, Volume 25, Issue 1, pp 293–304 | Cite as

Preparation of cellulose nanocrystals from lignin-rich reject material for oil emulsification in an aqueous environment

  • Jonna OjalaEmail author
  • Juho A. Sirviö
  • Henrikki Liimatainen
Original Paper


Cellulose nanocrystals (CNCs) with amphiphilic features were used in oil drop stabilization in diesel oil-in-water (o/w) emulsion. The functionalized CNCs were synthesized from a lignin-rich reject cellulose source from the pulp and paper industry, i.e., the non-bleached fines fractions of carton pulp. Partial periodate-chlorite oxidation, which was followed by reductive butylamination, was used to obtain surface-modified amphiphilic CNCs. All studied CNCs prevented droplet coalescence by stabilizing oil droplets in the emulsion thus resulting in stable o/w Pickering-like emulsions. CNCs from the fines fractions at concentrations 0.05–0.1% (weight by weight, w/w) provided high stability against creaming (i.e., phase separation), and they did not de-emulsify at low temperatures since the oil droplet size remained small at + 5 °C at a 0.05% (w/w) CNC concentration. Salinity improved the stability against creaming with the reference chemical pulp CNC, but negatively affected the emulsion creaming rate for CNCs that had a higher level of lignin. However, the non-bleached fines fraction of the pulp may provide one potential and cost-effective raw material source for the development of a novel bio-based chemical.


Nanocellulose Reject fiber fines Cellulose nanocrystals Oil in water emulsion Bio-based dispersant Lignin 



This study was funded by the Academy of Finland (283187). The support of the Ahti Pekkala Foundation and the Tiina and Antti Herlin Foundation is gratefully acknowledged. The contribution of Mr. Mikael Karjalainen in the raw material characterization and the experience of Dr. Ilkka Miinalainen in TEM measurements are also much appreciated. We thank Neste Oyj Finland for providing the marine diesel oil sample for the experiments.


