Advertisement

Cellulose

, Volume 18, Issue 6, pp 1499–1507 | Cite as

Thermal transformation of micro-crystalline cellulose in phosphoric acid

  • Gabriella Butera
  • Claudio De Pasquale
  • Antonella Maccotta
  • Giuseppe Alonzo
  • Pellegrino Conte
Article

Abstract

Use of crude oil derivatives such as diesel and gasoline is becoming unsuitable due to their detriment to environment and to the increasing worldwide energy demand which is driving crude oil reservoirs towards exhaustion. Replacement of diesel and gasoline with biofuels (i.e. biodiesel and bioethanol, respectively) is very desirable. In fact, biofuels are not only environmentally sustainable, but also potentially inexhaustible due to the large amounts of waste biomasses from which they can be retrieved. In the present study, a model compound (micro-crystalline cellulose) was dissolved in phosphoric acid and converted at 80 °C to glucose, thereby providing the possible substrate for fermentation to bioethanol. Results revealed that after 1 h heating, the reaction had the largest glucose yield as compared to similar studies done by using other acid catalysts. In addition, the temperature applied here was from 40 to 60 °C lower than those already reported in literature for acid-driven cellulose degradations. Phosphoric acid allowed both glucose and levulinic acid achievement. The latter is usually used to synthesize fuel additives, catalysts, solvents and herbicides, thereby enhancing the added value of the conversion of cellulose to glucose in phosphoric acid. Finally, 1H T1 NMR relaxometry showed its suitability to monitor cellulose degradation. The advantages of relaxomety are its quickness since only few minutes are needed to obtain relaxograms, and the possibility to use raw mixtures without the needing of sample preparation.

Keywords

Bioethanol Biofuel 13C NMR Cellulose degradation 1H T1 NMR relaxometry 

Notes

Acknowledgments

The high field NMR spectra were obtained at the “Centro Grandi Apparecchiature—Uninetlab” of the Università degli Studi di Palermo.

