DOI QR코드

DOI QR Code

Clean and Efficient Synthesis of Furfural From Xylose by Microwave-Assisted Biphasic System using Bio-Based Heterogeneous Acid Catalysts

  • Vo, Anh Thi Hoang (Green Process and Material R&D Group, Korea Institute of Industrial Technology (KITECH)) ;
  • Lee, Hong-shik (Green Process and Material R&D Group, Korea Institute of Industrial Technology (KITECH)) ;
  • Kim, Sangyong (Green Process and Material R&D Group, Korea Institute of Industrial Technology (KITECH)) ;
  • Cho, Jin Ku (Green Process and Material R&D Group, Korea Institute of Industrial Technology (KITECH))
  • Received : 2016.10.26
  • Accepted : 2016.11.11
  • Published : 2016.12.30

Abstract

As an attempt to replacing petroleum-based chemicals with bio-based ones, synthesis of furfural from biomass-derived xylose attracts much attention in recent days. Conventionally, furfural from xylose has been produced via the utilization of highly corrosive, toxic, and environmentally unfriendly mineral acids such as sulfuric acid or hydrochloric acid. In this study, microwave-assisted biphasic reaction process in the presence of novel bio-based heterogeneous acid catalysts was developed for the eco-benign and effective synthesis of furfural from xylose. The microwave was irradiated for reaction acceleration and a biphasic system consisting of $H_2O$ : MIBK (1 : 2) was designed for continuous extraction of furfural into the organic phase in order to reduce the undesired side products formed by decomposition/condensation/oligomerization in the acidic aqueous phase. Moreover, sulfonated amorphous carbonaceous materials were prepared from wood powder, the most abundant lignocellulosic biomass. The prepared catalysts were characterized by FT-IR, XPS, BET, elemental analysis and they were used as bio-based heterogeneous acid catalysts for the dehydration of xylose into furfural more effectively. For further optimization, the effect of temperature, reaction time, water/organic solvent ratio, and substrate/catalyst ratio on the xylose conversion and furfural yield were investigated and 100% conversion of xylose and 74% yield of furfural was achieved within 5 h at $180^{\circ}C$. The bio-based heterogeneous acid catalysts could be used three times without any significant loss of activity. This greener protocol provides highly selective conversion of xylose to furfural as well as facile isolation of product and bio-based heterogeneous acid catalysts can alternate the environmentally-burdened mineral acids.

