Trade-offs between sulfidity and physicochemical properties of recovered Eucalyptus kraft lignin
Source abstract
Abstract
Abstract Kraft lignin is a promising biopolymer for product diversification in the pulp and paper industry and integrated biorefinery concepts. This study evaluated the effect of white liquor sulfidity (0–40 %) on Eucalyptus spp. kraft lignin recovered by acid precipitation (CO 2 and HCl). The recovered lignins were characterized in terms of elemental composition, thermal behavior, and chemical structure. While sulfidity had a limited impact on the overall thermal stability and decomposition profiles, it strongly affected pulping performance, including total yield, H-factor, and cooking severity. Notably, the sulfur and sodium contents of the recovered lignin varied systematically with sulfidity, reflecting changes in the delignification pathway and black liquor chemistry. Higher sulfidity enhanced sulfide-assisted lignin fragmentation, leading to the incorporation of sulfur-containing functionalities (e.g., thiols and mercaptans) and a reduced dependence on sodium for lignin solubility. The outcomes provided insights into how sulfidity can influence lignin properties with implications for its subsequent use in advanced materials applications.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: Lignin and Wood Chemistry · Advanced Cellulose Research Studies · Wood Treatment and Properties
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Nuclear Energy in Agriculture Center, University of São Paulo (CENA/USP) , 303 Centenário Ave., 303 , 13416-000 Piracicaba , SP , Brazil
Luiz de Queiroz College of Agriculture, University of São Paulo (ESALQ/USP) , 11 Padua Dias Ave. , 13418-900 Piracicaba , SP , Brazil
Funding
This study was financially supported by the Coordination for the Improvement of Higher Education Personnel “Brazil (CAPES)”
References (47)
Show source-provided references
1. Argyropoulos, D.D.S., Crestini, C., Dahlstrand, C., Furusjö, E., Gioia, C., Jedvert, K., Henriksson, G., Hulteberg, C., Lawoko, M., Pierrou, C., et al.. (2023). Kraft lignin: a valuable, sustainable resource, opportunities and challenges. ChemSusChem 16: e202300492, https://doi.org/10.1002/cssc.202300492.10.1002/cssc.202300492 ↗
2. Bilhalva dos Santos, P., Erdocia, X., Gatto, D.A., and Labidi, J. (2014). Characterisation of kraft lignin separated by gradient acid precipitation. Ind. Crop Prod. 55: 149–154, https://doi.org/10.1016/j.indcrop.2014.01.023.10.1016/j.indcrop.2014.01.023 ↗
3. Brebu, M., Tamminen, T., and Spiridon, I. (2013). Thermal degradation of various lignins by TG-MS/FTIR and Py-GC-MS. J. Anal. Appl. Pyrolysis 104: 531–539, https://doi.org/10.1016/j.jaap.2013.05.016.10.1016/j.jaap.2013.05.016 ↗
4. Cardoso, M.S.; Gonçalez, J.C. (2016) Aproveitamento da casca do coco-verde (Cocos nucifera L.) para produção de polpa celulósica. Ciênc. Florest. 26: 321–330, https://doi.org/10.5902/1980509821126.10.5902/1980509821126 ↗
5. Chávez-Sifontes, M.; Domine, M.E (2013) Lignina, estructura y aplicaciones: métodos de despolimerización para la obtención de derivados aromáticos de interés industrial lignin, structure and applications: depolymerization methods for obtaining aromatic derivatives of industrial interest. Av. Cienc. Ing. 4: 15–46.
6. Dessbesell, L., Paleologou, M., Leitch, M., Pulkki, R., and Xu, C. (2020). Global lignin supply overview and kraft lignin potential as an alternative for petroleum-based polymers. Renew. Sustain. Energy Rev. 123: 109768, https://doi.org/10.1016/j.rser.2020.109768.10.1016/j.rser.2020.109768 ↗
7. Dorn, L., Thirion, A., Ghorbani, M., Olaechea, L.M., and Mayer, I. (2023). Exploring fully biobased adhesives: sustainable kraft lignin and 5-HMF adhesive for particleboards. Polymers 15: 2668, https://doi.org/10.3390/polym15122668.10.3390/polym15122668 ↗
8. Duarte, F.A.S. (2007). Avaliação da madeira de Betula pendula, Eucalyptus globulus e de híbrido de Eucalyptus grandis x Eucalyptus urophylla destinadas à produção de polpa celulósica kraft, Master’s thesis. University of São Paulo.
