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Kinetic Modeling and Mechanisms of Acid-Catalyzed Delignification of Sugarcane Bagasse by Aqueous Acetic Acid

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Abstract

Organosolv pretreatment of lignocellulose pertains to a biomass fractionation process to obtain cellulosic pulp, high-purity lignin, and hemicellulosic syrup. In the present work, sugarcane bagasse was delignified by aqueous acetic acid (AcH) under atmospheric pressure with addition of sulfuric acid (SA) as a catalyst. Based on the multilayered structure of plant cell wall and the inhibitive effect of dissolved lignin on delignification rate, a novel pseudo-homogeneous kinetic model was proposed by introducing the concept of “potential degree of delignification (d D)” into the model. It was found that delignification rate was a first-order reaction with respect to SA concentration, while AcH concentration showed a high reaction order to delignification rate. The activation energy for delignification was determined to be 64.41 kJ/mol. The relationships of kinetic constants and d D with reaction temperature, AcH, and SA concentrations were determined according to experimental data. Mechanism analysis indicated that cleavage of α-aryl ethers bonds were mainly responsible for the formation of lignin fragments. AcH concentration affected the solubility parameter (δ value) of AcH solution and the ability to form hydrogen bonds with lignin fragments. Therefore, the driving force for solubilizing lignin fragments increased with AcH concentration, and thus AcH concentration had a very significant influence on delignification rate.

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References

  1. Lau MW, Bals BD, Chundawat SPS, Jin M, Gunawan C, Balan V et al (2012) An integrated paradigm for cellulosic biorefineries: utilization of lignocellulosic biomass as self-sufficient feedstocks for fuel, food precursors and saccharolytic enzyme production. Energy Environ Sci. doi:10.1039/C2EE03596K

  2. Chundawat SPS, Donohoe BS, LdC S, Elder T, Agarwal UP, Lu F et al (2011) Multi-scale visualization and characterization of plant cell wall deconstruction during thermochemical pretreatment. Energy Environ Sci 4(3):973–984

    Article  CAS  Google Scholar 

  3. Zhao X, Cheng K, Liu D (2009) Organosolv pretreatment of lignocellulosic biomass for enzymatic hydrolysis. Appl Microbiol Biotechnol 82(5):815–827

    Article  PubMed  CAS  Google Scholar 

  4. Pan XJ, Sano Y (1999) Atmospheric acetic acid pulping of rice straw IV: physico-chemical characterization of acetic acid lignins from rice straw and woods. Part 1. Physical characteristics. Holzforschung 53(5):511–518

    Article  CAS  Google Scholar 

  5. Pan XJ, Sano Y (1999) Acetic acid pulping of wheat straw under atmospheric pressure. J Wood Sci 45(4):319–325

    Article  CAS  Google Scholar 

  6. Nimz HH, Granzow C, Berg A (1986) Acetosolv pulping. Holz Roh Werkstoff 44:362

    Article  CAS  Google Scholar 

  7. Nimz HH, Berg A, Granzow C, Casten R, Muladi S (1989) Pulping and bleaching by the acetosolv process. Papier 43(l0A):Vl02–Vl08

    Google Scholar 

  8. Nimz HH, Schöne M (1993) Non waste pulping and bleaching with acetic acid. In: Proc. 7th International Symposium on Wood and Pulping Chemistry, Vol. I. Beijing. pp. 258–265

  9. Zhao X, Liu D (2011) Fractionating pretreatment of sugarcane bagasse for increasing the enzymatic digestibility of cellulose. Chin J Biotechnol 27(3):384–392

    CAS  Google Scholar 

  10. Zhao X, Liu D (2010) Chemical and thermal characteristics of lignins isolated from Siam weed stem by acetic acid and formic acid delignification. Ind Crops Prod 32(3):284–291

    Article  CAS  Google Scholar 

  11. Parajo JC, Alonso JL, Santos V (1995) Kinetics of eucalyptus wood fractionation in acetic acid–HCl–water media. Bioresour Technol 51(2):153–162

    Article  CAS  Google Scholar 

  12. Vázquez G, Antorrena G, González J (1994) Kinetics and mechanism of acetic acid pulping of detannined Pinus pinaster bark. Wood Sci Technol 28(6):403–408

    Article  Google Scholar 

  13. Vázquez G, Antorrena G, González J (1995) Kinetics of acid-catalysed delignification of Eucalyptus globulus wood by acetic acid. Wood Sci Technol 29(4):267–275

    Article  Google Scholar 

  14. Vázquez G, Antorrena G, González J, Freire S, Lopez S (1997) Acetosolv pulping of pine wood. Kinetic modelling of lignin solubilization and condensation. Bioresour Technol 59(2–3):121–127

