Skip to main content
Log in

Liquid–Liquid Extraction of Phenolic Compounds from Spent Sulphite Liquor

  • Original Paper
  • Published:
Waste and Biomass Valorization Aims and scope Submit manuscript

Abstract

The sulphite pulping process for cellulose extraction consists of lignin depolymerisation of wood by sulphonation and hydrolysis leading to the production of spent sulphite liquor (SSL) as waste stream enriched in hemicellulose sugars and lignin derivatives. In this work, liquid–liquid extraction was used in order to separate phenolics from the sugar-rich SSL fraction. The effects of type of solvent, settling time, pH value, number of extraction stages and sample-to-solvent ratio were investigated. Folin–Ciocalteu and UNE-EN 16109 methods were used for the analysis of total phenolic content and total phenolic hydroxyl groups, respectively. The DPPH· method was used to determine the radical scavenging capacity of the extracts. Individual phenolic compounds were determined via HPLC–DAD analysis. Sugars and other compounds (5-hydroxymethylfurfural, furfural and acetic acid) were also quantified. Effective extraction of phenolic compounds was achieved using diethyl ether in a single extraction stage, at room temperature, at pH value of 3.6 and a sample-to-solvent ratio of 1:3 (v/v). The diethyl ether extract contained 6.31 g gallic acid equivalents per L, indicating strong antioxidant activity index (4.9), as well as 0.024 g/L 5-hydroxymethylfurfural, 0.025 g/L furfural, 2.89 g/L acetic acid and 1.4 g/L of sugars.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Santos, R.B., Hart, P.W., Jameel, H., Chang, H.M.: Wood based lignin reactions important to the biorefinery and pulp and paper industries. BioResources 8, 1456–1477 (2013)

    Google Scholar 

  2. Llano, T., Rueda, C., Quijorna, N., Blanco, A., Coz, A.: Study of the delignification of hardwood chips in a pulping process for sugar production. J. Biotechnol. 162, 422–429 (2012)

    Article  Google Scholar 

  3. Rueda, C., Lopez-Alvarez, J., Llano, T., Quijorna, N., Blanco, A., Viguri, J.R., Coz, A.: Physico-chemical characterization of a spent sulfite liquor oriented to its valorization options. In: 16th International Symposium on Wood, Fiber and Pulping Chemistry—Proceedings, ISWFPC, 1 Tianjin, China, pp. 584–587 (2011)

  4. Palmqvist, E., Hahn-Hägerdal, B.: Fermentation of lignocellulosic hydrolysates. II: inhibitors and mechanisms of inhibition. Bioresour. Technol. 74, 25–33 (2000)

    Article  Google Scholar 

  5. Willför, S.M., Ahotupa, M.O., Hemming, J.E., Reunanen, M.H.T., Eklund, P.C., Sjöholm, R.E., Eckerman, C.S.E., Pohjamo, S.P., Holmbom, B.R.: Antioxidant activity of knotwood extractives and phenolic compounds of selected tree species. J. Agric. Food Chem. 51, 7600–7606 (2003)

    Article  Google Scholar 

  6. Jönsson, L.J., Alriksson, B., Nilvebrant, N.-O.: Bioconversion of lignocellulose: inhibitors and detoxification. Biotechnol. Biofuels 6, 1–10 (2013)

    Article  Google Scholar 

  7. Garrote, G., Cruz, J.M., Moure, A., Domìnguez, H., Parajó, J.C.: Antioxidant activity of byproducts from the hydrolytic processing of selected lignocellulosic materials. Trends Food Sci. Technol. 15, 191–200 (2004)

    Article  Google Scholar 

  8. Alexandri, M., Llano, T., Gardeli, C., Papapostolou, H., Komaitis, M., Papanikolaou, S., Coz, A., Koutinas, A.: Solvent extraction and analysis of phenolic compounds derived from spent sulphite liquor for enhanced succinic acid fermentation. In: 36th Symposium on Biotechnology for Fuels and Chemicals (2014)

  9. Marinova, E.M., Yanishlieva, N.V.I., Kostova, I.V.: Antioxidative activity of extracts from selected species of the family Lamiaceae in sunflower oil. Food Chem. 58, 245–248 (1997)

    Article  Google Scholar 

  10. Fernández de Simón, B., Cadahía, E., Conde, E., García-Vallejo, M.C.: Low molecular weight phenolic compounds in Spanish oak woods. J. Agric. Food Chem. 44, 1507–1511 (1996)