9. Fearon, O., Kuitunen, S., Ruuttunen, K., Alopaeus, V., and Vuorinen, T. (2020). Detailed modeling of kraft pulping chemistry: delignification. Ind. Eng. Chem. Res. 59: 12977–12985, https://doi.org/10.1021/acs.iecr.0c02110.10.1021/acs.iecr.0c02110 ↗
10. Foelkel, C. (2023) As biorrefinarias integradas no setor brasileiro de fabricação de celulose e papel. Eucalyptus Online Book & Newsletter 29: 1–244.
11. Gierer, J. (1980). Chemical aspects of kraft pulping. Wood Sci. Technol. 14: 241–266, https://doi.org/10.1007/BF00383453.10.1007/BF00383453 ↗
12. Gomes, R.M. and Silva Júnior, F.G. (2020). Impact of sulfidity on the kraft pulping of Eucalyptus. BioResource 15: 3945–3961.10.15376/biores.15.2.3945-3961 ↗
13. Gomide, J.L., Demuner, B.J. (1986). Determinação do teor de lignina em material lenhoso: Método de Klason Modificado. O Papel, 47: 36–38.
14. Ház, A., Jablonský, M., Šurina, I., Kačík, F., Bubeníková, T., and Ďurkovič, J. (2019). Chemical composition and thermal behavior of kraft lignins. Forests 10: 483, https://doi.org/10.3390/f10060483.10.3390/f10060483 ↗
15. Henriksson, G., Germgård, U., and Lindström, M.E. (2024). A review on chemical mechanisms of kraft pulping. Nord. Pulp Pap. Res. J. 39: 297–311, https://doi.org/10.1515/npprj-2023-0015.10.1515/npprj-2023-0015 ↗
16. Ibarra, D., García-Fuentevilla, L., Rubio-Valle, J., Martín-Sampedro, R., Valencia, C., and Eugenio, M.E. (2023). Kraft lignins from different poplar genotypes obtained by selective acid precipitation and their use for the production of electrospun nanostructures. React. Funct. Polym. 191: 105685, https://doi.org/10.1016/j.reactfunctpolym.2023.105685.10.1016/j.reactfunctpolym.2023.105685 ↗
17. Khwanjaisakun, N., Amornraksa, S., Simasatitkul, L., Charoesnsuppanimit, P., and Assabumrungrat, S. (2020). Techno-economic analysis of vanillin production from kraft lignin: feasibility study of lignin valorization. Bioresour. Technol. 299: 122559, https://doi.org/10.1016/j.biortech.2019.122559.10.1016/j.biortech.2019.122559 ↗
18. Lehtonen, J., Johansson, P., Babaeipour, S., Nousiainen, P., Periyasamy, A.P., Österberg, M., and Vuorinen, T. (2025). Application of kraft lignin as a colorant for screen printing on cotton. Ind. Crops Prod. 230: 121056, https://doi.org/10.1016/j.indcrop.2025.121056.10.1016/j.indcrop.2025.121056 ↗
19. Liu, J., Li, X., Li, M., and Zheng, Y. (2022). Lignin biorefinery: lignin source, isolation, characterization, and bioconversion. In: Yebo, L., and Yuguang, Z. (Eds.). Advances in bioenergy, 7th v. Academic Press, pp. 211–270, https://doi.org/10.1016/bs.aibe.2022.05.004.10.1016/bs.aibe.2022.05.004 ↗
20. Lora, J. (2008). Industrial comercial lingins: sources, properties and applications. In: Naceur Belgacem, M., and Gandini, A. (Eds.). Monomers, polymers and composites from renewable resources. Elsevier B.V., Amsterdam, pp. 225–241.In10.1016/B978-0-08-045316-3.00010-7 ↗
21. Lora, J.H. and Glasser, W.G. (2002). Recent industrial application of lignin: a sustainable alternative to nonrenewable materials. J. Polym. Environ. 10: 39–48, https://doi.org/10.1023/A:1021070006895.10.1023/A:1021070006895 ↗
22. Madyaratri, E.W., Iswato, A.H., Nawawi, D.S., Lee, S.H., and Fatriasari, W. (2022). Improvement of thermal behavior of rattan by lignosulphonate impregnation treatment. Forests 13: 1773, https://doi.org/10.3390/f13111773.10.3390/f13111773 ↗
23. Marabezi, K. (2009). Estudo sistemático das reações envolvidas na determinação de teores de lignina e holocelulose em amostras de bagaço ou palha de cana – de – açúcar, Master’s thesis. University of São Paulo. http://www.teses.usp.br/teses/disponiveis/75/75131/tde-07102009-100309/.
