Author ORCID Identifier

https://orcid.org/0000-0003-4502-5415

Year of Publication

2017

Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation

College

Arts and Sciences

Department

Chemistry

First Advisor

Dr. Mark Crocker

Abstract

With the dwindling availability of petroleum, focus has shifted to renewable energy sources such as lignocellulosic biomass. Lignocellulosic biomass is composed of three main constituents, lignin, cellulose and hemicellulose. Due to the low value of cellulosic ethanol, utilization of the lignin component is necessary for the realization of an economically sustainable biorefinery model. Once depolymerized, lignin has the potential to replace petroleum-derived molecules used as bulk and specialty aromatic chemicals. Numerous lignin depolymerization strategies focus on cleavage of β-aryl ether linkages, usually at high temperatures and under reductive conditions.

Alternatively, selective benzylic oxidation strategies have recently been explored for lignin and lignin models. In this work, heterogeneous catalytic methods using supported base metals and layered-double hydroxides were evaluated for the oxidation of lignin models both before and after benzylic oxidation. Additionally, by studying putative reaction intermediates, insights were gained into the mechanisms of oxidative fragmentation of the model compounds.

Generally, it was found that after benzylic oxidation models were more susceptible to oxidative fragmentation. Indeed, several heterogeneous oxidation systems were found to convert lignin models to oxygenated aryl monomers (mainly benzoic acids and phenols) using inexpensive primary oxidants (i.e., hydrogen peroxide and molecular oxygen). Reactions were conducted at relatively mild temperatures and at low oxygen concentrations for the purpose of an easy transition to large-scale experiments. Finally, the catalytic systems that resulted in significant cleavage of lignin models were applied to a Kraft lignin. Oxidation of Kraft lignin resulted a mixture of products for which analytical data and increased solubility are consistent with interunit cleavage within the lignin macromolecule.

Digital Object Identifier (DOI)

https://doi.org/10.13023/ETD.2017.300

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