4.7 Article

Emulsion Stabilization by Cationic Lignin Surfactants Derived from Bioethanol Production and Kraft Pulping Processes

Journal

POLYMERS
Volume 14, Issue 14, Pages -

Publisher

MDPI
DOI: 10.3390/polym14142879

Keywords

lignin; amination; emulsion; bitumen; rheology; microstructure

Funding

  1. SUP&R ITN (FP7-PEOPLE-2013-ITN) [607524]
  2. GreenAsphalt project [802C1800001]
  3. 80% by FEDER European Programme
  4. 20% by Junta de Andalucia (Consejeria de Economia, Conocimiento, Empresas y Unversidades/AgenciaIDEA)
  5. Comunidad de Madrid
  6. MCIU/AEI/FEDER, UE [SUSTEC-CM S2018/EMT-4348, RTI2018-096080-B-C22]
  7. COST (European Cooperation in Science and Technology) [CA17128]

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Oil-in-water bitumen emulsions stabilized by biobased surfactants, specifically lignin derived from the kraft pulping and bioethanol industries, were investigated in this study. A comprehensive chemical characterization of the lignin samples was conducted, revealing differences in lignin concentration, molecular weight, and presence of carbohydrate residues and ashes. The emulsification ability of lignin-based cationic surfactants was evaluated on prototype silicone oil-in-water emulsions, with cationic kraft lignin showing the best performance. It successfully stabilized bitumen emulsions with a high bitumen content using small surfactant concentrations.
Oil-in-water bitumen emulsions stabilized by biobased surfactants such as lignin are in line with the current sustainable approaches of the asphalt industry involving bitumen emulsions for reduced temperature asphalt technologies. With this aim, three lignins, derived from the kraft pulping and bioethanol industries, were chemically modified via the Mannich reaction to be used as cationic emulsifiers. A comprehensive chemical characterization was conducted on raw lignin-rich products, showing that the kraft sample presents a higher lignin concentration and lower molecular weight. Instead, bioethanol-derived samples, with characteristics of non-woody lignins, present a high concentration of carbohydrate residues and ashes. Lignin amination was performed at pH = 10 and 13, using tetraethylene pentamine and formaldehyde as reagents at three different stoichiometric molar ratios. The emulsification ability of such cationic surfactants was firstly studied on prototype silicone oil-in-water emulsions, attending to their droplet size distribution and viscous behavior. Among the synthetized surfactants, cationic kraft lignin has shown the best emulsification performance, being used for the development of bitumen emulsions. In this regard, cationic kraft lignin has successfully stabilized oil-in-water emulsions containing 60% bitumen using small surfactant concentrations, between 0.25 and 0.75%, which was obtained at pH = 13 and reagent molar ratios between 1/7/7 and 1/28/28 (lignin/tetraethylene pentamine/formaldehyde).

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