24. Maximo, Y.I.; Hassegawa, M.; Verkerk, P.J.; Missio, A.L. (2022) Forest bioeconomy in Brazil: potential innovative products from the forest sector. Land 11: 1297, https://doi.org/10.3390/land11081297.10.3390/land11081297 ↗
25. Morais, S.A.; Nascimento, E.A.; Piló-Veloso, D. (1994) Determinação do grau de condensação e do número de grupos metoxila por unidade monomérica de ligninas do Eucalyptus grandis por espectroscopia FTIR. Química Nova 17: 5–8, https://typeset.io/pdf/determinacao-do-grau-de-condensacao-e-do-numero-de-grupos-4i8qthsn0r.pdf.
26. Mun, J.S. and Mun, S.P. (2024). Potential of hardwood kraft lignin as a bio-based dye for cotton fabrics. BioResources 19: 973–984, https://doi.org/10.15376/biores.19.1.973-984.10.15376/biores.19.1.973-984 ↗
27. Němec, M., Prokůpek, L., Obst, V., Pipíška, T., Král, P., and Hýsek, Š. (2024). Novel kraft-lignin-based adhesives for the production of particleboards. Compos. Struct. 344: 118344, https://doi.org/10.1016/j.compstruct.2024.118344.10.1016/j.compstruct.2024.118344 ↗
28. Palmeiras, L.P.S. (2010). Quantificação de metanol celulósico obtido a partir de licor negro de processos krfat de polpação, Master’s thesis. University of Sao Paulo.
29. Rahmati, H., Navace-Ardeh, S., and Aminian, H. (2007). Influence of sulfidity and active alkali on the proprieties of pulp produced Eucalyptus camaldulensis. J. Plant Sci. 2: 600–606, https://doi.org/10.3923/jps.2007.600.606.10.3923/jps.2007.600.606 ↗
30. Ramzan, H., Usman, M., Nadeem, F., Shahzaib, M., Rahman, M.U., Singhania, R.R., Jabeen, F., Patel, A.K., Qing, C., Liu, S., et al. (2023). Depolymerization of lignin: recent progress towards value-added chemicals and biohydrogen production. Bioresour. Technol. 386: 129492, https://doi.org/10.1016/j.biortech.2023.129492.10.1016/j.biortech.2023.129492 ↗
31. Ridho, M.R., Nawawi, D.S., Juliana, I., and Fatriasari, W. (2022). The kraft lignin characteristics of areca leaf sheath isolated by phosphoric acid. Bioresour. Technol. Rep. 23: 101569, https://doi.org/10.1016/j.biteb.2023.101569.10.1016/j.biteb.2023.101569 ↗
32. Rodrigues, J.S., Freitas, A.S.M., Maciel, C.C., Mendes, S.F., Diment, D., Balakshin, M., and Botaro, V.R. (2023). Selection of kraft lignin fractions as a partial substitute for phenol in synthesis of phenolic resins: structure-property correlation. Ind. Crops Prod. 191: 115948, https://doi.org/10.1016/j.indcrop.2022.115948.10.1016/j.indcrop.2022.115948 ↗
33. Saliba, E.O.S., Rodriguez, N.M., Morais, S.A.L., and Piló-Veloso, D. (2001). Lignin: methods of obtaining and chemical characterization. Ciênc. Rural 31: 917–928, Santa Maria https://doi.org/10.1590/S0103-84782001000500031.10.1590/S0103-84782001000500031 ↗
