Abstract
Zeolites (ZSM-5 and Beta) with different SiO2/Al2O3 ratios were synthesized as solid acids for hydrolyzing cellulose in an inorganic ionic liquid system (lithium bromide trihydrate solution, LBTH) under mild conditions. The results indicated that the texture properties of zeolite had little effect on catalytic activity, while acidity of zeolite was crucial to the cellulose hydrolysis. In the LBTH system, H-form zeolites released H+ into the solution from their acid sites via ion-exchange with Li+, which hydrolyzed the cellulose already dissolved. This unique homogeneous hydrolysis mechanism was the primary reason for the excellent performance of the zeolites in catalyzing cellulose hydrolysis in the LBTH system. It was found cellulose could be completely hydrolyzed to glucose and oligoglucan by 2% (w/w on cellulose) zeolite at 140 °C within 3 h with a single-pass glucose yield 61%. The zeolites could be recovered with 50% initial catalytic activity after regeneration and reused with stable catalytic activity.
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References
Cai H, Li C, Wang A, Xu G, Zhang T (2012) Zeolite-promoted hydrolysis of cellulose in ionic liquid, insight into the mutual behavior of zeolite, cellulose and ionic liquid. Appl Catal B 123–124:333–338. https://doi.org/10.1016/j.apcatb.2012.04.041
Chen TL, Xiong CR, Tao YS (2018) Enhanced hydrolysis of cellulose in ionic liquid using mesoporous ZSM-5. Molecules 23:1–10. https://doi.org/10.3390/molecules23030529
Cho HJ, Dornath P, Fan W (2014) Synthesis of hierarchical Sn-MFI as Lewis acid catalysts for isomerization of cellulosic sugars. ACS Catal 4:2029–2037. https://doi.org/10.1021/cs500295u
Chowdhury AD, Gascon J (2018) The curious case of ketene in zeolite chemistry and catalysis. Angew Chemie-Int Edn 57:14982–14985. https://doi.org/10.1002/anie.201808480
Chu S, Ln Yang, Guo X, Dong L, Chen X, Li Y, Mu X (2018) The influence of pore structure and Si/Al ratio of HZSM-5 zeolites on the product distributions of α-cellulose hydrolysis. Mol Catal 445:240–247. https://doi.org/10.1016/j.mcat.2017.11.032
Deng W, Kennedy JR, Tsilomelekis G, Zheng W, Nikolakis V (2015) Cellulose hydrolysis in acidified LiBr molten salt hydrate media. Ind Eng Chem Res 54:5226–5236. https://doi.org/10.1021/acs.iecr.5b00757
Etim UJ, Bai P, Wang Y, Subhan F, Liu Y, Yan Z (2019) Mechanistic insights into structural and surface variations in Y-type zeolites upon interaction with binders. Appl Catal A 571:137–149. https://doi.org/10.1016/j.apcata.2018.12.013
Ferreira Madeira F, Ben Tayeb K, Pinard L, Vezin H, Maury S, Cadran N (2012) Ethanol transformation into hydrocarbons on ZSM-5 zeolites: influence of Si/Al ratio on catalytic performances and deactivation rate. Study of the radical species role. Appl Catal A 443–444:171–180. https://doi.org/10.1016/j.apcata.2012.07.037
Franzyshen SK, Schiavelli MD, Stocker KD, Ingram MD (1990) Proton acidity and chemical reactivity in molten salt hydrates. J Phys Chem 94:2684–2688. https://doi.org/10.1021/j100369a082
Gonzalez-Rivera J, Galindo-Esquivel IR, Onor M, Bramanti E, Longo I, Ferrari C (2014) Heterogeneous catalytic reaction of microcrystalline cellulose in hydrothermal microwave-assisted decomposition: effect of modified zeolite Beta. Green Chem 16:1417–1425. https://doi.org/10.1039/c3gc42207k
Guo Y, Sun T, Liu X, Ke Q, Wei X, Gu Y, Wang S (2019) Cost-effective synthesis of CHA zeolites with controllable morphology and size. Chem Eng J 358:331–339. https://doi.org/10.1016/j.cej.2018.10.007
