Abstract
The main objective of biorefineries is the efficient conversion of lignocellulosic materials into valuable products. Lignin, a major abundant polymer not sufficiently exploited, is considered to be a promising substitute of phenol in phenol–formaldehyde resin synthesis. In this study, a lignin sample from a bioethanol production plant was modified under different experimental conditions by a depolymerisation treatment. The modification was intended to enhance the reactivity of lignin by increasing its functionality. The structural changes were studied with several characterisation techniques including size exclusion chromatography, Fourier transform infrared spectroscopy and nuclear magnetic resonance. The lignin reactivity towards formaldehyde was determined with a formaldehyde reactivity test. From the characterisation results of the reacted lignins, it was concluded that increasing the severity of the depolymerisation treatment (i.e. higher temperature, reaction time and catalyst content) resulted in an increase in active functional groups. Consequently, lignins depolymerised at more severe conditions were more reactive towards formaldehyde reaction. Due to their improved reactivity, the treated lignins could be successfully used as substitutes of phenol, converting them into a highly value-added product. An estimation of the cost of the proposed process is provided.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Chen CL, Robert D (1988) H and C NMR spectroscopy of lignin. In: Wood WA, Kellogg ST (eds) Methods in enzymology biomass, part B, vol 161. Academic Press, New York, pp 137–174
Chum HL, Johnson DK, Ratcliff M, Black S, Oiticica B, Wallace K, Schroeder HA, Robert D, Sarkanen KV (1985) Lignin characterization research: a process report. In: Biochemical conversion program semi-annual review meeting. Solar Energy Research Institute. Prepared for the U.S. Department of Energy. Contract No. DE-AC02-83CH10093, pp 25–50
de Wild PJ, Huijgen WJJ, Gosselink RJA (2014) Lignin pyrolysis for profitable lignocellulosic biorefineries. Biofuel Bioprod Biorefin 8:645–657
Doherty WOS, Mousavioun P, Fellows CM (2011) Value-adding to cellulosic ethanol: lignin polymers. Ind Crop Prod 33:259–276
El Mansouri NE, Salvadó J (2006) Structural characterization of technical lignins for the production of adhesives: application to lignosulfonate, kraft, soda-anthraquinone, organosolv and ethanol process lignins. Ind Crop Prod 24:8–16
El Mansouri NE, Farriol X, Salvadó J (2006) Structural modification and characterization of lignosulfonate by a reaction in an alkaline medium for its incorporation into phenolic resins. J Appl Polym Sci 102:3286–3292
El Mansouri NE, Pizzi A, Salvadó J (2007) Lignin-based wood panel adhesives without formaldehyde. Holz Roh Werkst 65:65–70
European Panel Federation (2015) Annual report 2014–2015
Faix O (1992) Fourier transform infrared spectroscopy. In: Lin SY, Dence CW (eds) Methods in lignin chemistry. Springer, Berlin, Heidelberg, pp 83–109
Farag S, Chaouki J (2015) Economics evaluation for on-site pyrolysis of kraft lignin to value-added chemicals. Bioresour Technol 175:254–261
Hu L, Pan H, Zhou Y, Zhang M (2011) Methods to improve lignin`s reactivity as a phenol substitute and as replacement for other phenolic compounds: a brief review. BioResources 6:3515–3525
Kleinert M, Barth T (2009) Phenols from Lignin. Chem Eng Technol 31:736–745
Laurichesse S, Avérous L (2014) Chemical modification of lignins: towards biobased polymers. Prog Polym Sci 39:1266–1290
Marketsandmarkets (2014) Phenolic resin market by type (Resol and Novolac) and by application (wood adhesive, molding, laminates, insulation, and others)—global trends & forecast to 2019. http://www.marketsandmarkets.com/Market-Reports/phenolic-resin-market-177821389.html. Accessed 01 Apr 2016
Pilato L (2013) Phenolic resins: 100 years and still going strong. React Funct Polym 73:270–277
Pizzi A, Mittal KL (1994) Handbook of adhesives technology. Marcel Dekker, New York
Ragauskas AJ, Beckham GT, Biddy MJ et al (2014) Lignin valorization: improving lignin processing in the biorefinery. Science 344:709
Stewart D (2008) Lignin as a base material for materials applications: chemistry, application and economics. Ind Crop Prod 27:202–207
Strassberger Z, Tanase S, Rothenberg G (2014) The pros and cons of lignin valorisation in an integrated biorefinery. RSC Adv 4:25310–25318
van Haveren J, Scott EL, Sanders J (2008) Bulk chemicals from biomass. Biofuel Bioprod Biorefin 2:41–57
Vishtal A, Kraslawski A (2011) Challenges in industrial applications of technical lignins. BioResources 6:3547–3568
Wooten AL, Sellers TJ, Tahir PM (1988) Reaction of formaldehyde with lignin. For Prod J 38:45–46
Acknowledgements
The authors would like to thank the European Commission, 7th Framework Program (NMP-2012 Project Eco2CO2 nr. 309701), for the financial support. In the framework of this project, lignin samples used in this study were kindly provided by Biochemtex. The research has also received funding from the University Rovira i Virgili, and Excma. Diputació Tarragona (‘Fuels from Biomass’ research programme). The research was also supported by the European Regional Development Funds (ERDF, FEDER Programa Competitividad de Catalunya 2007–2013). C.B. is grateful to the Spanish Ministry of Economy and Competitiveness (MINECO) for funding his Ramon y Cajal contract (RYC-2011-09202).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Lorente, E., Torras, C., Berrueco, C. et al. Transformation of lignin from bioethanol production for phenol substitution in resins. Wood Sci Technol 51, 1209–1225 (2017). https://doi.org/10.1007/s00226-017-0911-z
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00226-017-0911-z