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dc.contributor.authorOrejuela, Lourdes Magdalenaen_US
dc.date.accessioned2017-12-16T09:00:14Z
dc.date.available2017-12-16T09:00:14Z
dc.date.issued2017-12-15en_US
dc.identifier.othervt_gsexam:13945en_US
dc.identifier.urihttp://hdl.handle.net/10919/81255
dc.description.abstractAbstract Non-edible plant biomass (lignocellulose) is a valuable precursor for liquid biofuels, through the processes of pretreatment and saccharification followed by fermentation into products such as ethanol or butanol. However, it is difficult to gain access to the fermentable sugars in lignocellulose, and this problem is principally associated with limited enzyme accessibility. Hence, biomass pretreatments that destroy native cell wall structure and allows enzyme access are required for effective biomass conversion techniques. This research studied two novel pretreatment methods on two wood species: 1) a deep eutectic solvent (DES) that, under heat, swells lignocellulose and partially solubilizes cell wall materials by causing breakage of lignin-carbohydrate linkages and depolymerization of the biomass components, and 2) a chelator-mediated Fenton reaction (CMF) that chemically modifies the nanostructure of the cell wall through a non-enzymatic cell wall deconstruction. After pretreatment, utilizing analytical techniques such as nuclear magnetic spectroscopy, wide angle x-ray scattering, and gel permeation chromatography, samples were analyzed for chemical and structural changes in the solubilized and residual materials. After single stage DES (choline-chloride-glycerol) and two stage, CMF followed by DES pretreatments, lignin/carbohydrate fractions were recovered, leaving a cellulose-rich fraction with reduced lignin and hemicellulose content as determined by compositional analysis. Lignin and heteropolysaccharide removal by DES was quantified and the aromatic-rich solubilized biopolymer fragments were analyzed as water insoluble high molecular weight fractions and water-ethanol soluble low molecular weight compounds. After pretreatment for the hardwood sample, enzyme digestibility reached a saccharification yield of 78% (a 13-fold increase) for the two stage (DES/CMF) pretreated biomass even with the presence of some lignin and xylan remained on the pretreated fiber; only a 9-fold increase was observed after the other sequence of CMF followed by DES treatment. Single stage CMF treatment or single stage DES pretreatment improved 5-fold glucose yield compared to the untreated sample for the hardwood sample. The enhancement of enzymatic saccharification for softwood was less than that of hardwoods with only 4-fold increase for the sequence CMF followed by DES treatment. The other sequence of treatments reached up to 2.5-fold improvement. A similar result was determined for the single stage CMF treatment while the single stage DES treatment reached only 1.4-fold increase compared to the untreated softwood. Hence, all these pretreatments presented different degrees of biopolymer removal from the cell wall and subsequent digestibility levels; synergistic effects were observed for hardwood particularly in the sequence DES followed by CMF treatment while softwoods remained relatively recalcitrant. Overall, these studies revealed insight into two novel methods to enhance lignocellulosic digestibility of biomass adding to the methodology to deconstruct cell walls for fermentable sugars. General Audience Abstract Wood is a valuable material that can be used to produce liquid biofuels. Wood main components are biopolymers cellulose, hemicellulose and lignin that form a complex structure. Nature has locked up cellulose in a protective assembly that needs to be destroyed to gain access to cellulose, convert it to glucose and then ferment it to bioalcohol. This process is principally associated with limited enzyme accessibility. Therefore, biomass pretreatments that deconstruct native cell wall structure and allow enzyme access are required for effective biomass conversion techniques. This research studied two novel pretreatment methods on two wood species: 1) a deep eutectic solvent called glyceline that, under heat, swells wood and partially solubilizes cell wall materials by causing breakage of bonds and converting it into smaller molecules (monomers and oligomers), and 2) a chelator-mediated Fenton system (CMF) that chemically modifies the structure of the cell wall. Pretreatments were tested individually and in sequence in sweetgum and southern yellow pine. After pretreatments, utilizing analytical techniques, fractions were investigated for chemical and structural changes in the solubilized and residual materials. Treated wood samples were exposed to enzymatic conversion. A maximum 78% of glucose yield was obtained for the glyceline followed by CMF pretreated wood. For yellow pine only a 24% of glucose yield was obtained for the CMF followed by glyceline treatment. All these pretreatments presented different degrees of biopolymer removal from the cell wall and subsequent enzyme conversion levels. Overall, these studies revealed insight into two novel methods to enhance wood conversion adding to the methodology to deconstruct cell walls for fermentable sugars.en_US
dc.format.mediumETDen_US
dc.publisherVirginia Techen_US
dc.rightsThis item is protected by copyright and/or related rights. Some uses of this item may be deemed fair and permitted by law even without permission from the rights holder(s), or the rights holder(s) may have licensed the work for use under certain conditions. For other uses you need to obtain permission from the rights holder(s).en_US
dc.subjectDeep eutectic solvent (DES)en_US
dc.subjectchelator-mediated Fenton system (CMF)en_US
dc.subjectpretreatmenten_US
dc.subjectbiomass saccharificationen_US
dc.subjectstructural analysisen_US
dc.titleLignocellulose deconstruction using glyceline and a chelator-mediated Fenton systemen_US
dc.typeDissertationen_US
dc.contributor.departmentChemistryen_US
dc.description.degreePh. D.en_US
thesis.degree.namePh. D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen_US
thesis.degree.disciplineMacromolecular Science and Engineeringen_US
dc.contributor.committeechairRenneckar, Scott Harolden_US
dc.contributor.committeechairGoodell, Barryen_US
dc.contributor.committeememberFrazier, Charles E.en_US
dc.contributor.committeememberHelm, Richard F.en_US
dc.contributor.committeememberEdgar, Kevin J.en_US


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