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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: In this work, the thermochemical properties of municipal solid waste (MSW) are studied using the torrefaction process as the main method for investigation. Torrefaction experiments were carried out using an electric laboratory furnace, at temperatures of 200, 250, and 300 °C. The residence time was set to 90 min. Proximate and ultimate analysis were performed on the torrefied MSW samples and compared with the properties of the raw MSW samples. In addition, the thermal properties of the obtained torrefied MSW samples were evaluated by thermogravimetric analysis (TGA) and derivative thermogravimetric analysis (DTG). The following could be stated: the obtained results showed that mass and energy yields (MY and EY, respectively) decrease with increasing when torrefaction temperature, while the heating values (HHV) increased under the same conditions (from 24.3 to 25.1 MJ/kg). Elemental analysis showed an increase in carbon content (C), from 45.7 ± 0.9 to 52.8 ± 1.05 wt.%, and decrease in oxygen content (O), from 45.6 ± 0.9 to 39.5 ± 0.8 wt.%, when torrefaction temperature is increased, which is consistent with the general definition of the torrefaction process. In addition, enhancement factors (EFs) and fuel ratios (FRs) were calculated, which ranged from 1.00 to 1.02 and 0.16 to 0.23, respectively. Some anomalies were observed during the thermal analysis, which are assumed to be related to the composition of the selected MSW. This study therefore shows that torrefaction pretreatment can improve the physicochemical properties of raw MSW to a level comparable to coal, and could contribute to a better understanding of the conversion of MSW into a valuable, solid biofuel.
Keywords: biomass, municipal solid waste, torrefication, energy yield, thermogravimetric analysis
Published in DKUM: 10.05.2024; Views: 255; Downloads: 19
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Abstract: The main objective of this review is to present the latest research results regarding the importance of the torrefaction process for different biomass materials in the last 12-year period. Despite the fact that the potential of renewable energy sources has been analyzed, research regarding that of energy derived from waste biomass still remains in the infancy state. Torrefaction is known to be one of the most effective methods for enhancing the energy efficiency of biomass. Among different types of torrefactions, the focus in this study is mostly on dry torrefaction. The influential factors, like temperature and residence time, and physico-chemical properties of torrefied products, and the prospective of torrefaction due to its reduced impact on environment, are discussed in-depth. This review provides valuable insights into the torrefaction process, which is conducive to upgrading biomass for achieving net zero carbon emissions, as it has been stated in several works that torrefied biomass can be used instead of coal.
Keywords: torrefaction, lignocellulosic biomass, waste biomass, biomass properties
Published in DKUM: 22.03.2024; Views: 470; Downloads: 694
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Abstract: In Slovenia, approximately one third of electricity is produced in thermal power plants. Electricity prices have risen sharply recently. There are several reasons for this. One of them is the large increase in the price of CO2 coupons that thermal power plants have to buy, since they emit large amounts of greenhouse gas into the environment during the production of electricity. Emissions of the greenhouse gas CO2 are the result of burning fossil fuels, in this case coal. We want to use renewable energy sources to replace fossil fuels and reduce greenhouse gas emissions. More than half of Slovenia is covered with forest, and as a result, wood biomass energy represents a great energy potential. One possibility is the use of wood biomass in a classic thermal power plant for the production of electricity. This contribution presents the energy potential of Slovenian forests, before evaluating the replacement of the energy source in the existing coal-based thermal power plant with wood biomass. It has been discovered that there is enough wood biomass in Slovenia, and that all the electricity that is currently produced from coal can be produced from wood biomass. The cost of wood biomass is higher than the cost of coal. By changing the energy source, we save on the purchase of CO2 coupons. Therefore, the use of wood biomass represents an economically justified energy source for the production of electricity.
Keywords: wood biomass, thermal power plant, electricity production
Published in DKUM: 30.10.2023; Views: 443; Downloads: 6
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Abstract: In this doctorial dissertation subcritical water processes of lignocellulosic biomass to obtain value-added compounds are studied. The doctorial dissertation is divided into four main parts. In the first and second part of dissertation, model compounds (standards of cellulose and sugars and chestnut tannins) were primarly used in order to better understand processes of real biomass material. The degradation of cellulose and different sugars was performed in batch reactor with subcritical water. The different reaction temperatures and times were used. The main phases, such as water-soluble fraction, acetone-soluble fraction and solid residue were separated and analysed. The analysis of water-soluble phase was done by HPLC equipped with UV and RI detector, while acetone-soluble phase of cellulose was analysed by GC-MS. Total sugar content was determined by the phenol-sulphuric acid colorimetric method. The properties of char, obtained using cellulose as a treated material, such as: specific surface area, pore volume and pore diameter were determined by gas adsorption method. A water-soluble phase mainly consists of sugar monomers and monomer degradation products such as 5-hydroxymethylfurfural (5-HMF), furfural, erythrose, sorbitol, 1,6-anhydroglucose, glycolaldehyde, glycerlaldehyde, 1,3-dihydroxyacetone, pyruvaldehyde, formic, levulinic, lactic, oxalic and succinic acids, while acetone-soluble phase, referred to also as bio-oil, consists of furans, phenols, carboxylic acids, aldehydes, ketones and high molecular compounds. The reaction mechanism of cellulose and sugars in subcritical water has been proposed based on the obtained results. Furthermore, the results from cellulose and sugar hydrothermal degradation were utilized in further work to determine which industrially interesting products could be obtained by hydrothermal processing of paper waste in subcritical water. The optimum conditions ( temperature and reaction time), which gave us the highest yield of base chemicals (furfural, 5-HMF, levulinic acid) were determined. Sweet chestnut (Castanea Sativa) bark contains high level of tannins and various phenolic compounds which can be utilized in pharmaceutical, cosmetic, nutritional and medical purposes. The sweet chestnut tannins extract and sweet chestnut bark were used as materials highly rich in bioactive compounds for subcritical water processes which are presented in the second part of doctorial dissertation, respectively. The spectrophotometric methods were used to determine total tannins, phenols and carbohydrates content and antioxidant activity. The identified compounds were ellagic and gallic acid, ellagitannins (vescalagin, castalagin, 1-o-galloyl castalagin, vescalin and castalin), sugars (maltose, glucose, fructose and arabinose) and sugar derivatives (5-HMF, furfural and levulinic acid). The results obtained from hydrothermal hydrolysis were compared to results from acid hydrolysis. Finally, the optimization of reaction parameters of subcritical water processes has been done aiming to obtain the product highly rich in ellagic acid. Subcritical water extraction of horse chestnut (Aesculus hippocastanum) parts such as seeds, seed shell, bark and leaves was described in the third chapter of dissertation. The detected compounds in extracts, such as escins, esculin, fraxin, phenolic compounds (chlorogenic, neochlorogenic and gallic acids) and furfurals (5-hydroxymethyfurfural, furfural, and methylfufrual) are quantified using HPLC. The last part of dissertation proposes extraction of cocoa shell using green technologies (supercritical CO2 and subcritical water extraction) and also conventional methods (Soxhlet extraction with hexane and extraction with 50 % acetone) to obtain bioactive compounds in order to compare the results. The detected compouns were methylxanthines, phenolic compounds, sugars, fatty acids.
Keywords: Subcritical water, biomass, biowaste, extraction, hydrothermal degradation, hydrolysis, bioactive compounds.
Published in DKUM: 16.10.2020; Views: 1774; Downloads: 160
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