Recovery of Low-Ash and Ultrapure Lignins from Alkaline Liquor By-Product Streams

  • Mark C. ThiesEmail author
  • Adam S. Klett
Part of the Biofuels and Biorefineries book series (BIOBIO)


Although a number of treatment methods can be used to separate cellulose and lignin components from biomass, aqueous alkaline treatment methods are dominant. Typically, the cellulose is precipitated from solution, and the lignin ends up in the highly alkaline liquor by-product stream. Today the vast majority of this lignin is burned in situ as a fuel; however, it potentially has far more value as a renewable biopolymer. Here, two new technologies are presented for recovering lignin from alkaline liquor streams generated either from a pulp-and-paper mill or a lignocellulosic biofuels refinery. With SLRPTM technology, the lignin precipitation step is carried out at above-ambient conditions such that a liquid (and not a solid) lignin phase is formed. Thus, the SLRP process for producing low-ash (1–2 %) lignin is continuous, not batch. Furthermore, the “liquid-lignin” phase can be readily fractionated by pH into fractions having different bulk and molecular properties. The ALPHA process was developed with the express purpose of taking low-ash lignins produced from alkaline-liquor by-product streams to the “ultrapure” state. The technology uses adjustable mixtures of biorenewable acetic acid and water to create a unique liquid–liquid solvent system that can be used to simultaneously fractionate, purify, and solvate lignins. Metals contents in ALPHA lignins well below 100 ppm are readily achieved in fractions of both low and high molecular weight.


Alkaline pretreatment Lignin recovery Lignin fractionation Lignin extraction Liquid–liquid equilibrium Renewable solvents 



This material is based upon work supported by the National Science Foundation under Award Numbers CBET-1403873 and CBET-1236759.