34. Santos, P.S.B., Erdocia, X., Gatto, D.A., and Labidi, J. (2014). Characterisation of kraft lignin separated by gradient acid precipitation. Ind. Crops Prod. 55: 149–154, https://doi.org/10.1016/j.indcrop.2014.01.023.10.1016/j.indcrop.2014.01.023 ↗
35. Sameni, J., Krigstin, S., Rosa, D.D.S., Leão, A., and Sain, M. (2014). Thermal characteristics of lignin residue from industrial processes. BioResources 9: 725–737, https://doi.org/10.15376/biores.9.1.725-737.10.15376/biores.9.1.725-737 ↗
36. Sarkanen, K.V. and Ludwig, C.H. (Eds.) (1971). Lignins: occurrence, formation, structure and reactions. Wiley-Interscience, New York, pp. 241–266.
37. Scandinavian Standard - SCAN (1994). N 33: residual alkali (hydroxide ion content) in black liquor.
38. Silva, F.J., Gomide, J.L., Colodette, J.L., and Oliveira Filho, A.C. (2002). Efeito da redução da sulfidez com adição de antraquinona nas emissões poluentes e na qualidade da polpa kraft de eucalipto [Effect of reducing sulfidity with the addition of antraquinone on pollutants emission and on eucalyptus kraft pulp’s quality]. O Papel 62: 77–87.
39. Singh, R., Singh, S., Trimukhe, K.D., Pandare, K.V., Astawade, K.B., Gokhale, D.V., and Varma, A.J. (2005). Lignin–carbohydrate complexes from sugarcane bagasse: preparation, purification, and characterization. Carbohydr. Polym 62: 57–66, https://doi.org/10.1016/j.carbpol.2005.07.011.10.1016/j.carbpol.2005.07.011 ↗
40. Smook, G.A. (1994). Handbook for pulp & paper technologists. Angus Wide Publication, Vancouver, TAPPI.
41. Technical Association of the Pulp and Paper Industry - TAPPI (1985). T 625: analysis of soda and sulfate black liquor.
42. Technical Association of the Pulp and Paper Industry - TAPPI (1989). T 650: solids content of black liquor.
43. Technical Association of the Pulp and Paper Industry - TAPPI (2002). T 211: ash in wood, pulp, paper and paperboard: combustion at 525°C.
44. Toucini, R. (2013). Processos de polpação, lavagem, depuração e secagem da polpa. In: Celulose/SENAI - SP. São Paulo: Senai -SP Editora, pp. 59–126.
45. Wei, X., Liu, Y., Luo, Y., Shen, Z., Wang, S., Li, M., and Zhang, L. (2021). Effect of organosolv extraction on the structure and antioxidant activity of eucalyptus kraft lignin. Int. J. Biol. Macromol. 187: 462–470, https://doi.org/10.1016/j.ijbiomac.2021.07.082.10.1016/j.ijbiomac.2021.07.082 ↗
46. Wörner, M., Werner, L., Hornung, U., Canabarro, N.I., Baudouin, D., and Dahmen, N. (2024). The impact of sulfur-containing inorganic compounds during the depolymerization of lignin by hydrothermal liquefaction of black liquor. Energy Fuels 38: 6036–6047.10.1021/acs.energyfuels.3c04737 ↗
47. Zhang, H., Fu, S., and Chen, Y. (2020). Basic understanding of the color distinction of lignin and the proper selection of lignin in color-depended utilizations. Int. J. Biol. Macromol. 147: 607–615, https://doi.org/10.1016/j.ijbiomac.2020.01.105.10.1016/j.ijbiomac.2020.01.105 ↗