Towards sustainable production of renewable chemicals from lignin

Environmental concerns have brought attention to the requirement for more efficient and renewable processes for chemicals production. Lignin is the second most abundant natural polymer, and might serve as a sustainable resource for manufacturing fuels and aromatic derivatives for the chemicals indus...

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Main Author: Eshtaya, Majd
Format: Thesis (University of Nottingham only)
Language:English
English
Published: 2016
Subjects:
Online Access:https://eprints.nottingham.ac.uk/38392/
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author Eshtaya, Majd
author_facet Eshtaya, Majd
author_sort Eshtaya, Majd
building Nottingham Research Data Repository
collection Online Access
description Environmental concerns have brought attention to the requirement for more efficient and renewable processes for chemicals production. Lignin is the second most abundant natural polymer, and might serve as a sustainable resource for manufacturing fuels and aromatic derivatives for the chemicals industry after being depolymerised. In this work, two main approaches were investigated with the aim of treatment of lignin with a mediator, 2,2’-azinobis(3-ethylbenthiazoline-6-sulfonic acid) diammonium salt (ABTS), in 1-ethyl-3-methylimidazolium ethyl sulfate, ([C2mim][C2SO4]). In the first approach, laccase from Trametes versicolor (LTV) was used to treat organosolv lignin, using [C2mim][C2SO4] as a co-solvent in the presence of ABTS. LTV was shown to possess catalytic activity for the degradation of organolsov lignin in systems containing ionic liquid and syringaldehyde was found to be a major product obtained from the process. ABTS alone has been evaluated for its reaction with lignin by means of cyclic voltammetry (CV). Here, the non-phenolic lignin model compound veratryl alcohol and three types of lignin (organosolv, Kraft and lignosulfonate) were specifically examined. The presence of either veratryl alcohol or organosolv lignin increased the second oxidation peak of ABTS under select conditions, indicating the ABTS-mediated oxidation of these molecules at high potentials in [C2mim][C2SO4]. Furthermore, CV was applied as a quick and efficient way to explore the impact of water in the ABTS-mediated oxidation of both organosolv and lignosulfonate lignin. Higher catalytic efficiencies of ABTS were observed for lignosulfonate solutions either in sodium acetate buffer, or when [C2mim][C2SO4] (15% v/v) was present in an aqueous solution, whilst there was no change found in the catalytic efficiency of ABTS in neat [C2mim][C2SO4]-lignosulfonate mixtures relative to ABTS alone. In contrast, organosolv showed an initial increase in oxidation, followed by a significant decrease on increasing the water content of a [C2mim][C2SO4] solution. Despite enhanced lignin solubility in ionic liquids, the yields of small molecules attributed to depolymerisation in ionic liquids are often quite low. Since depolymerisation approaches examined herein are thought to proceed via free-radical mediated mechanisms, two different stable radicals 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ABTS were assessed for the rapid monitoring of radical activity of lignin-related compounds in ionic liquid systems. While these assays are successful in aqueous and organic solvent systems, the presence of the ionic liquids complicates the assay procedure, requiring further developmental work.
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spelling nottingham-383922025-02-28T13:35:30Z https://eprints.nottingham.ac.uk/38392/ Towards sustainable production of renewable chemicals from lignin Eshtaya, Majd Environmental concerns have brought attention to the requirement for more efficient and renewable processes for chemicals production. Lignin is the second most abundant natural polymer, and might serve as a sustainable resource for manufacturing fuels and aromatic derivatives for the chemicals industry after being depolymerised. In this work, two main approaches were investigated with the aim of treatment of lignin with a mediator, 2,2’-azinobis(3-ethylbenthiazoline-6-sulfonic acid) diammonium salt (ABTS), in 1-ethyl-3-methylimidazolium ethyl sulfate, ([C2mim][C2SO4]). In the first approach, laccase from Trametes versicolor (LTV) was used to treat organosolv lignin, using [C2mim][C2SO4] as a co-solvent in the presence of ABTS. LTV was shown to possess catalytic activity for the degradation of organolsov lignin in systems containing ionic liquid and syringaldehyde was found to be a major product obtained from the process. ABTS alone has been evaluated for its reaction with lignin by means of cyclic voltammetry (CV). Here, the non-phenolic lignin model compound veratryl alcohol and three types of lignin (organosolv, Kraft and lignosulfonate) were specifically examined. The presence of either veratryl alcohol or organosolv lignin increased the second oxidation peak of ABTS under select conditions, indicating the ABTS-mediated oxidation of these molecules at high potentials in [C2mim][C2SO4]. Furthermore, CV was applied as a quick and efficient way to explore the impact of water in the ABTS-mediated oxidation of both organosolv and lignosulfonate lignin. Higher catalytic efficiencies of ABTS were observed for lignosulfonate solutions either in sodium acetate buffer, or when [C2mim][C2SO4] (15% v/v) was present in an aqueous solution, whilst there was no change found in the catalytic efficiency of ABTS in neat [C2mim][C2SO4]-lignosulfonate mixtures relative to ABTS alone. In contrast, organosolv showed an initial increase in oxidation, followed by a significant decrease on increasing the water content of a [C2mim][C2SO4] solution. Despite enhanced lignin solubility in ionic liquids, the yields of small molecules attributed to depolymerisation in ionic liquids are often quite low. Since depolymerisation approaches examined herein are thought to proceed via free-radical mediated mechanisms, two different stable radicals 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ABTS were assessed for the rapid monitoring of radical activity of lignin-related compounds in ionic liquid systems. While these assays are successful in aqueous and organic solvent systems, the presence of the ionic liquids complicates the assay procedure, requiring further developmental work. 2016-12-13 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/38392/1/Majd%20Eshtaya_ID%204194525.pdf application/pdf en arr https://eprints.nottingham.ac.uk/38392/8/Majd%20Eshtaya_ID%204194525%20%282%29.pdf Eshtaya, Majd (2016) Towards sustainable production of renewable chemicals from lignin. PhD thesis, University of Nottingham. Biopolymers Lignin
spellingShingle Biopolymers
Lignin
Eshtaya, Majd
Towards sustainable production of renewable chemicals from lignin
title Towards sustainable production of renewable chemicals from lignin
title_full Towards sustainable production of renewable chemicals from lignin
title_fullStr Towards sustainable production of renewable chemicals from lignin
title_full_unstemmed Towards sustainable production of renewable chemicals from lignin
title_short Towards sustainable production of renewable chemicals from lignin
title_sort towards sustainable production of renewable chemicals from lignin
topic Biopolymers
Lignin
url https://eprints.nottingham.ac.uk/38392/