  1. 1.
    Patt R, Kordsachia O, and Süttinger R. Pulp. In: Ullmann’s encyclopedia of industrial chemistry. Weinheim: Wiley-VCH; 2011. P. 487–491.Google Scholar
  2. 2.
    Biermann CJ. Handbook of pulping and papermaking. 2nd ed. San Diego: Elsevier; 1996.Google Scholar
  3. 3.
    Gosselink RJA, et al. Co-ordination network for lignin-standardisation, production and applications adapted to market requirements (EUROLIGNIN). Ind Crop Prod. 2004;20:121–9.CrossRefGoogle Scholar
  4. 4.
    Doherty WOS, Mousavioun P, Fellows CM. Value-adding to cellulosic ethanol: lignin polymers. Ind Crop Prod. 2011;33:259–76.CrossRefGoogle Scholar
  5. 5.
    Adler E. Lignin chemistry – past, present and future. Wood Sci Technol. 1977;11:169–218.CrossRefGoogle Scholar
  6. 6.
    Tomani P. The lignoboost process. Cellul Chem Technol. 2010;44:53–8.Google Scholar
  7. 7.
    Kouisni L, et al. The LignoForce system: a new process for the production of high-quality lignin from black liquor. J Sci Technol For Prod Processes. 2012;2:6–10.Google Scholar
  8. 8.
    Lake MA, Blackburn JC. 2009. Process for recovering lignin. US Patent 9,260,464, FEb. 16, 2016.Google Scholar
  9. 9.
    LignoBoost plant at Domtar’s Plymouth mill in North Carolina. 2016. Accessed 10 May 2016.
  10. 10.
    Pulp and Paper Canada. West Fraser lignin project gets $6 million from SDTC. 2015. Accessed 10 May 2016.
  11. 11.
    Gordobil O, et al. Kraft lignin as filler in PLA to improve ductility and thermal properties. Ind Crops Prod. 2015;72:46–53.CrossRefGoogle Scholar
  12. 12.
    Hilburg SL, et al. A universal route towards thermoplastic lignin composites with improved mechanical properties. Polymer. 2013;55:995–1003.CrossRefGoogle Scholar
  13. 13.
    The National Archives, Department of Transport, United Kingdom. Renewable Transport Fuels Obligation (RTFO) order. 2013. Accessed 10 May 2016.Google Scholar
  14. 14.
    Gellerstedt G, Sjöholm E, Brodin I. The wood-based biorefinary: a source of carbon fiber? The Open Agric J. 2010;3:119–24.CrossRefGoogle Scholar
  15. 15.
    Compare AL et al. Low cost carbon fibers from renewable resources. Adv Affordable Mat Technol. 2001. Accessed 12 May 2016.
  16. 16.
    Arato C, Pye EK, Gjennestad G. The lignol approach to biorefining of woody biomass to produce ethanol and chemicals. Appl Biochem Biotechnol. 2005;121:871–82.CrossRefPubMedGoogle Scholar
  17. 17.
    Pan X, Sano Y. Acetic acid pulping of wheat straw under atmospheric pressure. J Wood Sci. 1999;45:319–25.CrossRefGoogle Scholar
  18. 18.
    Hasegawa I, et al. New pretreatment methods combining a hot water treatment and water/acetone extraction for thermo-chemical conversion of biomass. Energy Fuels. 2004;18:755–60.CrossRefGoogle Scholar
  19. 19.
    Kleinert TN. Organosolv pulping and recovery process. US Patent US3585104. 1968.Google Scholar
  20. 20.
    Iakovlev M, You X, van Heiningen A, Sixta H. SO2–ethanol–water (SEW) fractionation of spruce: kinetics and conditions for paper and viscose-grade dissolving pulps. RSC Adv. 2014;4:1938–50.CrossRefGoogle Scholar
  21. 21.
    Holladay JE, et al. Top value-added chemicals from biomass – volume II-results of screening for potential candidates from biorefinery lignin. Richland: Pacific Northwest National Laboratory; 2007.CrossRefGoogle Scholar
  22. 22.
    Thies MC, Klett AS, Bruce DA. Solvent and recovery process for lignin. U.S. Patent Application No. 2016/0137680 A1, May 19, 2016.Google Scholar
  23. 23.
    Klett AS, Chappell PV, Thies MC. Recovering ultraclean lignins of controlled molecular weight from Kraft black-liquor lignins. Chem Commun. 2015;51:12855–8.CrossRefGoogle Scholar
  24. 24.
    Sixta H. Handbook of pulp. Weinheim: Wiley-VCH Verlag GmbH; 2008.Google Scholar
  25. 25.
    Farrington A, Nelson P, Vanderhoek N. New alkaline pulping process. APPITA J. 1977;31(2):119–20.Google Scholar
  26. 26.
    Francis RC, et al. Positive and negative aspects of soda/anthraquinone pulping of hardwoods. Biores Technol. 2008;99(17):8453–7.CrossRefGoogle Scholar
  27. 27.
    Springer EL, Atalla RH, Reiner RS. Potential sulfur-free pulping methods. TAPPI fall technical conference and trade fair. Atlanta, GA; 2002.Google Scholar
  28. 28.
    Velez J, Thies MC. Solvated liquid-lignin fractions from a Kraft black liquor. Bioresour Technol. 2013;148:586–90.CrossRefPubMedGoogle Scholar
  29. 29.
    Velez J, Thies MC. Liquid lignin from the SLRP process: the effect of processing conditions and black-liquor properties. J Wood Chem and Technol. 2016;36:27–41.CrossRefGoogle Scholar
  30. 30.
    Zhu W, Westman G, Theliander H. Investigation and characterization of lignin precipitation in the Lignoboost process. J Wood Chem Technol. 2014;34:77–97.CrossRefGoogle Scholar
  31. 31.
    Norgren M, et al. Aggregation of kraft lignin derivatives under conditions relevant to the process, part I: phase behavior. Colloids Surf. 2001;194:85–96.CrossRefGoogle Scholar
  32. 32.
    Koda K, et al. Molecular weight-functional group relations in softwood residual kraft lignins. Holzforschung. 2005;59:612–9.CrossRefGoogle Scholar
  33. 33.
    Coen CJ, Blanch HW, Prausnitz JM. Salting out of aqueous proteins: phase equilibria and intermolecular potentials. AIChE J. 1995;41(4):996–1004.CrossRefGoogle Scholar
  34. 34.
    Bailey JE, Ollis DF. Biochemical engineering fundamentals. New York: McGraw-Hill; 1986.Google Scholar
  35. 35.
    Stoklosa RJ, et al. Correlating lignin structural features to phase partitioning behavior in a novel aqueous fractionation of softwood Kraft black liquor. Green Chem. 2013;15:2904–12.CrossRefGoogle Scholar
  36. 36.
    Velez J, Thies MC. Temperature effects on the molecular properties of liquid lignin recovered from Kraft black liquor. ACS Sustain Chem Eng. 2015;3(6):1032–8.CrossRefGoogle Scholar
  37. 37.
    Klett AS, Gamble JA, Thies MC, Roberts ME. Identifying thermal phase transitions of lignin-solvent mixtures using electrochemical impedance spectroscopy. Green Chem. 2016;18:1892–7.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Singapore 2016

Authors and Affiliations

  1. 1.Department of Chemical and Biomolecular EngineeringClemson UniversityClemsonUSA

Personalised recommendations