Abstract
In this study, bleached chemical pulp from hardwood was treated with different carboxylic acid choline chloride-based deep eutectic solvents (CA/ChCl DESs) including formic acid, acetic acid, ethanedioic acid, propanedioic acid and choline chloride. The dissolution and degradation of cellulose and hemicellulose in chemical pulps in these DESs were analyzed, while the relationships between the polarity parameters of DESs and the degradation and dissolution of cellulosic fibers were discussed. The results show that dicarboxylic acids/ChCl were more conducive to the solubility and degradation of cellulosic fibers compared to monocarboxylic acids/ChCl at a higher temperature. In addition, the increase in alkyl of the CA could reduce the solubility to cellulosic fiber. The further study reveals that the dissolution and degradation of cellulosic fibers are generally governed both by temperature and the ability of DESs hydrogen bond acidity (α), while temperature shows little effect on α. However, no remarkable relationships were found between the DESs hydrogen bond basicity (β) and cellulose degradation and dissolution.
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References
Abo-Hamad A, Hayyan M, AbdulHakim AlSaadi M et al (2015) Potential applications of deep eutectic solvents in nanotechnology. Chem Eng J 273:551–567. https://doi.org/10.1016/j.cej.2015.03.091
Alvarez-Vasco C, Ma R, Quintero MG et al (2016) Unique low-molecular-weight lignin with high purity extracted from wood by deep eutectic solvents (DES): a source of lignin for valorization. Green Chem 18:5133–5141. https://doi.org/10.1039/C6GC01007E
An Y, Li N, Wu H et al (2015a) Changes in the structure and the thermal properties of kraft lignin during its dissolution in cholinium ionic liquids. ACS Sustain Chem Eng 3:2951–2958. https://doi.org/10.1021/acssuschemeng.5b00915
An Y, Zong M, Wu H et al (2015b) Pretreatment of lignocellulosic biomass with renewable cholinium ionic liquids: biomass fractionation, enzymatic digestion and ionic liquid reuse. Bioresour Technol 192:165–171. https://doi.org/10.1016/j.biortech.2015.05.064
Chatterjee C, Pong F, Sen A (2014) Chemical conversion pathways for carbohydrates. Green Chem 17:4–71. https://doi.org/10.1039/c4gc01062k
D’Agostino C, Harris RC, Abbott AP et al (2011) Molecular motion and ion diffusion in choline chloride based deep eutectic solvents studied by 1H pulsed field gradient NMR spectroscopy. Phys Chem Chem Phys 13:21383–21391. https://doi.org/10.1039/c1cp22554e
Dai Y, van Spronsen J, Witkamp G et al (2013) Natural deep eutectic solvents as new potential media for green technology. Anal Chim Acta 766:61–68. https://doi.org/10.1016/j.aca.2012.12.019
Dwamena AK, Raynie DE (2020) Solvatochromic parameters of deep eutectic solvents: effect of different carboxylic acids as hydrogen bond donor. J Chem Eng Data 65:640–646. https://doi.org/10.1021/acs.jced.9b00872
Florindo C, Mcintosh AJS, Welton T et al (2018) A closer look into deep eutectic solvents: exploring intermolecular interactions using solvatochromic probes. Phys Chem Chem Phys 20(1):206–213. https://doi.org/10.1039/c7cp06471c
Francisco M, van den Bruinhorst A, Kroon MC (2012) New natural and renewable low transition temperature mixtures (LTTMs): screening as solvents for lignocellulosic biomass processing. Green Chem 14:2153. https://doi.org/10.1039/c2gc35660k
George A, Brandt A, Tran K et al (2015) Design of low-cost ionic liquids for lignocellulosic biomass pretreatment. Green Chem. https://doi.org/10.1039/C4GC01208A
Gross AS, Bell AT, Chu J (2011) Thermodynamics of cellulose solvation in water and the ionic liquid 1-Butyl-3-methylimidazolim chloride. J Phys Chem B 115:13433–13440. https://doi.org/10.1021/jp202415v
Hou X, Feng G, Ye M et al (2017) Significantly enhanced enzymatic hydrolysis of rice straw via a high-performance two-stage deep eutectic solvents synergistic pretreatment. Bioresour Technol 238:139–146. https://doi.org/10.1016/j.biortech.2017.04.027
Hou X, Li A, Lin K et al (2018) Insight into the structure-function relationships of deep eutectic solvents during rice straw pretreatment. Bioresour Technol 249(261):267. https://doi.org/10.1016/j.biortech.2017.10.019
Jablonský M, Škulcová A, Kamenská L et al (2015) Deep eutectic solvents: fractionation of wheat straw. BioResources 10:8039–8804. https://doi.org/10.15376/biores.10.4.8039-8047
Kumar AK, Parikh BS, Pravakar M (2016) Natural deep eutectic solvent mediated pretreatment of rice straw: bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue. Environ Sci Pollut Res 23:9265–9275. https://doi.org/10.1007/s11356-015-4780-4
Kumar V, Sandhu PP, Ahluwalia V et al (2019) Improved upstream processing for detoxification and recovery of xylitol produced from corncob. Bioresour Technol 291:121931. https://doi.org/10.1016/j.biortech.2019.
