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Conversion of Protein-Rich Waste Biomass into Value-Added Polymers Open Access


Other title
Sustainable Chemistry
Activation Energy
Reaction Kinetics
Protein-rich Biomass
Differential Scanning Calorimetry
Type of item
Degree grantor
University of Alberta
Author or creator
El-Thaher, Nayef
Supervisor and department
Choi, Phillip (Chemical and Materials Engineering)
Examining committee member and department
Xiao, Huining (Chemical Engineering - University of New Brunswick)
Bressler, David (Agricultural, Food and Nutritional Science)
Prasad, Vinay (Chemical and Materials Engineering)
Liu, Qi (Chemical and Materials Engineering)
Department of Chemical and Materials Engineering
Chemical Engineering
Date accepted
Graduation date
Doctor of Philosophy
Degree level
Conversion of protein-rich biomass waste into value-added industrial products via chemical cross-linking reactions was explored. Two types of cross-linking reagents were investigated: dialdehydes and epoxy resins. Reaction chemistry was the main focus of this investigation and the main reaction parameters selected for study were electrolytes and protein molecular weight since raw material modification usually involves these two parameters. First, the reaction chemistry of glutaraldehyde was investigated. Glutaraldehyde is a cheap and highly reactive cross-linking reagent. Its reaction chemistry, however, is poorly understood. At low reaction temperatures, protein amine groups form Schiff bases with carbonyl groups of glutaraldehyde. The resulting C═N bond is weak and can be easily broken by heat or dissolution in water. As the reaction temperature is increased, the more stable C—N bond is formed. A network with low water solubility and significantly improved thermal stability is produced. The presence of water has a dual effect. Water acts as a medium to disperse hydrolyzed proteins into glutaraldehyde and is also a hydrogen source to drive the reaction forward. However, water is a byproduct. Its presence suppresses the reaction from the standpoint of thermodynamic equilibrium, and it must therefore be driven off. Epoxy-protein reaction chemistry was also investigated. The effects of salt, molecular weight and viscosity, and mass ratio on the apparent activation energy of the cross-linking reaction of epoxy resins and protein hydrolysate were studied by nonisothermal differential scanning calorimetry. The presence of salts contributed to an increase in the apparent activation energy. The curing of epoxy resins with lower molecular weight protein hydrolysates was found to have lower activation energy and order of reaction. An increase in the concentration of curing groups resulted in a small increase in the order of reaction. The activation energy of curing bisphenol A diglycidyl ether, with viscosity 500–700 cP, was found to be significantly higher than the curing activation energy of polypropylene glycol diglycidyl ether (viscosity ~50 cP). Denaturant addition was also investigated and was found to be an energetically efficient alternative to higher degrees of protein hydrolysis for subsequent reactions.
Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
Citation for previous publication
El-Thaher, N.; Mekonnen, T.; Mussone, P.; Bressler, D.; Choi, P. Effects of Electrolytes, Water, and Temperature on Cross-linking of Glutaraldehyde and Hydrolyzed Specified Risk Material. Ind. Eng. Chem. Res. 2013, 52, 4987-4993El-Thaher, N.; Mekonnen, T.; Mussone, P.; Bressler, D.; Choi, P. Nonisothermal DSC Study of Epoxy Resins Cured with Hydrolyzed Specified Risk Material. Ind. Eng. Chem. Res. 2013, 52, 8189−8199El-Thaher, N.; Mussone, P.; Bressler, D.; Choi, P. Kinetics Study of Curing Epoxy Resins with Hydrolyzed Proteins and the Effect of Denaturants Urea and Sodium Dodecyl Sulfate. ACS Sustainable Chem. Eng. 2013. In Press. DOI: 10.1021/sc400316v

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