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황산 촉매를 이용한 글루코오스로부터 5-HMF 및 레불린산 생산을 위한 동역학적 연구

Kinetic Study of Glucose Conversion to 5-hydroxymethylfurfural and Levulinic Acid Catalyzed by Sulfuric Acid

  • Han, Seokjun (Department of chemical Engineering, Kyonggi University) ;
  • Lee, Seung Min (Department of chemical Engineering, Kyonggi University) ;
  • Kim, Jun Seok (Department of chemical Engineering, Kyonggi University)
  • 투고 : 2021.08.31
  • 심사 : 2021.12.14
  • 발행 : 2022.05.01

초록

바이오매스로부터 얻는 5-HMF(5-hydroxymethylfurfural)과 레불린산(LA; levulinic acid)는 그린 플랫폼 화학물질로, 폭넓은 응용분야를 가지며 바이오연료 및 바이오 화학물질로써 사용된다. 본 연구에서는, 글루코오스(D-glucose) 분해로부터 레불린산 형성의 kinetic를 다양한 온도 및 황산 농도를 통해 연구하였다. 실험은 황산 촉매(1-3 wt%)을 사용하였으며, 온도(140-200 ℃)는 넓은 범위에서 수행되었다. 글루코오스 용액은 10 ml 황산 용액에 글루코오스 1g을 용해시켜 만들었다. 반응 속도는 온도에 따라 증가하였고 활성화 에너지는 이전에 보고된 값과 유사한 경향을 보였다. 5-HMF의 최대 농도에 대한 반응 시간은 온도가 증가함에 따라 감소하였다. 또한, 산 농도가 증가함에 따라 5-HMF의 분해속도가 빨라졌다. 황산 촉매의 농도가 증가함에 따라 레불린산의 최대 농도에 도달하는 시간이 줄어들었다. 온도를 계속 높이는 것은 레불린산의 최대 농도를 감소시켰고 휴민의 양을 증가시켰다. 결과를 통해 얻은 kinetic parameters는 5-HMF과 레불린산의 mechanism를 이해하는데 도움을 준다. 또한, 이 연구의 결과는 바이오매스에서 고농도의 레불린산 및 5-HMF를 얻어내는데 유용한 정보를 제공한다.

5-HMF(5-Hydroxymethylfurfural) and LA(levulinic acid) derived from biomass are green platform chemicals, which have a wide of potential applications as biofules and biochemicals. In this study, the kinetics of LA formation from glucose decomposition with various concentration of sulfuric acid at different temperature was investigated. The experiments were performed in a broad temperature (140-200 ℃), using H2SO4 (1-3 wt%) as the catalyst. Glucose solution was made by dissolving 1 g of glucose in 10 ml of H2SO4 solution. The reactions rates increased with temperature and the activation energy showed a similar tendency to previous reported values. Reaction time for maximum concentration of 5-HMF decreased as the temperature increased. Furthermore, the decomposition of 5-HMF was fast as the acid concentration increased. Reaction time to reach maximum concentration of levulinic acid was reduced as the acid concentration increased. Continuing to raise the temperature decreased the maximum concentration of levulinic acid and increased the amount of humins. On the basis of results, kinetic parameters help to understand mechanism of LA and 5-HMF. In addition, this study provides useful information to achieve high concentration of LA and 5-HMF from biomass.

키워드

과제정보

본 연구는 2021학년도 경기대학교 대학원 연구원장학생 장학금 지원에 의하여 수행되었음.

