Production of renewable fuels is of growing interest due to the ongoing concerns associated with combustion of fossil fuel contributing to global warming. Biomass-derived bio-oil is a potential alternative replacement for conventional fuels. But negative properties such as lower energy density, higher water content and acidity prevent the direct use of bio-oil as a fuel. It is universally agreed that for production of a viable fuel bio-oils must be significantly upgraded. Present upgrading techniques, such as hydrodeoxygenation and esterification consume high amounts of expensive hydrogen or large volumes of alcohols, respectively. Production of low yields continues to be a challenge for hydrodeoxygenation. Therefore, development of more efficient upgrading methods would be desirable. The current research was divided into two parts: in the first part the raw bio-oil was pretreated prior to upgrading to reduce coke formation and catalyst deactivation during upgrading. In the second part pretreated bio-oils were further upgraded by several techniques. The second chapter describes application of an olefination process to raw bio-oil to produce a boiler fuel. In the third chapter, raw bio-oil was pretreated by novel oxidation pretreatment to convert bio-oil aldehydes to carboxylic acids. Aldehydes lead to coke formation and their conversion to carboxylic acids circumvents this issue. Following oxidation pretreatment to raw bio-oil acid anhydride pretreatment was applied to reduce water content which leads to catalyst deactivation during upgrading. The fourth chapter tests esterification of pretreated bio-oil by oxidation to produce boiler fuel with relatively high HHV. The fifth chapter discusses hydrodeoxygenation of oxidized bio-oil produced by oxidation to increase hydrocarbons yield and reduced charring during hydrodeoxygenation. The sixth chapter describes application of catalytic deoxygenation of pretreated bio-oil by oxidation in the presence of pressurized syngas to produce a liquid hydrocarbon mixture. In the seventh chapter we tested direct hydrocracking of pretreated bi-oil by oxidation to produce a liquid hydrocarbon mixture. The end products were analyzed by following the ASTM methods for HHV, water content, viscosity, density, acid value, elemental analysis. Best performing fuels based on high HHV and low acid value were analyzed by FTIR, GC-MS, DHA, 1HNMR and simulated distillation.

Studies of aging processes were conducted on pyrolysis oils produced from pine and cottonwood biomass (clear wood, whole tree, bark and needles/leaves). Accelerated aging at 80 °C for up to 504 h was employed to investigate the short and long-term effects of feedstock, phase separation, char particulates, and solvent addition on pyrolysis oil properties. Feedstock containing forestry residue was found to increase water content of neat pyrolysis oil and the collection method (total vs. fractionated) affects all of the properties with the largest impact on viscosity and as produced molecular weight. Post-condensation liquid filtration did not prevent aging-related water content or molecular weight increases during aging but did retard aging reactions in pine clear wood and pine bark pyrolysis oils. Methanol addition retarded the aging reactions in pine needle fractionated pyrolysis oil; at 15 wt% phase separation was prevented and molecular weight increased 11 % after 504 h of aging.

This thesis evaluates the possibility to use a iron-based catalyst as a pyrolysis vapour conversion catalyst. The iron catalyst was also compared with the mineral dolomite. The experiments were facilitated at Cortus Energy's demonstration plant in Koping, Sweden, by in situ instal- lation of the experimental setup to an outlet of the pyrolyser unit. The pyrolysis vapour from Cortus Energy was converted for a total of 8 hours by passing it through a packed bed reactor containing the iron-based catalyst while sampling gas and oil from the feed for analysis. The outset for the operation on the dolomite catalyst bed was the same as for the iron catalyst with a resulting collapse of the bed when the pyrolysis vapour was introduced. The permanent gases were analysed on site with a µ-GC unit while oil samples were condensed and analysed with GC-MS, H-NMR and Karl Ficher titration. The carbon laydown and surface area of the catalyst was determined as well as the phase changes of the catalyst surface with XRD. The results showed clear indications of bio-crude conversion with an eightfold increase of the H2 concentration of the synthetic gas from 3.38 % to 26.69 % on a dry gas basis. The oxygen to carbon (O:C) ratio decreased in the treated pyrolysis oil compared to the untreated oil while the hydrogen to carbon (H:C) ratio showed indications of dehydration of the oil. The gas and water content of the stream increased while 57.2 % of the oil was converted in the process. Lastly, the iron-based catalyst did not seem to favour the conversion of alkylated phenols.

