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Licensed Unlicensed Requires Authentication Published by De Gruyter September 8, 2018

Kinetic study on the decomposition of cellulose into 5-hydroxymethylfurfural in an ionic liquid/organic biphasic system

Heng Zhang EMAIL logo , Zhe Wang , Heng Yang and Hongyan Yang

Abstract

The kinetics of cellulose decomposition in an ionic liquid/organic solvent were investigated using microcrystalline cellulose as the raw material. Curve fitting of the cellulose degradation kinetic data was conducted using MATLAB. Results indicated that the catalytic decomposition reactions of cellulose, glucose and 5-hydroxymethylfurfural (5-HMF), along with the diffusion process of 5-HMF, were all first-order reactions in the biphasic system. The decomposition rate constants of cellulose, glucose and 5-HMF, along with the diffusion coefficient of 5-HMF (k5), in the biphasic system were obtained using the first-order reaction model. The organic solvent could suppress the formation of by-products to a certain extent and reduced the activation energy of cellulose, glucose and 5-HMF degradation by 4.24 %, 5.17 % and 3.73 %, respectively, compared with cellulose degradation in ionic liquid. The amount of organic solvent had little effect on glucose yield within the optimum reaction time and did not ascertain the presence of glucose in the organic solvent. k5 was relatively small and increased with an increase in temperature, reaction time and amounts of [BMIM]Cl, catalyst and organic solvent, with temperature exerting the greatest effect.

Award Identifier / Grant number: ZR2017MC032

Funding statement: This work was supported by Shandong Provincial Natural Science Foundation of China (Grant No. ZR2017MC032), open fund of Key Laboratory of Biomass Energy and Materials of Jiangsu Province (JSBEM201808).

  1. Conflict of interest: The authors declare no conflicts of interest.

References

Bhat, M. K., Bhat, S. (1997) Cellulose degrading enzymes and their potential industrial application. Biotechnol. Adv. 15(3–4):583–620.10.1016/S0734-9750(97)00006-2Search in Google Scholar

Bicker, M., Hirth, J., Vogel, H. (2003) Dehydration of fructose to 5-hydroxymethylfurfural in sub- and supercritical acetone. Green Chem. 5(2):280–284.10.1039/b211468bSearch in Google Scholar

Binder, J. B., Raines, R. T. (2009) Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals. J. Am. Chem. Soc. 131(5):1979–1985.10.1021/ja808537jSearch in Google Scholar PubMed

Bradbury, A. G. W., Sakai, Y., Shafizadeh, F. (1979) A kinetic model for pyrolysis of cellulose. J. Appl. Polym. Sci. 23(11):3271–3280.10.1002/app.1979.070231112Search in Google Scholar

Fang, Z. F., Liu, B., Luo, J. J., Ren, Y. S., Zhang, Z. H. (2014) Efficient conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed by the chromium-exchanged montmorillonite K-10 clay. Biomass Bioenergy 60(350):171–177.10.1016/j.biombioe.2013.12.002Search in Google Scholar

Girisuta, B., Janssen, L. P. B. M., Heeres, H. J. (2007) Kinetic Study on the Acid-Catalyzed Hydrolysis of Cellulose to Levulinic Acid. Ind. Eng. Chem. Res. 46(6):1696–1708.10.1021/ie061186zSearch in Google Scholar

Jae, J., Zheng, W. Q., Lobo, R. F., Vlachos, D. G. (2013) Production of Dimethylfuran from Hydroxymethylfurfural through Catalytic Transfer Hydrogenation with Ruthenium Supported on Carbon. ChemSusChem 6(7):1158–1162.10.1002/cssc.201300288Search in Google Scholar PubMed

Kim, J. H., Na, J. G., Yang, J. W., Chang, Y. K. (2013) Separation of galactose, 5-hydroxymethylfurfural and levulinic acid in acid hydrolysate of agarose by nanofiltration and electrodialysis. Bioresour. Technol. 140(7):64–72.10.1016/j.biortech.2013.04.068Search in Google Scholar PubMed

