Lignin oxidation with an organic peroxide and subsequent aromatic ring opening

Mónica R C Fernandes; Xiaoming Huang; Hendrikus C L Abbenhuis; Emiel J M Hensen

doi:10.1016/j.ijbiomac.2018.11.105

Lignin oxidation with an organic peroxide and subsequent aromatic ring opening

Int J Biol Macromol. 2019 Feb 15:123:1044-1051. doi: 10.1016/j.ijbiomac.2018.11.105. Epub 2018 Nov 17.

Authors

Mónica R C Fernandes¹, Xiaoming Huang², Hendrikus C L Abbenhuis³, Emiel J M Hensen⁴

Affiliations

¹ Schuit Institute of Catalysis, Laboratory of Inorganic Materials and Catalysis, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, the Netherlands; Hybrid Catalysies B.V., PO Box 513, 5600 MB Eindhoven, the Netherlands.
² Schuit Institute of Catalysis, Laboratory of Inorganic Materials and Catalysis, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, the Netherlands.
³ Hybrid Catalysies B.V., PO Box 513, 5600 MB Eindhoven, the Netherlands.
⁴ Schuit Institute of Catalysis, Laboratory of Inorganic Materials and Catalysis, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, the Netherlands. Electronic address: e.j.m.hensen@tue.nl.

PMID: 30458194
DOI: 10.1016/j.ijbiomac.2018.11.105

Abstract

The oxidation of an organosolv lignin with tert-butylhydroperoxide, initiated by titanium grafted into the lignin structure, was investigated. Titanation of reactive groups on lignin is responsible for the cross-linking of the lignin structure. IR and MAS ¹³C NMR spectroscopy spectra confirmed the oxidation of the lignin structure and other pronounced structural changes. A study with guaiacol as a model compound helped to recognise that aromatic ring opening occurs under the given conditions and is catalysed by the grafted titanium. The structure of the oxidised lignin becomes less robust and therefore potentially more susceptible to be depolymerised and converted into monomeric units.

Keywords: Aromatic ring opening; Biomass; Lignin; Oxidation.

MeSH terms

Carbon-13 Magnetic Resonance Spectroscopy
Guaiacol / chemistry
Hydrocarbons, Aromatic / chemistry*
Lignin / chemistry*
Models, Theoretical
Oxidation-Reduction
Peroxides / chemistry*
Proton Magnetic Resonance Spectroscopy

Substances

Hydrocarbons, Aromatic
Peroxides
Guaiacol
Lignin