참고문헌

  1. Lakshmanan, V. I. and Gorain, B. (Eds.). "Innovations and Breakthroughs in the Gold and Silver Industries: Concepts, Applications and Future Trends," Springer Nature. (2019).
  2. De Corato, U., De Bari, I., Viola, E. and Pugliese, M. "Assessing the Main Opportunities of Integrated Biorefining from Agrobioenergy co/by-products and Agro-industrial Residues Into High-value Added Products Associated to Some Emerging Markets: A Review," Renewable and Sustainable Energy Reviews, 88, 326-346(2018). https://doi.org/10.1016/j.rser.2018.02.041
  3. He, O., Zhang, Y., Wang, P., Liu, L., Wang, Q., Yang, N., Li, W., Champagne, P. and Yu, H., "Experimental and Kinetic Study on the Production of Furfural and HMF from Glucose," Catalysts, 11(1), 11(2021). https://doi.org/10.3390/catal11010011
  4. Ramli, Nur Aainaa Syahirah, and Nor Aishah Saidina Amin. "Optimization of Renewable Levulinic Acid Production from Glucose Conversion Catalyzed by Fe/HY Zeolite Catalyst in Aqueous Medium," Energy Conversion and Management 95, 10-19(2015). https://doi.org/10.1016/j.enconman.2015.02.013
  5. Alonso, D. M., Bond, J. Q. and Dumesic, J. A. "Catalytic Conversion of Biomass to Biofuels," Green Chemistry, 12(9), 1493-1513(2010). https://doi.org/10.1039/c004654j
  6. Rosatella, A. A., Simeonov, S. P., Frade, R. F. and Afonso, C. A. "Hydroxymethylfurfural (HMF) as a Building Block Platform: Biological Properties, Synthesis and Synthetic Applications," Green Chemistry, 13(4), 754-793(2011). https://doi.org/10.1039/c0gc00401d
  7. Tong, X., Ma, Y. and Li, Y. "Biomass into Chemicals: Conversion of Sugars to Furan Derivatives by Catalytic Processes," Applied Catalysis A: General, 385(1-2), 1-13(2010). https://doi.org/10.1016/j.apcata.2010.06.049
  8. Menegazzo, F., Ghedini, E. and Signoretto, M. "5-Hydroxymethylfurfural (HMF) Production from Real Biomasses," Molecules, 23(9), 2201(2018). https://doi.org/10.3390/molecules23092201
  9. Conner, A. H., Wood, B. F., Hill Jr, C. G. and Harris, J. F. "Kinetic Modeling of the Saccharification of Prehydrolyzed Southern Red Oak," Cellulose: Structure, Modification and Hydrolysis, 281-296(1986).
  10. Kabyemela, B. M., Adschiri, T., Malaluan, R. M. and Arai, K. "Glucose and Fructose Decomposition in Subcritical and Supercritical Water: Detailed Reaction Pathway, Mechanisms, and Kinetics," Industrial & Engineering Chemistry Research, 38(8), 2888-2895(1999). https://doi.org/10.1021/ie9806390
  11. Choudhary, V., Mushrif, S. H., Ho, C., Anderko, A., Nikolakis, V., Marinkovic, N. S., Frenkel, A. I., Sandler S. I. and Vlachos, D. G., "Insights into the Interplay of Lewis and Bronsted Acid Catalysts in Glucose and Fructose Conversion to 5-(hydroxymethyl) Furfural and Levulinic Acid in Aqueous Media," Journal of the American Chemical Society, 135(10), 3997-4006(2013). https://doi.org/10.1021/ja3122763
  12. Zhao, Yuan, et al. "Influence of a Lewis Acid and a Bronsted Acid on the Conversion of Microcrystalline Cellulose into 5- hydroxymethylfurfural in a Single-phase Reaction System of Water and 1,2-dimethoxyethane," RSC Advances 8.13, 7235-7242 (2018). https://doi.org/10.1039/C7RA13387A
  13. van Putten, Robert-Jan, et al. "Hydroxymethylfurfural, a Versatile Platform Chemical Made from Renewable Resources," Chemical Reviews 113.3, 1499-1597(2013). https://doi.org/10.1021/cr300182k
  14. Mukherjee, Agneev, Marie-Josee Dumont, and Vijaya Raghavan. "Sustainable Production of Hydroxymethylfurfural and Levulinic Acid: Challenges and Opportunities," Biomass and Bioenergy 72, 143-183(2015). https://doi.org/10.1016/j.biombioe.2014.11.007
  15. Fachri, B. A., Abdilla, R. M., Bovenkamp, H. H. V. D., Rasrendra, C. B. and Heeres, H. J., "Experimental and Kinetic Modeling Studies on the Sulfuric Acid Catalyzed Conversion of d-fructose to 5-hydroxymethylfurfural and Levulinic Acid in Water," ACS Sustainable Chemistry & Engineering, 3(12), 3024-3034(2015). https://doi.org/10.1021/acssuschemeng.5b00023
  16. Weiqi, W. and Shubin, W., "Experimental and Kinetic Study of Glucose Conversion to Levulinic Acid Catalyzed by Synergy of Lewis and Bronsted Acids," Chemical Engineering Journal, 307, 389-398(2017). https://doi.org/10.1016/j.cej.2016.08.099
  17. Girisuta, B., Janssen, L. P. B. M. and Heeres, H. J., "Green Chemicals: A Kinetic Study on the Conversion of Glucose to Levulinic Acid," Chemical Engineering Research and Design 84.5, 339-349(2006). https://doi.org/10.1205/cherd05038
  18. Chang, Chun, Xiaojian, M. A. and Peilin, C. E. N., "Kinetics of Levulinic Acid Formation from Glucose Decomposition at High Temperature," Chinese Journal of Chemical Engineering, 14.5, 708-712(2006). https://doi.org/10.1016/S1004-9541(06)60139-0
  19. Weingarten, Ronen, et al., "Kinetics and Reaction Engineering of Levulinic Acid Production from Aqueous Glucose Solutions," ChemSusChem 5.7, 1280-1290(2012). https://doi.org/10.1002/cssc.201100717
  20. Baugh, Kent D., and Perry L. McCarty, "Thermochemical Pretreatment of Lignocellulose to Enhance Methane Fermentation: I. Monosaccharide and Furfurals Hydrothermal Decomposition and Product Formation Rates," Biotechnology and bioengineering, 31.1, 50-61(1988). https://doi.org/10.1002/bit.260310109