass conversions: a review. Biomass Conver Bioref. https://doi.org/10.1007/s13399-021-01860-9
Tian D, Guo Y, Hu J, Yang G, Zhang J, Luo L, Xiao Y, Deng S, Deng O, Zhou W, Shen F (2020) Acidic deep eutectic solvents pretreatment for selective lignocellulosic biomass fractionation with enhanced cellulose reactivity. Int J Biol Macromol 142:288–297
Zhao Z, Chen X, Ali MF, Abdeltawab AA, Yakout SM, Yu G (2018) Pretreatment of wheat straw using basic ethanolamine-based deep eutectic solvents for improving enzymatic hydrolysis. Bioresour Technol 263:325–333
Satlewal A, Agrawal R, Bhagia S, Sangoro J, Ragauskas AJ (2018) Natural deep eutectic solvents for lignocellulosic biomass pretreatment: recent developments, challenges and novel opportunities. Biotechnol Adv 36:2032–2050
Manivannan H, Anguraj BL (2021) Valorization of fruit waste using DES pretreatment and hydrolysis over a heterogeneous catalyst for bioethanol production. Biomass Conver Bioref. https://doi.org/10.1007/s13399-021-01669-6
Li W-X, Xiao W-Z, Yang Y-Q, Wang Q, Chen X, Xiao L-P, Sun R-C (2021) Insights into bamboo delignification with acidic deep eutectic solvents pretreatment for enhanced lignin fractionation and valorization. Ind Crops Prod 170:113692
Li P, Zhang Q, Zhang X, Zhang X, Pan X, Xu F (2019) Subcellular dissolution of xylan and lignin for enhancing enzymatic hydrolysis of microwave assisted deep eutectic solvent pretreated Pinus bungeana Zucc. Bioresour Technol 288:121475
Guo Z, Zhang Q, You T, Zhang X, Xu F, Wu Y (2019) Short-time deep eutectic solvent pretreatment for enhanced enzymatic saccharification and lignin valorization. Green Chem 21:3099–3108
Zdanowicz M, Wilpiszewska K, Spychaj T (2018) Deep eutectic solvents for polysaccharides processing. A review. Carbohydr Polym 200:361–380
Tan YT, Chua ASM, Ngoh GC (2020) Deep eutectic solvent for lignocellulosic biomass fractionation and the subsequent conversion to bio-based products - a review. Bioresour Technol 297:122522
Hou XD, Li AL, Lin KP, Wang YY, Kuang ZY, Cao SL (2018) Insight into the structure-function relationships of deep eutectic solvents during rice straw pretreatment. Bioresour Technol 249:261–267
Zhang CW, Xia SQ, Ma PS (2016) Facile pretreatment of lignocellulosic biomass using deep eutectic solvents. Bioresour Technol 219:1–5
Thi S, Lee KM (2019) Comparison of deep eutectic solvents (DES) on pretreatment of oil palm empty fruit bunch (OPEFB): Cellulose digestibility, structural and morphology changes. Bioresour Technol 282:525–529
Shen XJ, Wen JL, Mei QQ, Chen X, Sun D, Yuan TQ, Sun RC (2019) Facile fractionation of lignocelluloses by biomass-derived deep eutectic solvent (DES) pretreatment for cellulose enzymatic hydrolysis and lignin valorization. Green Chem 21:275–283
Tan YT, Ngoh GC, Chua ASM (2018) Evaluation of fractionation and delignification efficiencies of deep eutectic solvents on oil palm empty fruit bunch. Ind Crops Prod 123:271–277
Bi W, Tian M, Row KH (2013) Evaluation of alcohol-based deep eutectic solvent in extraction and determination of flavonoids with response surface methodology optimization. J Chromatogr A 1285:22–30
Luo Y, Li D, Li R, Li Z, Hu C, Liu X (2020) Roles of water and aluminum sulfate for selective dissolution and utilization of hemicellulose to develop sustainable corn stover-based biorefinery. Renew Sustain Energy Rev 122:109724
Xu H, Peng J, Kong Y, Liu Y, Su Z, Li B, Song X, Liu S, Tian W (2020) Key process parameters for deep eutectic solvents pretreatment of lignocellulosic biomass materials: a review. Bioresour Technol 310:123416
Chen Y, Mu T (2019) Application of deep eutectic solvents in biomass pretreatment and conversion. Green Energ Environ 4:95–115
Li K, Qin JC, Liu CG, Bai FW (2016) Optimization of pretreatment, enzymatic hydrolysis and fermentation for more efficient ethanol production by Jerusalem artichoke stalk. Bioresour Technol 221:188–194
Sluiter A, Hames B, Ruiz RO, Scarlata C, Sluiter J, Templeton D (2004) Determination of structural carbohydrates and lignin in biomass. Biomass Anal Technol Team Lab Anal Proced 2011:1–14
