Journal of Materials Science

, Volume 49, Issue 22, pp 7824–7833 | Cite as

Polyurethanes preparation using proteins obtained from microalgae

  • Sandeep Kumar
  • Elodie Hablot
  • Jose Luis Garcia Moscoso
  • Wassim Obeid
  • Patrick G. Hatcher
  • Brandon Michael DuQuette
  • Daniel Graiver
  • Ramani Narayan
  • Venkatesh Balan


It is widely believed that the biofuels can be sustainably produced using microalgae that are known to convert CO2 from the atmosphere to lipids, in the presence of nutrient and accumulate them as their body mass. However, when algal biofuels are produced using thermochemical route, ~30–65 % of proteins present in algae are lost due to decomposition and some of the nitrogen from amino acids is incorporated into the biofuels. The algal protein is a valuable resource that can bring additional revenue to the biorefinery by converting this co-product to high-value polyurethanes. In this work, we have demonstrated a one-step removal of proteins from algae through hydrolysis of the proteins to smaller peptides and amino acids using environment friendly flash hydrolysis (FH) process. Subcritical water was used as a reactant and as a reaction media for hydrolyzing the algae proteins via FH. Scenedesmus spp., slurry in water (3.8 %), was used as the algal feed stock during the FH process which was run at 280 °C for a residence time of 10 s. The soluble amino acids and peptides were separated from the other insoluble algal biomass components (cell wall and lipids) by filtration followed by freeze-drying. The product was then characterized by ion chromatography and Fourier transform ion cyclotron resonance mass spectrometry to determine its composition. The freeze-dried peptide and amino acids were then reacted with diamine and ethylene carbonate to produce polyols that were further processed to produce polyurethane. The relatively high hydroxyl value of these amino acid-based polyols and their compatibility with other commercially available polyols made them particularly suitable for producing rigid polyurethane foams. Due to the presence of amines and secondary amines in these polyols, the polymerization process was self-catalytic and the resulting foams are less flammable than conventional rigid polyurethane foams. The conversion of algal proteins to high-value industrial products by a relatively simple process greatly improves the value of proteins extracted from algae.


Foam Microalgae Polyol Polyurethane Foam Biocrude 



The authors are thankful for the financial support from the National Science Foundation (Grant NSF-CBET-CAREER:1351413) and the U.S. Environmental Protection Agency (Grant EPA/P3-SU-83550101). We would like to acknowledge Mr. Siva Rama Krishna Chalasani for helping with the synthesis and characterization of the Glycine model compounds.


