Heterogeneous catalytic conversion of biomass-derived carbohydrates to furanic biofuel additives and chemicals
AdvisorHassan, El Barbary M.
CommitteeStreet, Jason Tyler
Jackson, Michael A.
Embargo TypeComplete embargo for 1 year
Embargo Lift Date2020-12-15
Increasing energy demand and various problems associated with fossil fuels such as environmental pollution, global warming and diminishing petroleum reserves have greatly stimulated production of fuels and chemicals from renewable sources. Lignocellulosic biomass has been considered as one of the potential sources for a variety of fuels and industrial chemicals. 5-Hydroxymethylfurfural (HMF) has been identiﬁed as an excellent platform molecule because it is a ﬂexible intermediate for the synthesis of bio-renewable fuels and materials. HMF can be easily obtained from acid-catalyzed hydration of biomass-derived carbohydrates (hexoses) in various media. HMF can be converted to energy products such as 2,5-bis(alkoxymethyl)furans (BAMFs), monomers for high-value polymers such as 2,5-bis(hydroxymethyl)furan (BHMF), and valuable intermediates for fine chemicals. Recently, magnetic nanoparticle based catalysts attracted more attention due to their good stability and easy separation from the reaction mixture by a permanent magnet. This unique magnetic separation property makes MNPs more effective than conventional filtration or centrifugation as it prevents loss of the catalyst. This dissertation work focuses on, firstly, studying the effectiveness of silica coated magnetite (Fe3O4) nanoparticles MNPs supported with sulfonic acid groups (Fe3O4@SiO2-SO3H) on the dehydration of glucose to HMF. Secondly, preparing a cost-effective catalytic transfer hydrogenation system for the selective transformation of HMF into BHMF via Meerwein-Ponndorf-Verley (MPV) reaction over the copper iron magnetic catalyst supported on activated carbon in ethanol solvent with the absence of molecular hydrogen. Thirdly, producing alkoxymethylfurans (AMFs) which are considered a potential biofuels by using two-step sequential reactions with cheap heterogeneous zinc-iron oxides magnetic nanocatalyst for the hydrogenation of HMF to furfuryl alcohols in various alcohols solvents in the absence of molecular hydrogen followed by solid Brønsted acid catalyst for the etherification reaction of furfuryl alcohol derivatives. All prepared heterogeneous catalysts were characterized by FTIR, XRD, H2-TPR, XPS, ICP-OES, HRTEM-EDX, and N2 adsorption-desorption isothermal analyses (BET and BJH) and were tested for recyclability. The chemical products were identified by high performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS), and products quantities were calculated by using calibration curves of chemical standards. Various reaction conditions such as reaction temperature, reaction time, catalyst amount, and alcohol type were optimized.