  1. Al-Majed AA, Adebayo AR, Hossain ME (2012) A sustainable approach to controlling oil spills. J Environ Manag 113:213–227. CrossRefGoogle Scholar
  2. Chevalier Y, Bolzinger M-A (2013) Emulsions stabilized with solid nanoparticles: Pickering emulsions. Colloids Surf Physicochem Eng Asp 439:23–34. CrossRefGoogle Scholar
  3. Daza EA, Misra SK, Scott J et al (2017) Multi-shell nano-carboscavengers for petroleum spill remediation. Sci Rep 7:41880. CrossRefGoogle Scholar
  4. du Noüy PL (1925) An interfacial tensiometer for universal use. J Gen Physiol 7:625–633.
  5. Ek M, Gellerstedt G, Henriksson G (eds) (2009) Pulping chemistry and technology. In: Pulp and paper chemistry and technology. De Gruyter, BerlinGoogle Scholar
  6. García A, Gandini A, Labidi J et al (2016) Industrial and crop wastes: a new source for nanocellulose biorefinery. Ind Crops Prod 93:26–38. CrossRefGoogle Scholar
  7. George-Ares A, Clark JR (2000) Aquatic toxicity of two Corexit® dispersants. Chemosphere 40:897–906. CrossRefGoogle Scholar
  8. Gharehkhani S, Sadeghinezhad E, Kazi SN et al (2015) Basic effects of pulp refining on fiber properties—a review. Carbohydr Polym 115:785–803. CrossRefGoogle Scholar
  9. Gosselink RJA, van Dam JEG, de Jong E et al (2011) Effect of periodate on lignin for wood adhesive application. Holzforschung. Google Scholar
  10. Guodong Q, Yupeng Z, Xuhe R, Jie C (2015) Research on development and effectiveness evaluation technology of new environment-friendly oil spill dispersant. Aquat Procedia 3:245–253. CrossRefGoogle Scholar
  11. Hu Z, Ballinger S, Pelton R, Cranston ED (2015a) Surfactant-enhanced cellulose nanocrystal Pickering emulsions. J Colloid Interface Sci 439:139–148. CrossRefGoogle Scholar
  12. Hu Z, Patten T, Pelton R, Cranston ED (2015b) Synergistic stabilization of emulsions and emulsion gels with water-soluble polymers and cellulose nanocrystals. ACS Sustain Chem Eng 3:1023–1031. CrossRefGoogle Scholar
  13. Jiang Y, Liu X, Chen Y et al (2014) Pickering emulsion stabilized by lipase-containing periodic mesoporous organosilica particles: a robust biocatalyst system for biodiesel production. Bioresour Technol 153:278–283. CrossRefGoogle Scholar
  14. Kalashnikova I, Bizot H, Cathala B, Capron I (2011) New Pickering emulsions stabilized by bacterial cellulose nanocrystals. Langmuir ACS J Surf Colloids 27:7471–7479. CrossRefGoogle Scholar
  15. Kalashnikova I, Bizot H, Bertoncini P et al (2013) Cellulosic nanorods of various aspect ratios for oil in water Pickering emulsions. Soft Matter 9:952–959. CrossRefGoogle Scholar
  16. Katz S, Beatson RP, Scallan AM (1984) The determination of strong and weak acidic groups in sulfite pulps. Sven Papperstidning 65:48–53Google Scholar
  17. Kester DR, Duedall IW, Connors DN, Pytkowicz RM (1967) Preparation of artificial seawater. Limnol Oceanogr 12:176–179. CrossRefGoogle Scholar
  18. Koskenhely K (2008) Refining of chemical pulp fibers. In: Paulapuro H (ed) Papermaking part 1, stock preparation and wet end. Finnish Paper Engineers’ Association. Espoo, FinlandGoogle Scholar
  19. Nyankson E, DeCuir MJ, Gupta RB (2015) Soybean lecithin as a dispersant for crude oil spills. ACS Sustain Chem Eng 3:920–931. CrossRefGoogle Scholar
  20. Ojala J, Sirviö JA, Liimatainen H (2016) Nanoparticle emulsifiers based on bifunctionalized cellulose nanocrystals as marine diesel oil–water emulsion stabilizers. Chem Eng J 288:312–320. CrossRefGoogle Scholar
  21. Orelma H, Tanaka A, Rautkoski H et al (2017) Mechanically ground softwood fines as a raw material for cellulosic applications. Cellulose 24:3869–3882. CrossRefGoogle Scholar
  22. Pi G, Li Y, Bao M et al (2016) Novel and environmentally friendly oil spill dispersant based on the synergy of biopolymer xanthan gum and silica nanoparticles. ACS Sustain Chem Eng 4:3095–3102. CrossRefGoogle Scholar
  23. Prince RC (2015) Oil spill dispersants: Boon or bane? Environ Sci Technol 49:6376–6384. CrossRefGoogle Scholar
  24. Rattaz A, Mishra SP, Chabot B, Daneault C (2011) Cellulose nanofibres by sonocatalysed-TEMPO-oxidation. Cellulose 18:585–593. CrossRefGoogle Scholar
  25. Saha A, Nikova A, Venkataraman P et al (2013) Oil emulsification using surface-tunable carbon black particles. ACS Appl Mater Interfaces 5:3094–3100. CrossRefGoogle Scholar
  26. Silva MC, Lopes OR, Colodette JL et al (2008) Characterization of three non-product materials from a bleached eucalyptus kraft pulp mill, in view of valorising them as a source of cellulose fibres. Ind Crops Prod 27:288–295. CrossRefGoogle Scholar
  27. Sirvio J, Hyvakko U, Liimatainen H et al (2011) Periodate oxidation of cellulose at elevated temperatures using metal salts as cellulose activators. Carbohydr Polym 83:1293–1297. CrossRefGoogle Scholar
  28. Tadros TF (ed) (2013) Emulsion formation and stability. Wiley-VCH, WeinheimGoogle Scholar
  29. Wang W, Zheng Y, Lee K (2013) Chemical dispersion of oil with mineral fines in a low temperature environment. Mar Pollut Bull 72:205–212. CrossRefGoogle Scholar
  30. Xhanari K, Syverud K, Stenius P (2011) Emulsions stabilized by microfibrillated cellulose: the effect of hydrophobization, concentration and O/W ratio. J Dispers Sci Technol 32:447–452. CrossRefGoogle Scholar
  31. Yu G, Dong J, Foster LM et al (2014) Breakup of oil jets into droplets in seawater with environmentally benign nanoparticle and surfactant dispersants. Ind Eng Chem Res. Google Scholar
  32. Zeinstra-Helfrich M, Koops W, Murk AJ (2015) The NET effect of dispersants—a critical review of testing and modelling of surface oil dispersion. Mar Pollut Bull 100:102–111. CrossRefGoogle Scholar
  33. Zhang Y, Chen D, Ennis AC et al (2013) Chemical dispersant potentiates crude oil impacts on growth, reproduction, and gene expression in Caenorhabditis elegans. Arch Toxicol 87:371–382. CrossRefGoogle Scholar

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© Springer Science+Business Media B.V., part of Springer Nature 2017

Authors and Affiliations

  1. 1.University of Oulu, Fibre and Particle EngineeringOuluFinland

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