Bio-oil produced from biomass by the fast pyrolysis method is promising as a renewable fuel and as sources of industrial chemicals. In this study, lower cost separation methods of organic acids such as acetic and formic acids and pyrolytic lignin fraction present in bio-oil were investigated to provide basic data needed for future industrial production procedures. The calcium oxide method and a quaternary ammonium anion-exchange resin method were studied to separate organic acids as respective salts and the methanol-and-water method was studied to separate the water-insoluble pyrolytic lignin fraction. The calcium oxide and anion-exchange methods were shown to be effective in separation of organic acids, although further improvements would be needed. The pyrolytic lignin separation method was also shown to give lignin fraction that is effective for up to 40% replacement of phenol in the oriented strand board core-layer binder PF resins.

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This dissertation addresses the surging global demand for sustainable energy alternatives and biobased products, driven by population growth and the imperative to shift away from finite fossil fuels amidst climate change. The research centers on the catalytic upgrading of rice straw bio-oil, employing bimetallic magnetic nano-catalysts on rice straw-derived biochar to align with the imperative for environmentally conscious energy solutions. In the initial phase, the study systematically explores upgrading processes using varied alcohols, specifically ethanol, and butanol, under mild conditions to enhance bio-oil quality. The detailed evaluation of catalyst composition reveals a notable reduction in oxygen content, coupled with a significant increase in energy density and calorific value. The upgraded bio-oil not only exhibits heightened stability but also undergoes a substantial shift towards a more desirable hydrocarbon-rich composition. The second part of the research optimizes upgrading process parameters catalyst concentration, reaction holding time, and reaction temperature using Response Surface Methodology based on the Box-Behnken experimental design. This optimization refines the catalytic upgrading process, enhancing its efficiency and reliability. Beyond catalytic efficacy, the study considers the magnetic recovery of catalysts for potential reuse, emphasizing sustainability on a broader scale. Set against the backdrop of global energy challenges, this research significantly contributes to advancing the understanding of bimetallic magnetic nano-catalysts. The dissertation unfolds in two parts, with the first segment focusing on Catalytic Upgrading of Rice Straw Bio-Oil via Esterification in Supercritical Ethanol Over Bimetallic Catalyst (CuO-Fe3O4/AcB), involving the variation of Cu and Fe metals on Rice Straw Biochar without hydrogen gas. The exploration continues with the Upgrading of Rice Straw Bio-Oil in Butanol and hydrogen gas Over a Sustainable Magnetic Bimetallic Nano-Catalyst (ZrO2-Fe3O4/AcB). The integrated analytical approach, utilizing XRD, SEM, FT-IR for synthesized catalysts, alongside GC-MS and the Bomb Calorimeter for bio-oil samples, establishes a nuanced understanding crucial for optimizing catalytic performance in sustainable biofuel production.

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Biomass waste has been recognised as a promising, renewable source for future transport fuels. With 1.7 million hectares of pine plantation forests and 12 million cubic meters of annual residue produced by sawmills and the pulp and paper industries, New Zealand presents a prime location where utilisation of these resources can take the next step towards creating a more environmentally friendly future. In this research, the process of fast pyrolysis was investigated using a laboratoryscale, nitrogen-blown fluidised bed pyrolyser at CRL Energy. This equipment can process 1–1.5 kg/h of woody biomass in a temperature range of 450–550°C. The purpose of this rig was to determine the impact of various processing parameters on bio-oil yields. Next, the pyrolysis liquids (bio-oil and tar) were processed downstream into bio-bitumen. Pyrolysis experiments were carried out on Pinus Radiata and Eucalyptus Nitens residue sawdust from sawmills and bark feedstock. The properties of the collected products, including pyrolysis liquids (bio-oil and tar), gas and solid bio-chars, were measured under different operational conditions. Further analysis was also performed to determine pH, volatile content, chemical composition and calorific values of the products. The ultimate goal for this project was to develop a feasible, advanced fast-pyrolysis system for a bio-bitumen production plant using various biomass feedstocks. Additionally, a design for a bio-bitumen production plant was developed, and techno-economic analysis was conducted on a number of plant production yield cases and bio-bitumen manufacture ratios.

