abstract
Development of innovative technologies for efficient, yet eco-friendly, biomass delignification is required to achieve higher sustainability than traditional processes. In this context, the use of deep eutectic solvents (DESs) for the delignification process could fulfil these requirements and stands today as a promising alternative. This work focuses on understanding the fundamental chemistry behind the cleavage of the beta-O-4 ether bond present in 2-phenoxy-1-phenylethanol (PPE), a lignin model compound, with three acidic DESs, including Propionic acid/Urea (PA : U), Lactic acid/Choline Chloride (LA : ChCl) and p-Toluenesulphonic acid/Choline chloride (pTSA : ChCl). The acidic nature of each DES influenced the efficiency of PPE cleavage and determined the extent of further side reactions of cleavage products. Although PA : U (2 : 1) demonstrated the ability to dissolve lignin, it is unable to cleave beta-O-4 ether linkage in PPE. On the other hand, LA : ChCl (10 : 1) allowed PPE cleavage, but an esterification between the PPE and lactic acid as well as oligomerization of lactic acid was detected. Among the examined solvents, pTSA : ChCl (1 : 1) demonstrated the highest performance in the PPE cleavage, although the high acidity of this system led to the condensation of cleavage products with prolonged time. The presence of water decreases the ability of DESs for cleavage, but the extension of undesired side reactions was also reduced. Finally, the analysis of intermediates and products of the reactions allowed the identification of a chlorinated species of PPE that precedes the cleavage reaction. A kinetic study using pTSA : ChCl (1 : 1) and pTSA : ChBr (1 : 1) was performed to unveil the role of the halide counterion present in DESs in the cleavage of the beta-O-4 ether bond and a new reaction mechanism was herein proposed and supported by density functional theory (DFT) calculations.
keywords
LIGNIN MODEL COMPOUNDS; IONIC LIQUID; LIGNOCELLULOSIC BIOMASS; AQUEOUS-SOLUTIONS; DEPOLYMERIZATION; DES; FRACTIONATION; PRETREATMENT; DEGRADATION; ACIDOLYSIS
subject category
Chemistry; Science & Technology - Other Topics
authors
Lopes, AMD; Gomes, JRB; Coutinho, JAP; Silvestre, AJD
our authors
André M. da Costa Lopes
External Researcher
Armando Jorge Domingues Silvestre
Full professor
José R. B. Gomes
Principal ResearcherGroups
G4 - Renewable Materials and Circular Economy
G6 - Virtual Materials and Artificial Intelligence
Projects
acknowledgements
This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, (UIDB/50011/2020 & UIDP/50011/2020), financed by national funds through the FCT/MCTES and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. The authors would like to thank the members of the ISPT Deep Eutectic Solvents in the pulp and paper industry consortium for their financial and in-kind contribution. This cluster consists of the following organisations: Altri - Celbi, Buckman, Crown Van Gelder, CTP, DS Smith Paper, ESKA, Essity, Holmen, ISPT, Mayr-Melnhof Eerbeek, Metsa Fibre, Mid Sweden University, Mondi, Omya, The Navigator Company, Sappi, Essity, Smurfit Kappa, Stora Enso, Eindhoven University of Technology, University of Aveiro, University of Twente, UPM, Valmet Technologies Oy, Voith Paper, VTT Technical Research Centre of Finland Ltd, WEPA and Zellstoff Pols. Furthermore, this project received funding from the Bio-Based Industries Joint Undertaking under the European Union's Horizon 2020 research and innovation programme under grant agreement Provides No. 668970 and was co-funded by TKI E&I with the supplementary grant `TKI-Toeslag' for Top consortia for Knowledge and Innovation (TKI's) of the Ministry of Economic Affairs and Climate Policy. The work was also funded by Fundacao para a Ciencia e Tecnologia (FCT) through the projects DeepBiorefinery (PTDC/AGR-TEC/1191/2014) and MultiBiorefinery (POCI-01-0145-FEDER-016403). The authors acknowledge ISPT for funding A. M. da Costa Lopes postdoctoral grant.