References

  1. Aguilar R, Ramirez JA, Garrote G, Vázquez M (2002) Kinetic study of the acid hydrolysis of sugar cane bagasse. J Food Eng 53:309–318CrossRefGoogle Scholar
  2. Bakhmutov VI (2004) Practical NMR relaxation for chemists. Wiley, EnglandGoogle Scholar
  3. Borgia GC, Brown RJS, Fantazzini P (1998) Uniform-penalty inversion of multiexponential decay data. J Magn Reson 132:65–77CrossRefGoogle Scholar
  4. Borgia GC, Brown RJS, Fantazzini P (2000) Uniform-penalty inversion of multiexponential decay data II: data spacing, T2 data, systematic data errors, and diagnostics. J Magn Reson 147:273–285CrossRefGoogle Scholar
  5. Bozell JJ, Moens L, Elliott DC, Wang Y, Neuenscwander GG, Fitzpatrick SW, Bilski RJ, Jarnefel JL (2000) Production of levulinic acid and use as a platform chemical for derived products. Resour Conserv Recy 28:227–239CrossRefGoogle Scholar
  6. Brown DE (1995) Fully automated baseline correction of 1D and 2D NMR spectra using Bernstein algorithm. J Magn Reson A 114:268–270CrossRefGoogle Scholar
  7. Calvini P, Gorassini A, Merlani AL (2008) On the kinetics of cellulose degradation: looking beyond the pseudo zero order rate equation. Cellulose 15:193–203CrossRefGoogle Scholar
  8. Conte P, Maccotta A, De Pasquale C, Bubici S, Alonzo G (2009) Dissolution mechanism of crystalline cellulose in H3PO4 as assessed by high-field NMR spectroscopy and fast field cycling NMR relaxometry. J Agr Food Chem 57:8748–8752CrossRefGoogle Scholar
  9. Escobar JC, Lora ES, Venturini OJ, Yáñez EE, Castillo EF, Almazan O (2009) Biofuels: environment, technology and food security. Renew Sust Energ Rev 13:1275–1287CrossRefGoogle Scholar
  10. Hayes DJ, Fitzpatrick SW, Hayes MHB, Ross JRH (2005) The biofine process: production of levulinic acid, furfural and formic acid from lignocellulosic feedstocks. In: Kamm B, Gruber VR, Kamm M (eds) Biorefineries, vol 1, principles and fundamentals. Wiley-VCH, Germany, pp 139–164Google Scholar
  11. Iranmahboob J, Nadim F, Monemi S (2002) Optimizing acid-hydrolysis: a critical step for production of ethanol from mixed wood chips. Biomass Bioenerg 22:401–404Google Scholar
  12. Isogai A, Atalla RH (1998) Dissolution of cellulose in acqueous NaOH solutions. Cellulose 5:309–319CrossRefGoogle Scholar
  13. Jayme G, Lang F (1963) Cellulose solvents. Methods Carbohydr Chem 3:75–83Google Scholar
  14. Jiang F, Zhu Q, Ma D, Liu X, Han X (2011) Direct conversion and NMR observation of cellulose to glucose and 5-hydroxymethylfurfural (HMF) catalyzed by the acidic ionic liquids. J Mol Catal A Chem 334:8–12CrossRefGoogle Scholar
  15. Jin H, Zha C, Gu L (2007) Direct dissolution of cellulose in NaOH/thiourea/urea aqueous solution. Carbohyd Res 342:851–858CrossRefGoogle Scholar
  16. Kimmich R, Anoardo E (2004) Field-cycling NMR relaxometry. Prog Nucl Mag Res Sp 44:257–320CrossRefGoogle Scholar
  17. Knill CJ, Kennedy JF (2003) Degradation of cellulose under alkaline conditions. Carbohyd Polym 51:281–300CrossRefGoogle Scholar
  18. Li H, Kim N-J, Jiang M, Kang JW, Chang HN (2009) Simultaneous saccharification and fermentation of lignocellulosic residues pretreated with phosphoric acid-acetone for bioethanol production. Bioresour Technol 100:3245–3251CrossRefGoogle Scholar
  19. Pagliaro M (1999) New iodination of cellulose in phosphoric acid. Carbohyd Res 315:350–353CrossRefGoogle Scholar
  20. Quin LD, Gordon MD, Lee SO (1974) Effects of some phosphorus substituents on the carbon-13 chemical shifts of alkyl chains. Org Magn Resonance 6:503–507CrossRefGoogle Scholar
  21. Rinaldi R, Palkovits R, Schüth F (2008) Depolymerization of cellulose using solid catalyst in ionic liquids. Angew Chem Int Edit 47:8047–8050CrossRefGoogle Scholar
  22. Saeman JF (1945) Kinetics of wood saccharification: hydrolysis of cellulose and decomposition of sugars in dilute acid at high temperature. Ind Eng Chem 37:43–52CrossRefGoogle Scholar
  23. Schacht C, Zetzl C, Brunner G (2008) From plant materials to ethanol by means of supercritical fluid technology. J Supercrit Fluid 46:299–321CrossRefGoogle Scholar
  24. Scheirs J, Camino G, Tumiatti W (2001) Overview of water evolution during the thermal degradation of cellulose. Eur Polym J 37:931–942CrossRefGoogle Scholar
  25. Sun Y, Cheng J (2002) Hydrolysis of lignocellulosic materials for ethanol production: a review. Bioresour Technol 83:1–11CrossRefGoogle Scholar
  26. Sun Y, Lin L, Pang C, Deng H, Peng H, Li J, He B, Liu S (2007) Hydrolysis of cotton fiber cellulose in formic acid. Energ Fuel 21:2386–2389CrossRefGoogle Scholar
  27. Sun Y, Zhuang J, Lin L, Ouyang P (2009) Clean conversion of cellulose into fermentable glucose. Biotechnol Adv 27:625–632CrossRefGoogle Scholar
  28. Timilsina GR, Shrestha A (2010) How much hope should we have for biofuels? Energy, in press. doi: 10.1016/j.energy.2010.08.023
  29. Wei S, Kumar V, Banker GS (1996) Phosphoric acid mediated depolymerisation and decrystallization of cellulose: preparation of low crystallinity cellulose—a new pharmaceutical eccipient. Int J Pharm 142:175–181CrossRefGoogle Scholar
  30. Wuebbles DJ, Jain AK (2001) Concerns about climate change and the role of fossil fuel use. Fuel Process Technol 71:99–119CrossRefGoogle Scholar
  31. Xiang Q, Lee YY, Pettersson PO, Torget RW (2003) Heterogeneous aspects of acid hydrolysis of α-cellulose. Appl Biochem Biotechnol 105–108:505–514Google Scholar
  32. Zakrzewska ME, Bogel-Lukasik E, Bogel-Lukasik R (2010) Solubility of carbohydrates in ionic liquids. Energ Fuel 24:737–745CrossRefGoogle Scholar
  33. Zhang Y-HP, Lynd LR (2003) Cellodextrin preparation by mixed-acid hydrolysis and chromatographic separation. Anal Biochem 322:225–232CrossRefGoogle Scholar
  34. Zhang Y-HP, Cui J-B, Lynd LR, Kuang LR (2006) A transition from cellulose swelling to cellulose dissolution by o-phosphoric acid: evidence from enzymatic hydrolysis and supramolecular structure. Biomacromolecules 7:644–648CrossRefGoogle Scholar
  35. Zhang Y-HP, Ding S-Y, Mielenz JR, Cui J-B, Elander RT, Laser M, Himmel ME, McMillan JR, Lynd LR (2007) Fractionating recalcitrant lignocellulose at modest reaction conditions. Biotechnol Bioeng 97:214–223CrossRefGoogle Scholar
  36. Zhang Y, Du H, Qian X, Chen EY-X (2010) Ionic liquid-water mixtures: enhanced Kw for efficient cellulosic biomass conversion. Energ Fuel 24:2410–2417CrossRefGoogle Scholar
  37. Zhao H, Kwak JH, Wang Y, Franz JA, White JM, Holladay JE (2006) Effects of crystallinity on dilute acid hydrolysis of cellulose by cellulose ball-milling study. Energ Fuel 20:807–811CrossRefGoogle Scholar
  38. Zhao H, Kwak JH, Zhang ZC, Brown HM, Arey BW, Holladay JE (2007) Studying cellulose fiber structure by SEM, XRD, NMR and acid hydrolysis. Carbohyd Polym 68:235–241CrossRefGoogle Scholar
  39. Zheng Y, Pan Z, Zhang R (2009) Overview of biomass pretreatment for cellulosic ethanol production. Int J Agric Biol Eng 2:51–68Google Scholar
  40. Zhu JY, Pan XJ (2010) Woody biomass pretreatment for cellulosic ethanol production: technology and energy consumption evaluation. Bioresour Technol 101:4992–5002CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  • Gabriella Butera
    • 1
  • Claudio De Pasquale
    • 1
  • Antonella Maccotta
    • 2
  • Giuseppe Alonzo
    • 1
  • Pellegrino Conte
    • 1
  1. 1.Dipartimento dei Sistemi Agro-AmbientaliUniversità degli Studi di PalermoPalermoItaly
  2. 2.Dipartimento di Scienze della Terra e del MareUniversità degli Studi di PalermoPalermoItaly

Personalised recommendations