BioEnergy Research

, Volume 6, Issue 1, pp 24–34 | Cite as

Compositional Characterization and Pyrolysis of Loblolly Pine and Douglas-fir Bark

  • Shaobo Pan
  • Yunqiao Pu
  • Marcus Foston
  • Arthur J. Ragauskas


Two potential biofuel resources, Douglas-fir and Loblolly pine bark, were subjected to extensive chemical and compositional analysis. The barks were initially extracted with dichloromethane, and the resulting extracted compounds were characterized by gas chromatography coupled with mass spectrometric analysis. Characterization of the major bark biocomponents indicated that Douglas-fir and Loblolly pine bark contained 22.5 and 13.2 % tannins, 44.2 and 43.5 % lignin, 16.5 and 23.1 % cellulose, and 7.6 and 14.1 % hemicellulose, respectively. Of particular interest is the high content of tannins and lignin, which make these barks excellent potential precursors for bio-oils and/or other value-added chemicals. 13C nuclear magnetic resonance (NMR) was used to characterize the chemical structure of the lignin and tannins. These samples were also analyzed by 31P NMR after phosphitylation of the hydroxyl groups in lignin and tannins. The NMR spectral data indicated that the lignin in both barks contained p-hydroxyphenyl (h) and guaiacyl (g) of lignin monomers with an h/g ratio of 10:90 and 22:78 for Douglas-fir and Loblolly pine bark, respectively. Gel permeation chromatography was used to analyze the molecular weight distributions of extracted tannins, isolated cellulose, and ball-milled lignin. The pyrolysis of Douglas-fir and pine bark at 500°C in a tubular reactor generated 48.2 and 45.2 % of total oil, of which the light oil contents are 14.1 and 20.7 % and heavy oil are 34.1 and 24.4 %. Similarly, fast pyrolysis at 375°C yielded 56.1 and 49.8 % of total oil for Douglas-fir and pine bark, respectively.


Loblolly pine bark Douglas-fir bark Extractive Inorganic elements Ball-milled lignin Tannin Cellulose 1331P NMR spectroscopy 



The authors wish to acknowledge financial support from Chevron Technology Ventures for these studies.


