Skip to main content

Advertisement

SpringerLink
Log in

Catalytic Performances of Various Solid Catalysts and Metal Halides for Microwave-Assisted Hydrothermal Conversion of Xylose, Xylan, and Straw to Furfural

  • Original Paper
  • Published:
Waste and Biomass Valorization Aims and scope Submit manuscript

Abstract

Purpose

Furfural is a multifunctional green chemical and a precursor for many furan-based chemicals. The drawbacks of the current furfural production on industrial scale are the processes with low yields, and the corrosive and non-environmental catalysts are being used in the processes. Here, the one pot catalytic conversion of xylose, xylan, and straw biomass (i.e., wheat straw, triticale straw and flax shives) to furfural was investigated in the only single-phase aqueous system using various solid catalysts and metal halides under microwave irradiation.

Methods

Four different solid catalysts (i.e., Amberlyst®-15 dry, Amberlyst®-36, Nafion®-NR50, and DOWEX 50WX8-200) were tested at selected ranges of temperatures (120–180 °C). Catalytic performance of 14 metal halides (i.e., FeCl3, LaCl3, CrCl3, AlCl3, NiCl2, MnCl2, MgCl2, CaCl2, LiCl, NaCl, KCl, LiBr, LiI, and NaBr) was evaluated at 180 °C. A substrate:liquid ratio of 1:15, a catalyst loading of 10% (w/w), a residence time of 20 min were employed as the fixed microwave process conditions.

Results

The Amberlyst-36 wet was the most efficient heterogeneous catalyst for the conversion of xylose at 180 °C, which resulted in a furfural yield of 25.34%. However, for the conversion of xylan under same reaction conditions, only ~ 1% furfural yield was observed. Among metal halides, FeCl3 was the best catalyst for the microwave-assisted hydrothermal conversion of wheat straw, triticale straw and flax shives to furfural with yields of 35.3, 41.6, and 65.3%, respectively.

Conclusions

Microwave-assisted hydrothermal treatment in the presence of FeCl3 can be applied for both the saccharification of straw biomass and production of furfural from straw biomass.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2

Similar content being viewed by others

References

  1. Himmel, M.E., Ding, S.-Y., Johnson, D.K., Adney, W.S., Nimlos, M.R., Brady, J.W., Foust, T.D.: Biomass recalcitrance: engineering plants and enzymes for biofuels production. Science 315, 804–807 (2007)

    Article  Google Scholar 

  2. Zhou, C.-H., Xia, X., Lin, C.-X., Tong, D.-S., Beltramini, J.: Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels. Chem. Soc. Rev. 40, 5588–5617 (2011)

    Article  Google Scholar 

  3. Zeitsch, K.J.: The Chemistry and Technology of Furfural and Its Many By-Products (Sugar Series 13). Elsevier, Amsterdam (2000)

    Google Scholar 

  4. Kamireddy, S.R., Li, J., Tucker, M., Degenstein, J., Ji, Y.: Effects and mechanism of metal chloride salts on pretreatment and enzymatic digestibility of corn stover. Ind. Eng. Chem. Res. 52, 1775–1782 (2013)

    Article  Google Scholar 

  5. Dallinger, D., Kappe, C.O.: Microwave-assisted synthesis in water as solvent. Chem. Rev. 107, 2563–2591 (2007)

    Article  Google Scholar 

  6. Richel, A., Jacquet, N.: Microwave-assisted thermochemical and primary hydrolytic conversions of lignocellulosic resources: a review. Biomass Convers. Biorefinery 5, 115–124 (2015)

    Google Scholar 

  7. Moreau, C., Durand, R., Peyron, D., Duhamet, J., Rivalier, P.: Selective preparation of furfural from xylose over microporous solid acid catalysts. Ind. Crops. Prod. 7, 95–99 (1998)

    Article  Google Scholar 

  8. Marcotullio, G., De Jong, W.: Chloride ions enhance furfural formation from d-xylose in dilute aqueous acidic solutions. Green Chem. 12, 1739–1746 (2010)

    Article  Google Scholar 

  9. Agirrezabal-Telleria, I., Larreategui, A., Requies, J., Güemez, M.B., Arias, P.L.: Furfural production from xylose using sulfonic ion-exchange resins (Amberlyst) and simultaneous stripping with nitrogen. Bioresour. Technol. 102, 7478–7485 (2011)