    Article  Google Scholar 

  11. Cruz, J.M., Domínguez, J.M., Dominguez, H., Parajó, J.C.: Solvent extraction of hemicellulosic wood hydrolysates: a procedure useful for obtaining both detoxified fermentation media and polyphenols with antioxidant activity. Food Chem. 67, 147–153 (1999)

    Article  Google Scholar 

  12. Faustino, H., Gil, N., Baptista, C., Duarte, A.P.: Antioxidant activity of lignin phenolic compounds extracted from kraft and sulphite black liquors. Molecules 15, 9308–9322 (2010)

    Article  Google Scholar 

  13. Cruz, J.M., Domínguez, H., Parajó, J.C.: Antioxidant activity of isolates from acid hydrolysates of Eucalyptus globulus wood. Food Chem. 90, 503–511 (2005)

    Article  Google Scholar 

  14. Waterhouse, A.L.: Determination of total phenolics. Curr. Protoc. Food Analyt. Chem. I1.1.1–I1.1.8 (2002)

  15. Standard UNE-EN 16109: Fertilizers-determination of complexed micro-nutrients ions in fertilizers. Identification of lignosulfonates. http://www.en.aenor.es/aenor/normas/normas/fichanorma.asp?tipo=N&codigo=N0049498&PDF=Si#.VffJbBHtmkp. Accessed Sept 2015 (2012)

  16. Scherer, R., Godoy, H.T.: Antioxidant activity index (AAI) by the 2,2-diphenyl-1-picrylhydrazyl method. Food Chem. 112, 654–658 (2009)

    Article  Google Scholar 

  17. Brand-Williams, W., Cuvelier, M.E., Berset, C.: Free radical method to evaluate antioxidant acitivity: Lebensm. Wiss. U. Technol. 28, 25–30 (1995)

    Article  Google Scholar 

  18. Guendez, R., Kallithraka, S., Makris, D.P., Kefalas, P.: Determination of low molecular weight polyphenolic constituents in grape (Vitis vinifera sp.) seed extracts: correlation with antiradical activity. Food Chem. 89, 1–9 (2005)

    Article  Google Scholar 

  19. Proestos, C., Sereli, D., Komaitis, M.: Determination of phenolic compounds in aromatic plants by RP-HPLC and GC-MS. Food Chem. 95, 44–52 (2006)

    Article  Google Scholar 

  20. Llano, T., Quijorna, N., Portilla, A.I., Andrés, A., Coz, A.: Analysis of sugars, intermediates and inhibitors in sulphite pulping by HPLC/RID. In: XXII TECNICELPA International Forest, Pulp and Paper Conference. Book of abstracts, 135 (2013)

  21. Parajó, J.C., Domínguez, H., Domínguez, J.M.: Biotechnological production of xylitol. Part 3: operation in culture media made from lignocellulose hydrolysates. Bioresour. Technol. 66, 25–40 (1998)

    Article  Google Scholar 

  22. Parajó, J.C., Domínguez, H., Dominguez, J.M.: Xylitol production from Eucalyptus wood hydrolysates extracted with organic solvents. Process. Biochem. 32, 599–604 (1997)

    Article  Google Scholar 

  23. Khoddami, A., Wilkes, M.A., Roberts, T.H.: Techniques for analysis of plant phenolic compounds. Molecules 18, 2328–2375 (2013)

    Article  Google Scholar 

  24. Neto, C.P., Belino, E., Evtuguin, D., Silvestre, A.J.D.: Total fractionation and analysis of organic components of industrial Eucalyptus globulus kraft black liquor. Appita J. 52, 213–225 (1999)

    Google Scholar 

  25. Marques, A.P., Evtuguin, D.V., Magina, S., Amado, F.M.L., Prates, A.: Chemical composition of spent liquors from acidic magnesium sulphite pulping of Eucalyptus globulus. J. Wood Chem. Technol. 29, 322–336 (2009)

    Article  Google Scholar 

  26. Klinke, H.B., Thomsen, A.B., Ahring, B.K.: Inhibition of ethanol-producing yeast and bacteria by degradation products produced during pre-treament of biomass. Appl. Microbiol. Biotechnol. 66, 10–26 (2004)

