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Abstract: Lignocellulosic biomass has been widely recognized as a renewable feedstock that has enormous potential for the production of bio-based fuels and platform chemicals. Obtained from the dehydration of sugars, 5-hydroxymethylfurfural (HMF) in particular has received extensive consideration due to its diverse functionality and versatility. However, despite its potential, major technical and economic challenges still need to be addressed before HMF valorization technologies can be competitive with current processes that rely on fossil fuels. This doctoral study specifically focuses on the catalytic hydrogenation of HMF into various platform chemicals while utilizing nickel-based catalysts. The overall goal of this dissertation is to advance these technologies through innovative catalyst design and catalyst characterization techniques that allowed for a systematic investigation into the major catalyst surface properties that influence activity and product selectivity. Various characterization techniques were applied to acquire relevant catalyst surface and structural properties including temperature-programmed reduction, temperature-programmed desorption, X-ray powder diffraction, and transition electron microscopy, N2 physisorption, and diffuse reflectance infrared Fourier transform spectroscopy. A detailed kinetic model was also established that takes into account the number of metallic active sites that provides comparative kinetic parameters to better understand catalyst activity. The main discoveries obtained during this doctoral thesis include the determination of the critical influence that the support material has on catalyst activity and tuning the reaction network. Particularly, it was found that carbon as a relatively neutral support was effective for hydrodeoxygenation, however, an alumina support was necessary to activate the furan ring and facilitate ring saturation and ring opening reactions. The solvent system was also found to be impactful where incorporating water as a co-solvent completely eliminated all dehydration side reactions. Structural-activity correlations indicate that both acid and basic active sites could play a pivotal role in dictating between the two competing reactions of ring saturation and ring opening. The results presented in this doctoral dissertation provide crucial details for more optimal catalyst design and operating conditions for the effective conversion of 5-hydroxymethylfurfural via hydrogenation for the purpose of advancing sustainable bio-based chemical production.
Keywords: biomass, catalysis, kinetics, hydrogenation, 5-hydroxymethylfurfural
Published in DKUM: 19.09.2024; Views: 0; Downloads: 5
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Abstract: Kinetics of hydrothermal degradation of colorless polyethylene terephthalate (PET) waste was studied at two temperatures (300 °C and 350 °C) and reaction times from 1 to 240 min. PET waste was decomposed in subcritical water (SubCW) by hydrolysis to terephthalic acid (TPA) and ethylene glycol (EG) as the main products. This was followed by further degradation of TPA to benzoic acid by decarboxylation and degradation of EG to acetaldehyde by a dehydration reaction. Furthermore, by-products such as isophthalic acid (IPA) and 1,4-dioxane were also detected in the reaction mixture. Taking into account these most represented products, a simplified kinetic model describing the degradation of PET has been developed, considering irreversible consecutive reactions that take place as parallel in reaction mixture. The reaction rate constants (k1–k6) for the individual reactions were calculated and it was observed that all reactions follow first-order kinetics.
Keywords: PET waste, subcritical water, kinetics, degradation, TPA
Published in DKUM: 18.09.2023; Views: 645; Downloads: 52
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Abstract: The saponification of an aromatic ester with an aqueous sodium hydroxide was studied within a heterogeneous reaction medium in order to determine the overall kinetics of the selected system. The extended thermo-kinetic model was developed compared to the previously used simple one. The reaction rate within a heterogeneous liquid-liquid system incorporates a chemical kinetics term as well as mass transfer between both phases. Chemical rate constant was obtained from experiments within a homogeneous medium, whilst the mass-transfer coefficient was determined separately. The measured thermal profiles were then the bases for determining the overall reaction-rate. This study presents the development of an extended kinetic model for considering mass transfer regarding the saponification of ethyl benzoate with sodium hydroxide within a heterogeneous reaction medium. The time-dependences are presented for the mass transfer coefficient and the interfacial areas at different heterogeneous stages and temperatures. The results indicated an important role of reliable kinetic model, as significant difference in $k_La$ product was obtained with extended and simple approach.
Keywords: chemical kinetics, mass transfer, saponification, heterogeneous system
Published in DKUM: 25.08.2017; Views: 1794; Downloads: 226
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Abstract: Spent BRINE from the regeneration of exhausted resins has to be properly treated before its disposal. The heterotrophic denitrification of regenerated brine was studied in present work. Molasses which served as a carbon source has until now not been applied during brine denitrification. The nitrate and nitrite consumptions were observed according to different ratios between total organic carbon and nitrate (TOC / NO3 ratios) and the influence of NaCl was studied during batch experiments. This work ascertained that molasses is a very good source of carbon, and no addition of other nutrients is necessary. The complete nitrate removal from regenerated brine could be achieved using molasses.
Keywords: nitrate, denitrification, regeneration brine, molasses, kinetics
Published in DKUM: 05.07.2017; Views: 1326; Downloads: 409
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Abstract: The aim of this study was to activate inert PET surfaces in order to introduce the surfaces’ carboxyl groups and to obtain its hydrophilic character, which was important for the chitosan bonding to it. Films where chitosan was attached to the PET could be used as active packaging material for food like fresh poultry meat. For PET activation two advanced and environmentally friendly techniques were used: 1) O2 plasma activation; and 2) CO2 plasma activation. Differently treated PET foils deposited on Au quartz crystals (model studies - adsorption and desorption) and real films were characterized. Later on, real films were studied in the terms of carboxylic/amino group content, hydrophobic/hydrophilic character, surface composition and adsorption/desorption of chitosan onto/from the surface. Results clearly showed that the use of both surfaces’ activation processes increased the ability of PET foils to adsorb chitosan, but CO2 plasma gave a higher concentration of carboxyl groups on the PET surface and consequently, due to the chemical bonding the chitosan layers were more stable. Even though CO2 plasma pre-treated PET foils gave better results during the experimental work, we could not avoid layer by layer adhesion of chitosan which resulted in non-bound molecules. Pre-treated foils and with chitosan functionalized foils were tested preliminarily with ASTME E1 (2002) microbiological tests. Functionalized CO2 plasma pre-treated foils gave the broadest spectra of antimicrobial activity, and therefore they were chosen for further microbiological analyses, where chitosan`s influence on inoculated poultry models towards selected standard strains, typical for poultry meat, was being tested. By determining the MIC (minimal inhibitory concentration) for selected microorganisms we have proven, that chitosan possesses antimicrobial properties at low concentrations. During the transfer of the experiment to a larger scale (food models, which are a very complex environment), it has been shown that on PET bonded chitosan did not have the inhibitory effect to that extent, with the exception of Staphylococcus aureus, as was expected. Similar results were expressed using both these methods: Colony count technique and real-time PCR. In the end, the organoleptic properties of the chicken models exposed to foils have shown that chitosan changes the color and taste of meat immediately after exposure, but samples were staying edible longer. Therefore, functionalized PET, which has an inhibitory influence towards variety of microorganisms, may be applied as an active packaging system for poultry meat after some optimization of the coating procedure in binding chitosan onto the PET surfaces.
Keywords: PET/chitosan/antimicrobial packaging/adsorption-desorption kinetics/microbiological tests
Published in DKUM: 22.10.2014; Views: 2494; Downloads: 209
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