    Article  Google Scholar 

  15. Dapía S, Santos V, Parajó JC (2002) Study of formic acid as an agent for biomass fractionation. Biomass Bioenergy 22(3):213–221

    Article  Google Scholar 

  16. Fan Y (2007) Delignification mechanism and chemical reactions in the formic acid pulping process of wheat straw. PhD thesis, Beijing Forestry University

  17. Tu Q, Fu S, Zhan H, Chai X, Lucia LA (2008) Kinetic modeling of formic acid pulping of bagasse. J Agric Food Chem 56(9):3097–3101

    Article  PubMed  CAS  Google Scholar 

  18. Villaverde JJ, Ligero P, de Vega A (2010) Formic and acetic acid as agents for a cleaner fractionation of Miscanthus × giganteus. J Cleaner Prod 18(4):395–401

    Article  Google Scholar 

  19. Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D et al (2008) Laboratory Analytical Procedure (LAP), National Renewable Energy Laboratory

  20. Zhao X, Zhou Y, Liu D (2012) Kinetic model for glycan hydrolysis and formation of monosaccharides during dilute acid hydrolysis of sugarcane bagasse. Bioresour Technol 105:160–168

    Article  PubMed  CAS  Google Scholar 

  21. Zhao X, Zhang L, Liu D (2012) Biomass recalcitrance. Part I: the chemical compositions and physical structures affecting the enzymatic hydrolysis of lignocellulose. Biofuels Bioprod Biorefin. doi:10.1002/bbb.1333

  22. Muurinen E (2000) Organosolv pulping—a review and distillation study related to peroxyacid pulping. PhD thesis, University of Oulu

  23. Chen N (2004) Studies on delignification mechanism and kinetics of formic acid based wheat straw cooking processes. Master thesis, Beijing Forestry University

  24. Wang IC, Kuo ML, Ku YC (1993) Alcohol pulping of plantation Taiwania and Eucalyptus part II. Scanning electron microscope observations. Bull Taiwan Forest Res Inst 8:177–185

    Google Scholar 

  25. Paszner L, Behera NC (1989) Topochemistry of softwood delignification by alkali earth metal salt catalyzed organosolv pulping. Holzforschung 43:159–168

    Article  CAS  Google Scholar 

  26. Zhao X, Zhang T, Zhou Y, Liu D (2007) Preparation of peracetic acid from hydrogen peroxide. Part I: kinetics for peracetic acid synthesis and hydrolysis. J Mol Catal A Chem 271(1–2):246–252

    Article  CAS  Google Scholar 

  27. Zhao X, Cheng K, Hao J, Liu D (2008) Preparation of peracetic acid from hydrogen peroxide, part II: kinetics for spontaneous decomposition of peracetic acid in the liquid phase. J Mol Catal A Chem 284(1–2):58–68

    Article  CAS  Google Scholar 

  28. Sama KB (1998) Lignin depolymerization and condensation during acidic organosolv delignification of Norway spruce (Picea abies). PhD thesis, State University of New York

  29. McDonough TJ (1993) The chemistry of organosolv delignification. TAPPI J 76(8):186–193

    CAS  Google Scholar 

  30. Xu F, Sun RC, Zhan HY (2004) Progress of organosolv pulping. Trans Chin Pulp Pap 19(2):152–156

    CAS  Google Scholar 

  31. Feng J, Glasser WG (1986) The chemical structure of bagasse lignin. Chin Pulp Pap 5(3):10–18

    CAS  Google Scholar 

  32. Ni Y, Hu Q (1995) Alcell lignin solubility in ethanol–water mixtures. J Appl Polym Sci 57(12):1441–1446

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors are grateful for the support of this work by the National Natural Science Foundation of China (No. 21106081), National Basic Research Program of China (973 Program) (No. 2011CB707406), and International Cooperation Project of the Ministry of Science and Technology of China (No. 2010DFB40170).

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  1. Xuebing Zhao

    Present address: Institute of Applied Chemistry, Department of Chemical Engineering, Tsinghua University, Haidian District, Beijing, 100084, China

Authors and Affiliations

  1. Institute of Applied Chemistry, Department of Chemical Engineering, Tsinghua University, Haidian District, Beijing, 100084, China

    Dehua Liu

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Correspondence to Xuebing Zhao.

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Zhao, X., Liu, D. Kinetic Modeling and Mechanisms of Acid-Catalyzed Delignification of Sugarcane Bagasse by Aqueous Acetic Acid. Bioenerg. Res. 6, 436–447 (2013). https://doi.org/10.1007/s12155-012-9265-4

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