  1. 1.
    Stöcker M (2008) Biofuels and biomass-to-liquid fuels in the biorefinery: catalytic conversion of lignocellulosic biomass using porous materials. Angew Chem Int Ed 47:9200–9211CrossRefGoogle Scholar
  2. 2.
    Ragauskas AJ, Williams CK, Davison BH, Britovsek G, Cairney J, Eckert CA et al (2006) The path forward for biofuels and biomaterials. Sci 311:484–489CrossRefGoogle Scholar
  3. 3.
    Pu Y, Zhang D, Singh PM, Ragauskas AJ (2008) The new forestry biofuels sector. Biofuels Bioprod Bioref 2:58–73CrossRefGoogle Scholar
  4. 4.
    McKeever DB (1998) Wood residual quantities in the United States. BioCycle 39:65–68Google Scholar
  5. 5.
    Mun SP, Hassan EBM (2004) Liquefaction of lignocellulosic biomass with dioxane/polar solvent mixture in the presence of an acid catalyst. J Ind Eng Chem 10(3):473–477Google Scholar
  6. 6.
    Mun SP, Hassan EBM (2004) Liquefaction of lignocellulosic biomass with mixture of ethanol and small amounts of phenol in the presence of methanesulfonic acid catalyst. J Ind Eng Chem 10(5):722–727Google Scholar
  7. 7.
    Açıkalın K, Karaca F, Bolat E (2005) Central composite rotatable design for liquefaction of pine barks. Fuel Process Technol 87:17–24CrossRefGoogle Scholar
  8. 8.
    Şensöz S (2003) Slow pyrolysis of wood barks from Pinus brutia Ten. and product compositions. Biores Technol 89:307–311CrossRefGoogle Scholar
  9. 9.
    Chaala A, Ba T, Garcia-Perez M, Roy C (2004) Colloidal properties of bio-oils obtained by vacuum pyrolysis of softwood bark: aging and thermal stability. Energy Fuel 18:1535–1542CrossRefGoogle Scholar
  10. 10.
    Ingram L, Mohan D, Bricka M, Steele P, Strobel D, Crocker D et al (2008) Pyrolysis of wood and bark in an auger reactor: physical properties and chemical analysis of the produced bio-oils. Energy Fuel 22:614–625CrossRefGoogle Scholar
  11. 11.
    Amen-Chen C, Riedl B, Wang X, Roy C (2002) Softwood bark pyrolysis oil-PF resols. Part 1. Resin synthesis and OSB mechanical properties. Holzforschung 56(2):167–175CrossRefGoogle Scholar
  12. 12.
    Amen-Chen C, Riedl B, Roy C (2002) Softwood bark pyrolysis oil-PF resols. Part 2. Thermal analysis by DSC and TG. Holzforschung 56(3):273–280Google Scholar
  13. 13.
    McGinnis GD, Parikh S (1975) The chemical constituents of loblolly pine bark. Wood Sci 7(4):295–297Google Scholar
  14. 14.
    Laver ML, Fang H, Loveland PM, Zerrudo JV, Chen C, Liu YL (1977) Chemical constituents of Douglas-Fir bark: a review of more recent literature. Wood Sci 10(2):85–92Google Scholar
  15. 15.
    Labosky P Jr (1979) Chemical constituents of four southern pine barks. Wood Sci 12(2):80–85Google Scholar
  16. 16.
    Harun J, Labosky P Jr (1985) Chemical constituents of five northeastern barks. Wood Fiber Sci 17(2):274–280Google Scholar
  17. 17.
    Vázquez G, Antorrena G, Parajó JC (1987) Studies on the utilization of Pinus pinaster bark. Part 1: Chemical constituents. Wood Sci Technol 21:65–74Google Scholar
  18. 18.
    Fradinho DM, Pascoal Neto C, Evtuguin D, Jorge FC, Irle MA, Gil MH et al (2002) Chemical characterisation of bark and of alkaline bark extracts from maritime pine grown in Portugal. Ind Crop Prod 16:23–32CrossRefGoogle Scholar
  19. 19.
    Huang F, Singh PM, Ragauskas AJ (2011) Characterization of milled wood lignin (MWL) in Loblolly pine stem wood, residue and bark. J Agric Food Chem 59:12910–12916PubMedCrossRefGoogle Scholar
  20. 20.
    Ragauskas AJ, Nagy M, Kim DH, Eckert CA, Hallett JP, Liotta CL (2006) From wood to fuels: integrating biofuels and pulp production. Ind Biotechnol 2(1):55–65CrossRefGoogle Scholar
  21. 21.
    TAPPI (1993) Ash in wood, pulp, paper and paperboard. TAPPI test methods. TAPPI, AtlantaGoogle Scholar
  22. 22.
    Allison L, Ragauskas AJ, Hsieh J (2000) Metal profiling of southeastern U.S. softwood and hardwood Furnish. Tappi J 83(8):97–102Google Scholar
  23. 23.
    TAPPI (2006) Gross heating value of black liquor. TAPPI test methods. TAPPI, AtlantaGoogle Scholar
  24. 24.
    Pietarinen SP, Willför SM, Vikström FA, Holmbom BR (2006) Aspen knots, a rich source of flavonoids. J Wood Chem Technol 26:245–258CrossRefGoogle Scholar
  25. 25.
    Berg A, Navarrete P, Olave L (2007) Biochemicals and standardized solid fuels from radiata pine bark. 15th European Biomass Conference & Exhibition, Berlin, GermanyGoogle Scholar
  26. 26.
    TAPPI (1988) Acid-insoluble lignin in wood and pulp. TAPPI test methods. TAPPI, AtlantaGoogle Scholar
  27. 27.
    Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D et al (2008) Determination of structural carbohydrates and lignin in biomass. Laboratory Analytical Procedure; National Renewable Energy Laboratory, GoldenGoogle Scholar
  28. 28.
    Lin S, Dence C (eds) (1992) Methods in lignin chemistry. Springer series in wood science. Springer, Berlin, 578 ppGoogle Scholar
  29. 29.
    Guerra A, Mendonça R, Ferraz A, Lu F, Ralph J (2004) Structural characterization of lignin during Pinus taeda wood treatment with Ceriporiopsis subvermispora. Appl Environ Microbiol 70(7):4073–4078PubMedCrossRefGoogle Scholar
  30. 30.
    Holtman KM, Chang H, Jameel H, Kadla JF (2006) Quantitative 13C NMR characterization of milled wood lignins isolated by different milling techniques. J Wood Chem Technol 26:21–34CrossRefGoogle Scholar
  31. 31.
    Sun R, Mott L, Bolton J (1998) Isolation and fractional characterization of ball-milled and enzyme lignins from oil palm runk. J Agric Food Chem 46:718–723PubMedCrossRefGoogle Scholar