Li, Z. Y., Qin, W., Dai, Y. Y. (2002) Liquid−Liquid Equilibria of Acetic, Propionic, Butyric, and Valeric Acids with Trioctylamine as Extractant. J. Chem. Eng. Data 47(4):843–848.10.1021/je015526tSearch in Google Scholar

Li, S., Zhou, Y., Liu, J. Chemical Kinetics. Advanced Education Press, Beijing, China, 2009.Search in Google Scholar

Liu, B., Zhang, Z., Zhao, Z. K. (2013) Microwave-assisted catalytic conversion of cellulose into 5-hydroxymethylfurfural in ionic liquids. Chem. Eng. J. 215–2016(3):517–521.10.1016/j.cej.2012.11.019Search in Google Scholar

Mai, N. L., Ahn, K., Koo, Y. M. (2014a) Methods for recovery of ionic liquids – A review. Process Biochem. 49(5):872–881.10.1016/j.procbio.2014.01.016Search in Google Scholar

Mai, N. L., Ha, S. H., Koo, Y. M. (2014b) Efficient pretreatment of lignocellulose in ionic liquids/co-solvent for enzymatic hydrolysis enhancement into fermentable sugars. Process Biochem. 49(7):1144–1151.10.1016/j.procbio.2014.03.024Search in Google Scholar

Mamo, W., Chebude, Y., MárquezÁlvarez, C., Díaz, I., Sastre, E. (2016) Comparison of glucose conversion to 5-HMF using different modified mordenites in ionic liquid and biphasic media. Catal. Sci. Technol. 6(8):2766–2774.10.1039/C5CY02070KSearch in Google Scholar

Pagàntorres, Y. J., Wang, T., Gallo, J. M. R., Shanks, B. H., Dumesic, J. A. (2012) Production of 5-hydroxymethylfurfural from glucose using a combination of Lewis and Brønsted acid catalysts in water in a biphasic reactor with an alkylphenol solvent. ACS Catal. 2(6):930–934.10.1021/cs300192zSearch in Google Scholar

Pidko, E. A., Degirmenci, V., van Santen, R. A., Hensen, E. J. (2010) Glucose activation by transient Cr2+ dimers. Angew. Chem., Int. Ed. Engl. 49(14):2530–2534.10.1002/anie.201000250Search in Google Scholar PubMed

Remsing, R. C., Swatloski, R. P., et al. (2006) Mechnism of cellulose dissolution in ionic liquid 1-n-butyl-3-methylimidazoluim chloride: a 13C and 35/37Cl NMR relaxation study on model systems. Chem. Commun. 28(12):1271–1273.10.1039/b600586cSearch in Google Scholar PubMed

Román-Leshkov, Y., Chheda, J. N., Dumesic, J. A. (2006) Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science 312(5782):1933–1937.10.1126/science.1126337Search in Google Scholar PubMed

Seddon, K. R., Stark, A., Torres, M. J. (2001) Influence of chloride, water, and organic solvents on the physical properties of ionic liquids. Pure Appl. Chem. 72(12):2275–2287.10.1351/pac200072122275Search in Google Scholar

Shen, Y., Sun, J. K., Yi, Y. X., Li, M. F., et al. (2014) InCl3-catalyzed conversion of carbohydrates into 5-hydroxymethylfurfural in biphasic system. Bioresour. Technol. 172:457–460.10.1016/j.biortech.2014.09.077Search in Google Scholar PubMed

Smay, G. L. (1985) The Characteristics of high-temperature resistant organic polymers and the feasibility of their use as glass coating materials. J. Mater. Sci. 20(4):1494–1500.10.1007/BF01026347Search in Google Scholar

Sun, Y. C., Xu, J. K., Xu, F., Sun, R. C. (2013) Structural comparison and enhanced enzymatic hydrolysis of eucalyptus cellulose via pretreatment with different ionic liquids and catalysts. Process Biochem. 48(5–6):844–852.10.1016/j.procbio.2013.03.023Search in Google Scholar

Sun, J. K., Yuan, X. D., Shen, Y., Yi, Y. X., Wang, B. et al. (2015) Conversion of bamboo fiber into 5-hydroxymethylfurfural catalyzed by sulfamic acid with microwave assistance in biphasic system. Ind. Crop. Prod. 70:266–271.10.1016/j.indcrop.2015.03.044Search in Google Scholar