  1. 1.
    Schenk PM, Thomas-Hall SR, Stephens E, Marx UC, Mussgnug JH, Posten C, Olaf Kruse A, Hankamer B (2008) Second generation biofuels: high-efficiency microalgae for biodiesel production. Bioenerg Res 1:20–43CrossRefGoogle Scholar
  2. 2.
    Huesemann MH, Benemann JR (2009) Biofuels from microalgae: review of products, processes and potential, with special focus on Dunaliella sp. In: Ben-Amotz JEWP A, Subba Rao DV (eds) The Alga Dunaliella: biodiversity, physiology, genomics, and biotechnology, vol 14. Science Publishers, New Hampshire, pp 445–474CrossRefGoogle Scholar
  3. 3.
    Chisti Y (2013) Constraints to commercialization of algal fuels. J Biotechnol 167(3):201–214. doi: 10.1016/j.jbiotec.2013.07.020 CrossRefGoogle Scholar
  4. 4.
    Clarke S, Graiver D, Habibie S (2010) Bio-fuels. In: Lever C (ed) Routledge handbook of climate change and society. Taylor and Francis Group, London, pp 297–307Google Scholar
  5. 5.
    Stucki S, Vogel F, Ludwig C, Haiduc AG, Brandenberger M (2009) Catalytic gasification of algae in supercritical water for biofuel production and carbon capture. Energy Environ Sci 2(5):535–541CrossRefGoogle Scholar
  6. 6.
    Davis R, Aden A, Pienkos PT (2011) Techno-economic analysis of autotrophic microalgae for fuel production. Appl Energy 88(10):3524–3531. doi: 10.1016/j.apenergy.2011.04.018 CrossRefGoogle Scholar
  7. 7.
    Safi C, Charton M, Pignolet O, Silvestre F, Vaca-Garcia C, Pontalier P-Y (2013) Influence of microalgae cell wall characteristics on protein extractability and determination of nitrogen-to-protein conversion factors. J Appl Phycol 25(2):523–529. doi: 10.1007/s10811-012-9886-1 CrossRefGoogle Scholar
  8. 8.
    Kebelmann K, Hornung A, Karsten U, Griffiths G (2013) Intermediate pyrolysis and product identification by TGA and Py-GC/MS of green microalgae and their extracted protein and lipid components. Biomass Bioenergy 49:38–48. doi: 10.1016/j.biombioe.2012.12.006 CrossRefGoogle Scholar
  9. 9.
    Chronakis IS (2000) Biosolar proteins from aquatic algae. In: Doxastakis G, Kiosseoglou V (eds) Developments in food science, vol 41. Elsevier, London, pp 39–75Google Scholar
  10. 10.
    Philp JC, Ritchie RJ, Guy K (2013) Biobased plastics in a bioeconomy. Trends Biotechnol 31(2):65–67. doi: 10.1016/j.tibtech.2012.11.009 CrossRefGoogle Scholar
  11. 11.
    Narayan R (2011) Carbon footprint of bioplastics using biocarbon content analysis and life cycle assessment. MRS Bull 36:716–721Google Scholar
  12. 12.
    Narayan R (2006) Rationale, drivers, standards, and technology for biobased materials. In: Graziani M, Fornasiero P (eds) Renewable resources and renewable energy. CRC Press, Boca RatonGoogle Scholar
  13. 13.
    Szycher M (1999) Handbook of polyurethanes. CRC Press, Boca RatonGoogle Scholar
  14. 14.
    Shogren RL, Petrovic ZS, Liu Z, Erhan SZ (2004) Biodegradation behavior of some vegetable oil-based polymers. J Polym Environ 12:173CrossRefGoogle Scholar
  15. 15.
    Zlatanic A, Lava C, Zhang W, Petrovic ZS (2004) Effect of structure on properties of polyols and polyurethanes based on different vegetable oils. J Polym Sci B 42:809CrossRefGoogle Scholar
  16. 16.
    Sims REH, Mabee W, Saddler JN, Taylor M (2010) An overview of second generation biofuel technologies. Bioresour Technol 101(6):1570–1580. doi: 10.1016/j.biortech.2009.11.046 CrossRefGoogle Scholar
  17. 17.
    Lin Y, Hsieh F, Huff HE (1997) Water-blown flexible polyurethane foam extended with biomass materials. J Appl Polym Sci 65(4):695–703. doi: 10.1002/(sici)1097-4628(19970725)65:4<695:aid-app8>;2-f CrossRefGoogle Scholar
  18. 18.
    Lin Y, Hsieh F, Huff HE, Iannotti E (1996) Physical, mechanical, and thermal properties of water-blown rigid polyurethane foam containing soy protein isolate. Cereal Chem 73(2):189–196Google Scholar
  19. 19.
    Rokicki G, Piotrowska A (2002) A new route to polyurethanes from ethylene carbonate, diamines and diols. Polymer 43(10):2927–2935. doi: 10.1016/S0032-3861(02)00071-X CrossRefGoogle Scholar
  20. 20.
    Chung I-D, Britt P, Xie D, Harth E, Mays J (2005) Synthesis of amino acid-based polymers via atom transfer radical polymerization in aqueous media at ambient temperature. Chem Commun 8:1046–1048CrossRefGoogle Scholar
  21. 21.
    Mensitieri G, Di Maio E, Buonocore GG, Nedi I, Oliviero M, Sansone L, Iannace S (2011) Processing and shelf life issues of selected food packaging materials and structures from renewable resources. Trends Food Sci Technol 22(2–3):72–80. doi: 10.1016/j.tifs.2010.10.001 CrossRefGoogle Scholar
  22. 22.
  23. 23.
    Garcia-Moscoso JL, Obeid W, Kumar S, Hatcher PG (2013) Flash hydrolysis of microalgae (Scenedesmus sp.) for protein extraction and production of biofuels intermediates. J Supercrit Fluids 82:183–190. doi: 10.1016/j.supflu.2013.07.012 CrossRefGoogle Scholar
  24. 24.
    Chen C-Y, Yeh K-L, Aisyah R, Lee D-J, Chang J-S (2011) Cultivation, photobioreactor design and harvesting of microalgae for biodiesel production: a critical review. Bioresour Technol 102(1):71–81. doi: 10.1016/j.biortech.2010.06.159 CrossRefGoogle Scholar
  25. 25.
    Singh RN, Sharma S (2012) Development of suitable photobioreactor for algae production: a review. Renew Sustain Energy Rev 16(4):2347–2353. doi: 10.1016/j.rser.2012.01.026 CrossRefGoogle Scholar
  26. 26.
    Kumar S, Hatcher PG (2011) Fractionation of proteins and lipids from microalgae. USA PatentGoogle Scholar
  27. 27.
    Zhu X, Zhu C, Zhao L, Cheng HB (2008) Amino acids production from fish proteins hydrolysis in subcritical water. Chin J Chem Eng 16(3):456–460. doi: 10.1016/S1004-9541(08)60105-6 CrossRefGoogle Scholar
  28. 28.
    Levine RB, Sierra COS, Hockstad R, Obeid W, Hatcher PG, Savage PE (2013) The use of hydrothermal carbonization to recycle nutrients in algal biofuel production. Environ Prog Sustain Energy 32(4):962–975. doi: 10.1002/ep.11812 CrossRefGoogle Scholar
  29. 29.
    D1980-87 A standard test method for acid value of fatty acids and polymerized fatty acidsGoogle Scholar
  30. 30.
    D2073-92 A standard test methods for total, primary, secondary, and tertiary amine values of fatty amines, amidoamines, and diamines by referee potentiometric methodGoogle Scholar
  31. 31.
    D1957-86 A standard test method for hydroxyl value of fatty oils and acidsGoogle Scholar
  32. 32.
    Chakinala AG, Brilman DWF, van Swaaij WPM, Kersten SRA (2010) Catalytic and non-catalytic supercritical water gasification of microalgae and glycerol. Ind Eng Chem Res 49(3):1113–1122CrossRefGoogle Scholar
  33. 33.
    Wool R, Sun S (2005) Bio-based polymers and composites. Academic Press, BurlingtonGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • Sandeep Kumar
    • 1
  • Elodie Hablot
    • 3
  • Jose Luis Garcia Moscoso
    • 1
  • Wassim Obeid
    • 2
  • Patrick G. Hatcher
    • 2
  • Brandon Michael DuQuette
    • 3
  • Daniel Graiver
    • 3
  • Ramani Narayan
    • 3
  • Venkatesh Balan
    • 3
  1. 1.Department of Civil and Environmental EngineeringOld Dominion UniversityNorfolkUSA
  2. 2.Department of Chemistry and BiochemistryOld Dominion UniversityNorfolkUSA
  3. 3.Department of Chemical Engineering and Material ScienceMichigan State UniversityEast LansingUSA

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