  32. 32.
    Río D, Rencoret J, Marques G, Li J, Gellerstedt G et al (2009) Structural characterization of the lignin from jute (Corchorus capsularis) fibers. J Agric Food Chem 57:10271–10281PubMedCrossRefGoogle Scholar
  33. 33.
    Aimi H, Matsumoto Y, Meshitsuka G (2005) Structure of small lignin fragments retained in water-soluble polysaccharides extracted from birch MWL isolation residue. J Wood Sci 51:303–308CrossRefGoogle Scholar
  34. 34.
    Rio D, Marques G, Rencoret J, Martiänez A, Gutierrez A (2007) Occurrence of naturally acetylated lignin units. J Agric Food Chem 55:5461–5468PubMedCrossRefGoogle Scholar
  35. 35.
    Granata A, Argyropoulos DS (1995) 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, a reagent for the accurate determination of the uncondensed and condensed phenolic moieties in lignins. J Agric Food Chem 43(6):1538–1544CrossRefGoogle Scholar
  36. 36.
    Cohen R, Jensen KA Jr, Houtman CJ, Hammel KE (2002) Significant levels of extracellular reactive oxygen species produced by brown rot basidiomycetes on cellulose. FEBS Lett 531:483–488PubMedCrossRefGoogle Scholar
  37. 37.
    Fang P, McGinnis GD, Parish EJ (1976) Thermogravimetric analysis of loblolly pine bark components. Wood and Fiber 7(2):136–145Google Scholar
  38. 38.
    Harder ML, Einspahr DW (1980) Levels of some essential metals in bark. TAPPI 63(12):110–112Google Scholar
  39. 39.
    Harkin JM, Rowe JW (1971) Bark and its possible uses. US Department of Agriculture, Forest Service, research note FPL-091, Forest Products Laboratory, Madison, WisconsinGoogle Scholar
  40. 40.
    Yin C (2010) Emerging usage of plant-based coagulants for water and wastewater treatment. Process Biochem 45:1437–1444CrossRefGoogle Scholar
  41. 41.
    Navarrete P, Mansouri HR, Pizzi A, Tapin-Lingua S, Benjelloun-Mlayah B, Pasch H et al (2010) Wood panel adhesives from low molecular mass lignin and tannin without synthetic resins. J Adhes Sci Technol 24:1597–1610CrossRefGoogle Scholar
  42. 42.
    Rutkowski P (2011) Pyrolysis of cellulose, xylan and lignin with the K2CO3 and ZnCl2 addition for bio-oil production. Fuel Process Technol 92:517–522CrossRefGoogle Scholar
  43. 43.
    Eriksson G, Hedman H, Boström D, Pettersson E, Backman R, Öhman M (2009) Combustion characterization of rapeseed meal and possible combustion applications. Energy Fuel 23:3930–3939CrossRefGoogle Scholar
  44. 44.
    Gutarowska B, Cichocka A (2010) Application of ergosterol determination for rapid estimation of fungal contamination in various stages of paper production. Przeglad Papierniczy 66:45–47Google Scholar
  45. 45.
    Nagy M, Kerr BJ, Ziemer CJ, Ragauskas AJ (2009) Phosphitylation and quantitative 31P NMR analysis of partially substituted biodiesel glycerols. Fuel 88:1793–1797CrossRefGoogle Scholar
  46. 46.
    Zhang P, Jarnefeld J, Wen B (2005) A new process for biodiesel production from waste cooking oils. 229th ACS national meeting, San Diego, CA, March 13-17, AGFD-164Google Scholar
  47. 47.
    Xiang T, Amin RAM (2011) Water-based mud lubricant using fatty acid polyamine salts and fatty acid esters. U.S. Pat. Appl. Publ. US 20110036579Google Scholar
  48. 48.
    Holtman KM, Chang H, Kadla JF (2004) Solution-state nuclear magnetic resonance study of the similarities between milled wood lignin and cellulolytic enzyme lignin. J Agric Food Chem 52(4):720–726PubMedCrossRefGoogle Scholar
  49. 49.
    Capanema EA, Balakshin MY, Kadla JF (2004) A comprehensive approach for quantitative lignin characterization by NMR spectroscopy. J Agric Food Chem 52(7):1850–1860PubMedCrossRefGoogle Scholar
  50. 50.
    Capanema EA, Balakshin MY, Kadla JF (2005) Quantitative characterization of a hardwood milled wood lignin by nuclear magnetic resonance spectroscopy. J Agric Food Chem 53(25):9639–9649PubMedCrossRefGoogle Scholar
  51. 51.
    Sannigrahi P, Ragauskas AJ, Miller SJ (2008) Effects of two-stage dilute acid pretreatment on the structure and composition of lignin and cellulose in loblolly pine. Bioenerg Res 1:205–214CrossRefGoogle Scholar
  52. 52.
    Guerra A, Filpponen I, Lucia LA, Argyropoulos DS (2006) Comparative evaluation of three lignin isolation protocols for various wood species. J Agric Food Chem 54:9696–9705PubMedCrossRefGoogle Scholar
  53. 53.
    Kraus TEC, Yu Z, Preston CM, Dahlgren RA, Zasoski RJ (2003) Linking chemical reactivity and protein precipitation to structural characteristics of foliar tannins. J Chem Ecol 29(3):703–730PubMedCrossRefGoogle Scholar
  54. 54.
    Grigsby WJ, Hill SJ, McIntosh CD (2003) NMR estimation of extractables from bark: analysis method for quantifying tannin extraction from bark. J Wood Chem Technol 23(2):179–195CrossRefGoogle Scholar
  55. 55.
    Bate-Smith EC (1977) Astringent tannins of Acer species. Phytochem 16(9):1421–1426CrossRefGoogle Scholar
  56. 56.
    Hallac BB, Sannigrahi P, Pu Y, Ray M, Murphy RJ, Ragauskas AJ (2009) Biomass characterization of Buddleja davidii: a potential feedstock for biofuel production. J Agric Food Chem 57:1275–1281PubMedCrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Shaobo Pan
    • 1
    • 2
  • Yunqiao Pu
    • 1
  • Marcus Foston
    • 2
  • Arthur J. Ragauskas
    • 1
    • 2
  1. 1.Institute of Paper Science and TechnologyGeorgia Institute of TechnologyAtlantaUSA
  2. 2.School of Chemistry and BiochemistryGeorgia Institute of TechnologyAtlantaUSA

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