Hammerer F, Loots L, Do JL, Therien JPD, Nickels CW, Friscic T, Auclair K (2018) Solvent-free enzyme activity: quick, high-yielding mechanoenzymatic hydrolysis of cellulose into glucose. Angew Chemie-Int Edn 57:2621–2624. https://doi.org/10.1002/anie.201711643
Huang Y-B, Fu Y (2013) Hydrolysis of cellulose to glucose by solid acid catalysts. Green Chem 15:1095–1111. https://doi.org/10.1039/C3GC40136G
Huang L et al (2019) Enhanced hydrolysis of cellulose by catalytic polyethersulfone membranes with straight-through catalytic channels. Biores Technol 294:122119. https://doi.org/10.1016/j.biortech.2019.122119
Ji Y, Yang H, Yan W (2019) Effect of alkali metal cations modification on the acid/basic properties and catalytic activity of ZSM-5 in cracking of supercritical n-dodecane. Fuel 243:155–161. https://doi.org/10.1016/j.fuel.2019.01.105
Jiang C-W, Zhong X, Luo Z-H (2014) An improved kinetic model for cellulose hydrolysis to 5-hydroxymethylfurfural using the solid SO42 −/Ti-MCM-41 catalyst. RSC Adv 4:15216–15224. https://doi.org/10.1039/C4RA00167B
Jiang L-q, Zheng A-q, Meng J-g, Wang X-b, Zhao Z-l, Li H-b (2019) A comparative investigation of fast pyrolysis with enzymatic hydrolysis for fermentable sugars production from cellulose. Biores Technol 274:281–286. https://doi.org/10.1016/j.biortech.2018.11.098
Kim KD, Wang Z, Jiang Y, Hunger M, Huang J (2019) The cooperative effect of Lewis and Brønsted acid sites on Sn-MCM-41 catalysts for the conversion of 1,3-dihydroxyacetone to ethyl lactate. Green Chem 21:3383–3393. https://doi.org/10.1039/C9GC00820A
Li N, Pan X, Alexander J (2016) A facile and fast method for quantitating lignin in lignocellulosic biomass using acidic lithium bromide trihydrate (ALBTH). Green Chem 18:5367–5376. https://doi.org/10.1039/C6GC01090C
Li N, Li Y, Yoo CG, Yang X, Lin X, Ralph J, Pan X (2018a) An uncondensed lignin depolymerized in the solid state and isolated from lignocellulosic biomass: a mechanistic study. Green Chem 20:4224–4235. https://doi.org/10.1039/C8GC00953H
Li X, Peng K, Xia Q, Liu X, Wang Y (2018b) Efficient conversion of cellulose into 5-hydroxymethylfurfural over niobia/carbon composites. Chem Eng J 332:528–536. https://doi.org/10.1016/j.cej.2017.06.105
Liao Y, Pang Z, Pan X (2019) Fabrication and mechanistic study of aerogels directly from whole biomass. ACS Sustain Chem Eng 7:17723–17736. https://doi.org/10.1021/acssuschemeng.9b04032
Marianou AA, Michailof CM, Pineda A, Iliopoulou EF, Triantafyllidis KS, Lappas AA (2018) Effect of Lewis and Brønsted acidity on glucose conversion to 5-HMF and lactic acid in aqueous and organic media. Appl Catal A 555:75–87. https://doi.org/10.1016/j.apcata.2018.01.029
Mu B, Xu H, Li W, Yang Y (2019) Quantitation of fast hydrolysis of cellulose catalyzed by its substituents for potential biomass conversion. Biores Technol 273:305–312. https://doi.org/10.1016/j.biortech.2018.11.039
Onda A, Ochi T, Yanagisawa K (2008) Selective hydrolysis of cellulose into glucose over solid acid catalysts. Green Chem 10:1033–1037. https://doi.org/10.1039/B808471H
Rinaldi R, Schuth F (2010) Acid hydrolysis of cellulose as the entry point into biorefinery schemes. Chemsuschem 3:296. https://doi.org/10.1002/cssc.201090010
Saeman JF (1945) Kinetics of wood saccharification - hydrolysis of cellulose and decomposition of sugars in dilute acid at high temperature. Ind Eng Chem 37:43–52. https://doi.org/10.1021/ie50421a009
Shrotri A, Kobayashi H, Fukuoka A (2018) Cellulose depolymerization over heterogeneous catalysts. Acc Chem Res 51:761–768. https://doi.org/10.1021/acs.accounts.7b00614
Shuai L, Yang Q, Zhu JY, Lu FC, Weimer PJ, Ralph J, Pan XJ (2010) Comparative study of SPORL and dilute-acid pretreatments of spruce for cellulosic ethanol production. Biores Technol 101:3106–3114. https://doi.org/10.1016/j.biortech.2009.12.044