Khare L, Karve T, Jain R, Dandekar P (2021) Menthol based hydrophobic deep eutectic solvent for extraction and purification of ergosterol using response surface methodology. Food Chem 340:127979
Jessop PG, Jessop DA, Fu D, Phan L (2012) Solvatochromic parameters for solvents of interest in green chemistry. Green Chem 14:1245
Yu Q, Song Z, Zhuang X, Liu L, Qiu W, Shi J, Wang W, Li Y, Wang Z, Yuan Z (2019) Catalytic conversion of herbal residue carbohydrates to furanic derivatives in a deep eutectic solvent accompanied by dissolution and recrystallisation of choline chloride. Cellulose 26:8263–8277
Procentese A, Raganati F, Olivieri G, Russo ME, Rehmann L, Marzocchella A (2018) Deep eutectic solvents pretreatment of agro-industrial food waste. Biotechnol Biofuels 11:37
Ao T, Luo Y, Chen Y, Cao Q, Liu X, Li D (2020) Towards zero waste: a valorization route of washing separation and liquid hot water consecutive pretreatment to achieve solid vinasse based biorefinery. J Clean Prod 248:119253
Chen L, Yu Q, Wang Q, Wang W, Qi W, Zhuang X, Wang Z, Yuan Z (2019) A novel deep eutectic solvent from lignin-derived acids for improving the enzymatic digestibility of herbal residues from cellulose. Cellulose 26:1947–1959
Kumar AK, Shah E, Patel A, Sharma S, Dixit G (2018) Physico-chemical characterization and evaluation of neat and aqueous mixtures of choline chloride + lactic acid for lignocellulosic biomass fractionation, enzymatic hydrolysis and fermentation. J Mol Liq 271:540–549
Shi N, Liu Q, Cen H, Ju R, He X, Ma L (2019) Formation of humins during degradation of carbohydrates and furfural derivatives in various solvents. Biomass Convers Biorefinery 10:277–287
van Zandvoort I, Wang Y, Rasrendra CB, van Eck ER, Bruijnincx PC, Heeres HJ, Weckhuysen BM (2013) Formation, molecular structure, and morphology of humins in biomass conversion: influence of feedstock and processing conditions. Chemsuschem 6:1745–1758
Dee SJ, Bell AT (2011) A study of the acid-catalyzed hydrolysis of cellulose dissolved in ionic liquids and the factors influencing the dehydration of glucose and the formation of humins. Chemsuschem 4:1166–1173
Zulkefli S, Abdulmalek E, Abdul Rahman MB (2017) Pretreatment of oil palm trunk in deep eutectic solvent and optimization of enzymatic hydrolysis of pretreated oil palm trunk. Renew Energ 107:36–41
Yu Q, Zhang A, Wang W, Chen L, Bai R, Zhuang X, Wang Q, Wang Z, Yuan Z (2018) Deep eutectic solvents from hemicellulose-derived acids for the cellulosic ethanol refining of Akebia’ herbal residues. Bioresour Technol 247:705–710
Funding
This work was supported by the National Key Research and Development Program (2018YFB1501401), the National Natural Science Foundation of China (21978167), and the Natural Science Foundation of Shanghai (19160745300).
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Tian-Jie Ao: investigation, methodology, writing the original draft. Kai Li: investigation, methodology. Muhammad Aamer Mehmood: conceptualization, writing—review and editing. Xin-Qing Zhao: conceptualization. Feng-Wu Bai: supervision, funding acquisition, project administration. Raj Boopathy: writing—review and editing. Chen-Guang Liu: supervision, funding acquisition, project administration, conceptualization, writing- review and editing.
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Highlights
• DES was employed for an effective pretreatment of corn stover (CS).
• The DES pretreatment was optimized via RSM and the single-factor approach.
• Humins were wrapped around the pretreated CS, causing poor enzymatic efficiency.
• The DES pretreatment efficiency was fully maintained after 3 repeated cycles.
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Ao, TJ., Li, K., Mehmood, M.A. et al. Process optimization for acidic deep eutectic solvent pretreatment of corn stover to enhance enzymatic saccharification. Biomass Conv. Bioref. 14, 6215–6228 (2024). https://doi.org/10.1007/s13399-022-02738-0
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DOI: https://doi.org/10.1007/s13399-022-02738-0