Lee HW, Lee H, Kim Y et al (2019) Recent application of biochar on the catalytic biorefinery and environmental processes. Chin Chem Lett 30:2147–2150. https://doi.org/10.1016/j.cclet.2019.05.002
Loow Y-L, Wu TY, Yang GH et al (2018) Deep eutectic solvent and inorganic salt pretreatment of lignocellulosic biomass for improving xylose recovery. Bioresour Technol 249:818–825. https://doi.org/10.1016/j.biortech.2017.07.165
Lynam JG, Kumar N, Wong MJ (2017) Deep eutectic solvents’ ability to solubilize lignin, cellulose, and hemicellulose; thermal stability; and density. Bioresour Technol 238:684–689. https://doi.org/10.1016/j.biortech.2017.04.079
Ma X, Long Y, Chao D et al (2017) Facilitate hemicelluloses separation from chemical pulp in ionic liquid/water by xylanase pretreatment. Ind Crops Prod 109:459–463. https://doi.org/10.1016/j.indcrop.2017.08.063
Meenakshisundaram S, Fayeulle A, Leonard E et al (2021) Fiber degradation and carbohydrate production by combined biological and chemical/physicochemical pretreatment methods of lignocellulosic biomass—a review. Bioresour Technol 331:125053. https://doi.org/10.1016/j.biortech.2021.125053
Mosier N, Wyman C, Dale B et al (2005) Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresour Technol 96:673–686. https://doi.org/10.1016/j.biortech.2004.06.025
Procentese A, Johnson E, Orr V et al (2015) Deep eutectic solvent pretreatment and subsequent saccharification of corncob. Bioresour Technol 192:31–36. https://doi.org/10.1016/j.biortech.2015.05.053
Segal L, Creely JJ, Martin AE et al (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794. https://doi.org/10.1177/004051755902901003
Sharma M, Mukesh C, Mondal D et al (2013) Dissolution of α-chitin in deep eutectic solvents. Rsc Adv 3:18149. https://doi.org/10.1039/c3ra43404d
Sun S, Chen W, Tang J et al (2016) Synergetic effect of dilute acid and alkali treatments on fractional application of rice straw. Biotechnol Biofuels 9:217. https://doi.org/10.1186/s13068-016-0632-9
Taherzadeh M, Karimi K (2008) Pretreatment of lignocellulosic wastes to improve ethanol and biogas production: a review. Int J Mol Sci 9:1621–1651. https://doi.org/10.3390/ijms9091621
Tan YT, Ngoh GC, Chua ASM (2019) Effect of functional groups in acid constituent of deep eutectic solvent for extraction of reactive lignin. Bioresour Technol 281:359–366. https://doi.org/10.1016/j.biortech.2019.02.010
Teles A, Capela EV, Carmo RS et al (2017) Solvatochromic parameters of deep eutectic solvents formed by ammonium-based salts and carboxylic acids. Fluid Phase Equilib 448:15–21. https://doi.org/10.1016/j.fluid.2017.04.020
Tong Z, Meng J, Liu S et al (2021) Room temperature dissolving cellulose with a metal salt hydrate-based deep eutectic solvent. Carbohyd Polym 272:118473. https://doi.org/10.1016/j.carbpol.2021.118473
Vigier KDO, Chatel G, Jérôme F (2015) Contribution of deep eutectic solvents for biomass processing: opportunities, challenges, and limitations. ChemCatChem 7:1250–1260. https://doi.org/10.1002/cctc.201500134
**a Q, Liu Y, Meng J et al (2018) Multiple hydrogen bond coordination in three-constituent deep eutectic solvents enhances lignin fractionation from biomass. Green Chem 20:2711–2721. https://doi.org/10.1039/C8GC00900G
**ng T, Miao Z, Zheng L et al (2017) Green processing of lignocellulosic biomass and its derivatives in deep eutectic solvents. Chemsuschem 13(10):2696–2706. https://doi.org/10.1002/cssc.201700457
**ong R, Zhang X, Tian D et al (2012) Comparing microcrystalline with spherical nanocrystalline cellulose from waste cotton fabrics. Cellulose 19:1189–1198. https://doi.org/10.1007/s10570-012-9730-4
Xu G, Ding J, Han R et al (2016) Enhancing cellulose accessibility of corn stover by deep eutectic solvent pretreatment for butanol fermentation. Bioresour Technol 203:364–369. https://doi.org/10.1016/j.biortech.2015.11.002
Xue B, Yang Y, Zhu M et al (2018) Lewis acid-catalyzed biphasic 2-methyltetrahydrofuran/H2O pretreatment of lignocelluloses to enhance cellulose enzymatic hydrolysis and lignin valorization. Bioresour Technol 270:55–61. https://doi.org/10.1016/j.biortech.2018.09.028
Zhang C, **a S, Ma P (2016) Facile pretreatment of lignocellulosic biomass using deep eutectic solvents. Bioresour Technol 219:1–5. https://doi.org/10.1016/j.biortech.2016.07.026
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 Energy 107:36–41. https://doi.org/10.1016/j.renene.2017.01.037
Acknowledgements
This work was supported by the National Natural Science Foundation of China (31770632) and Innovation Fund from Fujian Agriculture and Forestry University CXZX2017296 and CXZX2017037 and Excellent Master Fund of Fujian Agriculture and Forestry University 1122YS01005.