Keywords

References

  1. Geilen, F. M. A., Engendahl, B., Harwardt, A., Marquardt, W., Klankermayer, J., and Leitner, W., "Selective and Flexible Transformation of Biomass-Derived Platform Chemicals by a Multifunctional Catalytic System," Angew. Chem. Int. Ed., 49(32), 5510-5514 (2010). https://doi.org/10.1002/anie.201002060
  2. Wu, C., Chen, W., Zhong, L., Peng, X., Sun, R., Fang, J., and Zheng, S., "Conversion of Xylose into Furfural Using Lignosulfonic Acid as Catalyst in Ionic Liquid," J. Agric. Food Chem., 62(30), 7430-7435 (2014). https://doi.org/10.1021/jf502404g
  3. Menon, V. and Rao, M., "Trends in bioconversion of lignocellulose: Biofuels, platform chemicals & Amp; Biorefinery Concept," Progr. Energy Combust. Sci., 38(4), 522-550 (2012). https://doi.org/10.1016/j.pecs.2012.02.002
  4. Barbosa, B. M., Colodette, J. L., Longue Junior, D., Gomes, F. J. B., and Martino, D. C., "Preliminary Studies on Furfural Production from Lignocellulosics," J. Wood Chem. Technol., 34(3), 178-190 (2014). https://doi.org/10.1080/02773813.2013.844167
  5. Weingarten, R., Cho, J., Conner, J.W. C., and Huber, G. W., "Kinetics of Furfural Production by Dehydration of Xylose in a Biphasic Reactor with Microwave Heating," Green Chem., 12(8), 1423-1429 (2010). https://doi.org/10.1039/c003459b
  6. Yang, W., Li, P., Bo, D., Chang, H., Wang, X., and Zhu, T., "Optimization of Furfural Production from d-xylose with Formic Acid as Catalyst in a Reactive Extraction System," Bioresour. Technol., 133, 361-369 (2013). https://doi.org/10.1016/j.biortech.2013.01.127
  7. Amiri, H., K. Karimi, K., and Roodpeyma, S., "Production of Furans from Rice Straw by Single-Phase and Biphasic Systems," Carbohydr. Res., 345(15), 2133-2138 (2010). https://doi.org/10.1016/j.carres.2010.07.032
  8. Jimenez-Morales, I., Moreno-Recio, M., Santamaria-Gonzalez, J., Maireles-Torres, P., and Jimenez-Lopez, A., "Production of 5-Hydroxymethyl furfural from Glucose using Aluminium Doped MCM-41 Silica as Acid Catalyst," Appl. Catal. B: Environ., 164, 70-76 (2015). https://doi.org/10.1016/j.apcatb.2014.09.002
  9. Weingarten, R., Tompsett, G. A., Conner Jr, W. C., and Huber, G. W., "Design of Solid Acid Catalysts for Aqueous-Phase Dehydration of Carbohydrates: The Role of Lewis and Bronsted Acid Sites," J. Catal., 279(1), 174-182 (2011). https://doi.org/10.1016/j.jcat.2011.01.013
  10. Molina, M. J. C., Granados, M. L., Gervasini, A., and Carniti, P., "Exploitment of Niobium Oxide Effective Acidity for Xylose Dehydration to Furfural," Catal. Today, 254, 90-98 (2015). https://doi.org/10.1016/j.cattod.2015.01.018
  11. vom Stein, T., Grande, P. M., Leitner, W., and de Maria, P. D., "Iron-Catalyzed Furfural Production in Biobased Biphasic Systems: From Pure Sugars to Direct use of Crude Xylose Effluents as Feedstock," ChemSusChem, 4(11), 1592-1594 (2011). https://doi.org/10.1002/cssc.201100259
  12. Lucas-Torres, C., Lorente, A., Cabanas, B., and Moreno, A., "Microwave Heating for the Catalytic Conversion of Melon Rind Waste into Biofuel Precursors," J. Cleaner Prod., 138, Part 1, 59-69 (2016). https://doi.org/10.1016/j.jclepro.2016.03.122
  13. Rathi, A. K., Gawande, M. B., Zboril, R., and Varma, R. S., "Microwave-Assisted Synthesis - Catalytic Applications in Aqueous Media," Coord. Chem. Rev., 291, 68-94 (2015). https://doi.org/10.1016/j.ccr.2015.01.011
  14. Yang, Y., Hu, C. -W., and Abu-Omar, M. M., "Conversion of Carbohydrates and Lignocellulosic Biomass into 5-hydroxymethylfurfural using $AlCl_3{\cdot}6H_2O$ Catalyst in a Biphasic Solvent System," Green Chem., 14(2), 509-513 (2012). https://doi.org/10.1039/C1GC15972K
  15. Suganuma, S., Nakajima, K., Kitano, M., Yamaguchi, D., Kato, H., Hayashi, S., and Hara, M., "Hydrolysis of Cellulose by Amorphous Carbon Bearing $SO_3H$, COOH, and OH Groups," J. Am. Chem. Soc., 130(38), 12787-12793 (2008). https://doi.org/10.1021/ja803983h
  16. Karinen, R., Vilonen, K., and Niemela, M., "Biorefining: Heterogeneously Catalyzed Reactions of Carbohydrates for the Production of Furfural and Hydroxymethylfurfural," Chem-SusChem, 4(8), 1002-1016 (2011).
  17. Zhang, T., Kumar, R., and Wyman, C. E., "Enhanced Yields of Furfural and Other Products by Simultaneous Solvent Extraction During Thermochemical Treatment of Cellulosic Biomass," RSC Adv., 3(25), 9809-9819 (2013). https://doi.org/10.1039/c3ra41857j
  18. Guenic, S. L., Delbecq, F., Ceballos, C., and Len, C., "Microwave-Assisted Dehydration of D-xylose into Furfural by Diluted Inexpensive Inorganic Salts Solution in a Biphasic System," J. Mol. Catal. A: Chem., 410, 1-7 (2015). https://doi.org/10.1016/j.molcata.2015.08.019
  19. Karl, J. Z., The Chemistry and Technology of Furfural and its Many By-Products, Sugar Series Vol. 13, Elsevier, The Netherlands, 2000.
  20. Zhang, T., Li, W., Xu, Z., Liu, Q., Ma, Q., Jameel, H., Chang, H. M., and Ma, L., "Catalytic Conversion of Xylose and Corn Stalk into Furfural over Carbon Solid Acid Catalyst in Gamma-Valerolactone," Bioresour. Technol., 209, 108-114 (2016). https://doi.org/10.1016/j.biortech.2016.02.108