Tamada, J. A., King, C. J. (1990) Extraction of carboxylic acids with amine extractants. 2. Chemical interactions and interpretation of data. Ind. Eng. Chem. Res. 29(7):1327–1333.10.1021/ie00103a036Search in Google Scholar

Vigier, K. D. O., Benguerba, A., Barrault, J., Jérôme, F. (2011) Conversion of fructose and inulin to 5-hydroxymethylfurfural in sustainable betaine hydrochloride-based media. Green Chem. 14(2):285–289.10.1039/C1GC16236ESearch in Google Scholar

Xu, J. K., Sun, Y. C., Sun, R. C. (2015) Synergistic effects of ionic liquid plus alkaline pretreatments on eucalyptus: Lignin structure and cellulose hydrolysis. Process Biochem. 50(6):955–965.10.1016/j.procbio.2015.03.014Search in Google Scholar

Yan, L., Liu, N., Yu, W., Machida, H., Qi, X. (2014) Production of 5-hydroxymethylfurfural from corn stalk catalyzed by corn stalk-derived carbonaces solid acid catalyst. Bioresour. Technol. 173:462–466.10.1016/j.biortech.2014.09.148Search in Google Scholar PubMed

Yang, L. Yan, X., Xu, S., Chen, H., et al. (2015) One-pot synthesis of 5-hydroxymethylfurfural from carbohydrates using an inexpensive FePO4 catalyst. RSC Adv. 5(26):19900–19906.10.1039/C4RA16145ASearch in Google Scholar

Zhang, Z. H., Zhao, Z. B. K. (2010) Microwave-assisted conversion of lignocellulosic biomass into furans in ionic liquid. Bioresour. Technol. 101(3):1111–1114.10.1016/j.biortech.2009.09.010Search in Google Scholar PubMed

Zhang, Z. H., Wang, W. Q., Liu, X. Y., Wang, Q., et al. (2012) Kinetic study of acid-catalyzed cellulose hydrolysis in 1-butyl-3-methylimidazolium chloride. Bioresour. Technol. 112(3):151–155.10.1016/j.biortech.2012.02.071Search in Google Scholar PubMed

Zhang, H., Song X, Li S. X., Li, P. F., Li, J. X. (2016a) Preparation of 5-(Hydroxymethyl)furfural by the Catalytic Degradation of Cellulose in an Ionic Liquid/Organic Biphasic System. BioResources 11(2):5190–5203.10.15376/biores.11.2.5190-5203Search in Google Scholar

Zhang, H., Li, S. X., Xu, L., Sun, J. H., Li, J. X. (2016b) Kinetic Study of the decomposition of cellulose to 5-Hydroxymethylfurfural in ionic liquid. BioResources 11(2):4268–4280.10.15376/biores.11.2.4268-4280Search in Google Scholar

Zhao, H. B., Holladay, J. E., Brown, H., Zhang, Z. C. (2007) Metal chlorides ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science 316(5831):1597–1600.10.1126/science.1141199Search in Google Scholar PubMed

Zhou, L., Liang, R., Ma, Z., Wu, T., Wu, Y. (2013) Conversion of cellulose to HMF in ionic liquid catalyzed by bifunctional ionic liquids. Bioresour. Technol. 129(2):450–455.10.1016/j.biortech.2012.11.015Search in Google Scholar PubMed

Zhou, J. X., Xia, Z., Huang, T. Y., Yan, P. F., et al. (2015a) An ionic liquid–organics–water ternary biphasic system enhances the 5-hydroxymethylfurfural yield in catalytic conversion of glucose at high concentrations. Green Chem. 17(8):4206–4216.10.1039/C5GC01039JSearch in Google Scholar

Zhou, L. L., He, Y. M., Ma, Z. W., Liang, R. J., Wu, T. H. (2015b) One-step degradation of cellulose to 5-hydroxymethylfurfural in ionic liquid under mild conditions. Carbohydr. Polym. 117:694–700.10.1016/j.carbpol.2014.10.062Search in Google Scholar PubMed

Received: 2018-03-20
Accepted: 2018-06-05
Published Online: 2018-09-08
Published in Print: 2018-09-25

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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