    Article  Google Scholar 

  10. Weingarten, R., Tompsett, G.A., Conner, W.C., Huber, G.W.: Design of solid acid catalysts for aqueous-phase dehydration of carbohydrates: the role of Lewis and Brønsted acid sites. J. Catal. 279, 174–182 (2011)

    Article  Google Scholar 

  11. Qi, X., Watanabe, M., Aida, T.M., Smith, R.L.: Fast transformation of glucose and di-/polysaccharides into 5-hydroxymethylfurfural by microwave heating in an ionic liquid/catalyst system. ChemSusChem 3, 1071–1077 (2010)

    Article  Google Scholar 

  12. Zhang, Z., Zhao, Z.K.: Microwave-assisted conversion of lignocellulosic biomass into furans in ionic liquid. Bioresour. Technol. 101, 1111–1114 (2010)

    Article  Google Scholar 

  13. Sluiter, J.B., Ruiz, R.O., Scarlata, C.J., Sluiter, A.D., Templeton, D.W.: Compositional analysis of lignocellulosic feedstocks. 1. Review and description of methods. J. Agric. Food Chem. 58, 9043–9053 (2010)

    Article  Google Scholar 

  14. Yemiş, O., Mazza, G.: Acid-catalyzed conversion of xylose, xylan and straw into furfural by microwave-assisted reaction. Bioresour.Technol. 102, 7371–7378 (2011)

    Article  Google Scholar 

  15. AOAC: Official Method 960.16, Furfural in Distilled Liquor, Official Methods of Analysis, 18th edn. AOAC International, Gaithersburg (2005)

    Google Scholar 

  16. Thammasouk, K., Tandjo, D., Penner, M.H.: Influence of extractives on the analysis of herbaceous biomass. J. Agric. Food Chem. 45, 437–443 (1997)

    Article  Google Scholar 

  17. Guenic, L.S.: Dehydration in aqueous media (2015)

  18. Guenic, L.S., Gergela, D., Celablos, C., Delbecq, F., Len, C.: Furfural production from D-xylose and xylan by using stable Nafion NR50 and NaCl in a microwave-assisted biphasic reaction. Molecules 21, 1102–1112 (2016)

    Article  Google Scholar 

  19. O’Neil, R., Ahmad, M.N., Vanoye, L., Aiouache, F.: Kinetics of aqueous phase dehydration of xylose into furfural catalyzed by ZSM-5 zeolite. Ind. Eng. Chem. Res. 48, 4300–4306 (2009)

    Article  Google Scholar 

  20. Rinaldi, R., Schüth, F.: Design of solid catalysts for the conversion of biomass. Energy Environ. Sci. 2, 610–626 (2009)

    Article  Google Scholar 

  21. Ando, H., Sakaki, T., Kokusho, T., Shibata, M., Uemura, Y., Hatate, Y.: Decomposition behavior of plant biomass in hot-compressed water. Ind. Eng. Chem. Res. 39, 3688–3693 (2000)

    Article  Google Scholar 

  22. Möller, M., Harnisch, F., Schröder, U.: Microwave-assisted hydrothermal degradation of fructose and glucose in subcritical water. Biomass Bioenergy 39, 389–398 (2012)

    Article  Google Scholar 

  23. Möller, M., Schröder, U.: Hydrothermal production of furfural from xylose and xylan as model compounds for hemicelluloses. RSC Adv. 3, 22253–22260 (2013)

    Article  Google Scholar 

  24. Guenic, S.L., Delbecq, F., Ceballos, C., Len, C.: Microwave-assisted dehydration of D-xylose into furfural by diluted inexpensive inorganic salts solution in a biphasic system. J. Mol. Catal. A 410, 1–7 (2015)

    Article  Google Scholar 

  25. Rasrendra, C.B., Makertihartha, I.G.B.N., Adisasmito, S., Heeres, H.J.: Green chemicals from D-glucose: systematic studies on catalytic effects of inorganic salts on the chemo-selectivity and yield in aqueous solutions. Top. Catal. 53, 1241–1247 (2010)

    Article  Google Scholar 

  26. Yang, Y., Hu, C.-W., Abu-Omar, M.M.: Synthesis of furfural from xylose, xylan, and biomass using AlCl3⋅6 H2O in biphasic media via xylose isomerization to xylulose. ChemSusChem 5, 405–410 (2012)

    Article  Google Scholar 

  27. Choudhary, V., Sandler, S.I., Vlachos, D.G.: Conversion of xylose to furfural using Lewis and Brønsted acid catalysts in aqueous media. ACS Catal. 2, 2022–2028 (2012)