    Article  Google Scholar 

  27. Garrote, G., Cruz, J.M., Domínguez, H., Parajó, J.C.: Valorisation of waste fractions from autohydrolysis of selected lignocellulosic materials. J. Chem. Technol. Biotechnol. 78, 392–398 (2003)

    Article  Google Scholar 

  28. Bonoli, M., Verardo, V., Marconi, E., Caboni, M.F.: Antioxidant phenols in barley (Hordeum vulgare L.) flour: comparative spectrophotometric study among extraction methods of free and bound phenolic compounds. J. Agric. Food Chem. 52, 5195–5200 (2004)

    Article  Google Scholar 

  29. Molyneux, P.: The use of the stable free radical diphenylpicrylhydrazyl (DPPH) for estimating antioxidant activity. Songklanakarin J. Sci. Technol. 26, 211–219 (2004)

    Google Scholar 

  30. González, J., Cruz, J.M., Domínguez, H., Parajó, J.C.: Production of antioxidants from Eucalyptus globulus wood by solvent extraction of hemicellulose hydrolysates. Food Chem. 84, 243–251 (2004)

    Article  Google Scholar 

  31. Kähkönen, M.P., Hopia, A.I., Vuorela, H.J., Rauha, J.P., Pihlaja, K., Kujala, T.S., Heinonen, M.: Antioxidant activity of plant extracts containing phenolic compounds. J. Agric. Food Chem. 47, 3954–3962 (1999)

    Article  Google Scholar 

  32. Shevchenko, Y., Hemmerich, I., Helfert, J., Smetanska, I.: Influence of Stevia—additives on antioxidant properties of different green teas. Agro Food Ind. Hi. Tech. 24, 22–26 (2013)

    Google Scholar 

  33. Villaño, D., Fernández-Pachón, M.S., Moyá, M.L., Troncoso, A.M., García-Parrilla, M.C.: Radical scavenging ability of polyphenolic compounds towards DPPH free radical. Talanta 71, 230–235 (2007)

    Article  Google Scholar 

  34. Rice-Evans, C., Miller, N., Paganga, G.: Antioxidant properties of phenolic compounds. Trends Plants Sci. 2, 152–159 (1997)

    Article  Google Scholar 

  35. Fukumoto, L.R., Mazza, G.: Assessing antioxidant and prooxidant activities of phenolic compounds. J. Agric. Food Chem. 48, 3597–3604 (2000)

    Article  Google Scholar 

  36. Lai, Y.Z., Guo, X.P.: Variation of the phenolic hydroxyl group content in wood lignins. Wood Sci. Technol. 25, 467–472 (1991)

    Article  Google Scholar 

  37. Chandel, A.K., da Silva, S.S., Singh, O.V.: Detoxification of lignocellulose hydrolysates: biochemical and metabolic engineering toward white biotechnology. Bioenerg. Res. 6, 388–401 (2013)

    Article  Google Scholar 

  38. Santos, S.A.O., Villaverder, J.J., Sousa, A.F., Coelho, J.F.J., Neto, C.P., Silvestre, A.J.D.: Phenolic composition and antioxidant activity of industrial cork by-products. Ind. Crops Prod. 47, 262–269 (2013)

    Article  Google Scholar 

  39. Vermerris, W., Nicholson, R.: Phenolic Compound Biochemistry. Springer, Heidelberg (2008)

    Google Scholar 

  40. Bjørsvik, H.R., Liguori, L.: Organic processes to pharmaceutical chemicals based on fine chemicals from lignosulfonates. Org. Process Res. Dev. 6, 279–290 (2002)

    Article  Google Scholar 

  41. Mateo, S., Roberto, I.C., Sánchez, S., Moya, A.J.: Detoxification of hemicellulose hydrolysate from olive tree pruning residue. Ind. Crops and Prod. 49, 196–203 (2013)

    Article  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the financial support by KBBE-2012-6-311935 BRIGIT research project. www.brigit-project.eu. Ms. Tamara Llano acknowledges the Erasmus Mobility Program for her research stay in the Agricultural University of Athens during the Ph.D. study.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to A. Koutinas or A. Coz.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Llano, T., Alexandri, M., Koutinas, A. et al. Liquid–Liquid Extraction of Phenolic Compounds from Spent Sulphite Liquor. Waste Biomass Valor 6, 1149–1159 (2015). https://doi.org/10.1007/s12649-015-9425-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12649-015-9425-9

Keywords

Navigation