| Title: | Reaction mechanism and microkinetics of heterogeneously catalysed lignin depolymerisation and (de)functionalization : dissertation |
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| Authors: | ID Ročnik, Tina (Author)
ID Jasiukaityte, Edita (Mentor) More about this mentor... 
ID Grilc, Miha (Mentor) More about this mentor... |
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| Files: |  Disertation_Rocnik_Kozmelj_sep_24.pdf (5,04 MB)
MD5: 5D077B633C4C7F98ABECCB23528E2001
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| Language: | English |
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| Work type: | Doctoral dissertation |
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| Typology: | 2.08 - Doctoral Dissertation |
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| Organization: | FPŠ - Graduate School
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| Abstract: | Lignin, a complex aromatic polymer derived from lignocellulosic biomass, is a renewable resource for the production of aromatic-like chemicals and materials. However, its complex nature, depolymerisation and valorisation remain a major challenge for the bio-based community within biorefinery concepts. For this reason, lignin model compounds have been used to understand and design lignin depolymerisation, but insufficient attention has been paid to linking knowledge between simpler systems and applying it to a more complex problem. The objectives of this thesis were formulated accordingly to address the aforementioned gap in the literature. The objectives included a systematic approach correlating studies of lignin model compounds with lignin. Hydrodeoxygenation, cleavage of the β-O-4 bond and depolymerisation were investigated to evaluate the process- and structure-dependent correlations, effects on product distribution and kinetic parameters.
The catalytic reactions were carried out in batch reactor and the conditions were applied and intensified according to the knowledge gained during the experimental work. The liquid samples for monomer yield evaluation were analysed by GC-MS, while the structural characteristics of lignin and oligomeric fragments, e.g. molecular weight, functionality/reactivity and structural features, were examined by SEC, quantitative 31P and 2D-HSQC NMR. Kinetic modelling was performed to determine the kinetic parameters (e.g. kinetic constants and activation energies) describing defunctionalisation, β-O-4 bond cleavage and depolymerisation.
The study with monomeric lignin compounds contributed to the understanding of the key parameters leading to condensation during hydrotreatment. The unsaturated alkyl side-chain of eugenol and the reactive hydroxyl groups bound irreversibly and formed the carbonaceous species, while 4-propylphenol and 4-propylguaiacol provided important insights into the contribution of steric hindrances to a favourable reaction mechanism. An initial assessment of β-O-4 cleavage was performed with β-O-4-model compound, 2-phenoxy-1-phenylethanol, and linked to the lignin macromolecule by process- and structure-dependent correlations. Although the lignin model compound lacks the structural complexity of lignin, important insights into possible reaction processes were gained and accurate kinetic parameters were determined. Furthermore, lignin isolated in 50 vol% EtOH/H2O solutions was depolymerised and the optimal
reaction conditions were defined at a temperature of 275 °C and a pressure of 1.5 MPa with regard to the product distribution and the changes in the structural characteristics of the corresponding oligomeric fragments. Depolymerisation of lignins isolated in different EtOH/H2O solutions showed the importance of the structural features, especially ethoxylation degree and the content of β-O-4 or α-ethoxylated β-O-4 bonds. A higher ethoxylation degree of lignin reduced its potential to depolymerise and achieve the theoretical monomer yield. Therefore, the structural characteristics of lignin play the main role in designing and prediction of lignin depolymerisation.
The thesis represents a systematic approach of increasing the complexity of structures exposed to hydrodeoxygenation and depolymerisation. The approach contributed to incorporating the knowledge gained from less complex model compounds to real lignin samples by tailoring and designing lignin depolymerisation to exploit the potential of lignin for biorefinery concepts. |
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| Keywords: | model compounds, hydrodeoxygenation, organosolv lignin, depolymerisation, structural characteristics, kinetic modelling, dissertations |
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| Publication status: | Published |
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| Publication version: | Version of Record |
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| Place of publishing: | Nova Gorica |
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| Place of performance: | Nova Gorica |
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| Publisher: | T. Ročnik Kozmelj |
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| Year of publishing: | 2024 |
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| Year of performance: | 2024 |
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| Number of pages: | 116 str. |
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| PID: | 20.500.12556/RUNG-9414 |
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| COBISS.SI-ID: | 215687427 |
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| UDC: | 620.1/.2 |
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| NUK URN: | URN:SI:UNG:REP:SBGS1ZQG |
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| Publication date in RUNG: | 08.11.2024 |
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| Views: | 218 |
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| Downloads: | 0 |
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