    Article  Google Scholar 

  28. Choudhary, V., Mushrif, S.H., Ho, C., Anderko, A., Nikolakis, V., Marinkovic, N.S., Frenkel, A.I., Sandler, S.I., Vlachos, D.G.: Insights into the interplay of lewis and Brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media. J. Am. Chem. Soc. 135, 3997–4006 (2013)

    Article  Google Scholar 

  29. Peng, L., Lin, L., Zhang, J., Zhuang, J., Zhang, B., Gong, Y.: Catalytic conversion of cellulose to levulinic acid by metal chlorides. Molecules 15, 5258–5272 (2010)

    Article  Google Scholar 

  30. Liu, C., Wyman, C.E.: The enhancement of xylose monomer and xylotriose degradation by inorganic salts in aqueous solutions at 180 °C. Carbohydr. Res. 341, 2550–2556 (2006)

    Article  Google Scholar 

  31. Loow, Y.L., Wu, T.Y., Tan, K.A., Lim, Y.S., Siow, L.F., Jahim, M.J., Mohammad, A.W., Teoh, W.H.: Recent advances in the application of inorganic salt pretreatment for transforming lignocellulosic biomass into reducing sugars. J. Agric. Food Chem. 63, 8349–8363 (2015)

    Article  Google Scholar 

  32. Marcotullio, G., De Jong, W.: Furfural formation from D-xylose: the use of different halides in dilute aqueous acidic solutions allows for exceptionally high yields. Carbohydr. Res. 346, 1291–1293 (2011)

    Article  Google Scholar 

  33. Hellman, H., Laitinen, R.S., Kaila, L., Jalonen, J., Hietapelto, V., Jokela, J., Sarpola, A., Rämö, J.: Identification of hydrolysis products of FeCl3·6H2O by ESI-MS. J. Mass Spectrom. 41, 1421–1429 (2006)

    Article  Google Scholar 

  34. Pińkowska, H., Wolak, P., Złocińska, A.: Hydrothermal decomposition of xylan as a model substance for plant biomass waste—hydrothermolysis in subcritical water. Biomass Bioenergy 35, 3902–3912 (2011)

    Article  Google Scholar 

  35. Yan, Y., Li, T., Ren, Z., Li, G.: A study on catalytic hydrolysis of peat. Bioresour. Technol. 57, 269–273 (1996)

    Article  Google Scholar 

  36. Liu, L., Sun, J., Cai, C., Wang, S., Pei, H., Zhang, J.: Corn stover pretreatment by inorganic salts and its effects on hemicellulose and cellulose degradation. Bioresour. Technol. 100, 5865–5871 (2009)

    Article  Google Scholar 

  37. Liu, L., Sun, J., Li, M., Wang, S., Pei, H., Zhang, J.: Enhanced enzymatic hydrolysis and structural features of corn stover by FeCl3 pretreatment. Bioresour. Technol. 100, 5853–5858 (2009)

    Article  Google Scholar 

Download references

Acknowledgements

The technical aid of Lana Fukumoto and David Godfrey is gratefully acknowledged. The authors would also like to thank the anonymous reviewers for their constructive criticisms and suggestions. Oktay Yemis thanks the Scientific and Technological and Research Council of Turkey (TUBITAK) for the scholarship (BIDEB-2219, Postdoctoral Research Scholarship).

Author information

Authors and Affiliations

  1. Summerland Research and Development Centre, Agriculture and Agri-Food Canada, 4200 Highway 97, Summerland, BC, V0H 1Z0, Canada

    Oktay Yemiş & Giuseppe Mazza

  2. Department of Food Engineering, Faculty of Engineering, Sakarya University, Esentepe Campus, 54187, Serdivan, Sakarya, Turkey

    Oktay Yemiş

  3. Mazza Innovation Ltd., 7901 Progress Way, Delta, BC, V4G 1A3, Canada

    Giuseppe Mazza

Authors
  1. Oktay Yemiş
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Giuseppe Mazza
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Oktay Yemiş.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 320 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yemiş, O., Mazza, G. Catalytic Performances of Various Solid Catalysts and Metal Halides for Microwave-Assisted Hydrothermal Conversion of Xylose, Xylan, and Straw to Furfural. Waste Biomass Valor 10, 1343–1353 (2019). https://doi.org/10.1007/s12649-017-0144-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12649-017-0144-2

Keywords

Search

Navigation