Swift TD, Nguyen H, Erdman Z, Kruger JS, Nikolakis V, Vlachos DG (2016) Tandem Lewis acid/Brønsted acid-catalyzed conversion of carbohydrates to 5-hydroxymethylfurfural using zeolite beta. J Catal 333:149–161. https://doi.org/10.1016/j.jcat.2015.10.009
Woolery GL, Kuehl GH, Timken HC, Chester AW, Vartuli JC (1997) On the nature of framework Brønsted and Lewis acid sites in ZSM-5. Zeolites 19:288–296. https://doi.org/10.1016/S0144-2449(97)00086-9
Wu T, Yuan G, Chen S, Xue Y, Li S (2017) Synthesis of ZSM-5 and its application in butylene catalytic cracking. J Fuel Chem Technol 45:182–188. https://doi.org/10.1016/S1872-5813(17)30013-0
Wu T, Yuan G, Chen S-L, Zhao D, Xu J, Fan T, Cao Y (2018) Butylene catalytic cracking to propylene over a hierarchical HZSM-5 zeolite: location of acid sites controlling the reaction pathway. Mol Catal 453:161–169. https://doi.org/10.1016/j.mcat.2018.04.026
Xiang M, Wu D (2019) Facile preparation of pore- and morphology-controllable ETS-10 zeolite with enhanced biomass hydrogenation activity. Chem Eng J 369:180–194. https://doi.org/10.1016/j.cej.2019.03.058
Xue N et al (2018) Hydrolysis of zeolite framework aluminum and its impact on acid catalyzed alkane reactions. J Catal 365:359–366. https://doi.org/10.1016/j.jcat.2018.07.015
Yang XH, Li N, Lin XL, Pan XJ, Zhou YH (2016) Selective cleavage of the aryl ether bonds in lignin for depolymerization by acidic lithium bromide molten salt hydrate under mild conditions. J Agric Food Chem 64:8379–8387. https://doi.org/10.1021/acs.jafc.6b03807
Yu J, Wang J, Wang Z, Zhou M, Wang H (2018) Catalytic performance of silicalite-1 modified HY zeolite in the hydrolysis of cellulose. J Fuel Chem Technol 46:1447–1453. https://doi.org/10.1016/S1872-5813(18)30058-6
Zhang Z, Zhao ZK (2009) Solid acid and microwave-assisted hydrolysis of cellulose in ionic liquid. Carbohyd Res 344:2069–2072. https://doi.org/10.1016/j.carres.2009.07.011
Zhou L, Liu Z, Shi M, Du S, Su Y, Yang X, Xu J (2013) Sulfonated hierarchical H-USY zeolite for efficient hydrolysis of hemicellulose/cellulose. Carbohyd Polym 98:146–151. https://doi.org/10.1016/j.carbpol.2013.05.074
Acknowledgments
This study was supported by National Science Foundation (NSF) (CBET 1703519). The Chinese Scholarship Council supported Tao Wu for his visiting study and research at University of Wisconsin-Madison.
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XP initiated this study. All authors contributed to the study conception and design. Material preparation, data collection, and analysis were performed by TW and XP. The first draft of the manuscript was prepared by TW, and all authors commented and revised the manuscript. All authors read and approved the final manuscript.
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The online version of this article contains supplementary material. Detailed synthetic process of ZSM-5 zeolite; relative crystallization, crystal size and SEM images of zeolites; Control experiments of cellulose hydrolysis; Correlation between glucose yield and Beta-30 loading at 120 °C and 0.5 h; Py-FTIR spectra and acidity of used zeolites and regenerated zeolites. (DOCX 601 kb)
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Wu, T., Li, N., Pan, X. et al. Homogenous hydrolysis of cellulose to glucose in an inorganic ionic liquid catalyzed by zeolites. Cellulose 27, 9201–9215 (2020). https://doi.org/10.1007/s10570-020-03411-3
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DOI: https://doi.org/10.1007/s10570-020-03411-3