La production d'énergie à partir de biomasse ligno-cellulosique via la technologie de gazéification est une option intéressante dans le contexte énergétique actuel. La combinaison d‘une pyrolyse rapide décentralisée de la biomasse pour produire les bio-huiles, suivie par le transport et le vaporeformage dans des bio-raffineries, est apparue comme l'une des méthodes économiquement les plus viables pour la production de gaz de synthèse (H2+CO). L‘objectif de ce travail est de combler le manque de connaissances concernant les processus de transformation physicochimique de l‘huile de pyrolyse en gaz de synthèse utilisant la gazéification non catalytique dans des réacteurs à flux entrainé. Il s‘agit d‘un processus complexe, mettant en oeuvre la vaporisation, les réactions de craquage thermique avec formation de gaz, de tars et de deux résidus solides : le char et les suies, qui sont des produits indésirables. Ceci est suivi par le reformage des gaz et des tars, ainsi que la conversion du char et des suies. Pour mieux comprendre le processus, la première étape de la gazéification (la pyrolyse), et par la suite l'ensemble du processus (pyrolyse + gazéification) ont été étudiés. L‘étude de la pyrolyse est focalisée sur l‘influence de la vitesse de chauffe, de la température ainsi que de la teneur en cendres dans la bio-huile, sur les rendements en char, tars et gaz. A très grande vitesse de chauffe le rendement en char est inferieur à 1%. Les cendres semblent favoriser les réactions de polymérisation et provoquent la diminution du rendement en gaz. Concernant la gazéification, l'effet de la température sur le rendement et la composition du gaz de synthèse a été étudié. Une augmentation de la température de réaction implique une augmentation du rendement en hydrogène et une conversion très élevée du carbone solide. Un calcul d'équilibre thermodynamique a montré que l'équilibre a été atteint à 1400°C. Finalement les mécanismes de formation et d‘oxydation des suies ont été étudiés expérimentalement sous différentes atmosphères : inerte (pyrolyse), riche en vapeur d‘eau (gazéification) et en présence d‘oxygène (oxydation partielle). Un modèle semi empirique est proposé et validé. Il est fondé sur la chimie détaillée pour décrire les réactions en phase gaz, une seule réaction basée sur la concentration de C2H2 pour décrire la formation des suies et principalement une réaction hétérogène pour décrire l‘oxydation des suies. / Energy production from ligno-cellulosic biomass via gasification technology appears as an attractive option in the current energy context. The combination of decentralized fast pyrolysis of biomass to produce bio-oil, followed by transportation and gasification of bio-oil in bio-refinery has appeared as one of the most economically viable methods for syngas (H2+CO) production. The objective of this work is to bridge the lack of knowledge concerning the physicochemical transformation of bio-oil into syngas using non catalytic steam gasification in entrained flow reactors. This complex process involves vaporization, thermal cracking reactions with formation of gas, tars and two solid residues - char and soot - that are considered as undesirable products. This is followed by steam reforming of gas and tars, together with char and soot conversion. To better understand the process, the first step of gasification (pyrolysis) and thereafter the whole process (pyrolysis + gasification) were studied. The pyrolysis study focused on the influence of the heating rate, the final pyrolysis temperature and the ash content of bio-oil on char, tars and gas yields. At the higher heating rate char yield is smaller than 1%. In addition, ash seems to promote polymerization reactions and causes a decrease of gas yield. Concerning gasification, the effect of temperature on syngas yield and composition was studied. An increase in the reaction temperature implies higher hydrogen yield and higher solid carbon conversion. A thermodynamic equilibrium calculation showed that equilibrium was reached at 1400°C. Finally, the soot formation and oxidation mechanisms were investigated through experiments in three different atmospheres: inert (pyrolysis), rich in steam (gasification) and in the presence of oxygen (partial oxidation). A semi-empirical model was proposed and validated. It is based on detailed chemistry to describe gas phase reactions, a single reaction using C2H2 concentration to describe soot formation and one main heterogeneous reaction to describe soot oxidation.

Com a crescente demanda de energia no mundo, a busca por novas fontes alternativas de energia tem motivado novos estudos por fontes energéticas renováveis que permitam substituir gradualmente os combustíveis fósseis, responsáveis por emissões de níveis de poluentes superiores aos associados aos biocombustíveis. O aumento populacional aliado à melhoria da eficiência do tratamento de esgoto implica diretamente o aumento da produção do lodo de esgoto, que é o principal resíduo sólido gerado nessas estações. O lodo de esgoto pode ser aplicado em processos tecnológicos, como a pirólise, a gaseificação e a combustão, para produção de energia alternativa. A pirólise é uma tecnologia promissora, favorece a produção de quatro frações quando aplicada ao lodo residual: bio-óleo (fração líquida orgânica), fração aquosa, fração sólida e gasosa, com elevado potencial combustível. Este artigo tem como objetivo avaliar o processo de pirólise aplicado a lodo residual doméstico como uma fonte alternativa de energia e identificar as condições de processo que resultaram em maiores rendimentos do bio-óleo produzido. / With the growing demand for energy in the world, the search for new sources of energy have motivated new studies about renewable energy sources that allow us to replace fossil fuels gradually, as they are responsible for higher levels of pollutants emission if compared to biofuels. Population growth together with the improvement of sewage treatment efficiency, that directly impacts the growth of sewage sludge production, which is the main solid waste generated in the Sewage Treatment Stations. The sludge can be used in technological processes, like pyrolysis, gasification and combustion, in order to produce alternative energy. The pyrolysis applied in sludge is a promising technology that favor the production of four fractions: biooil (organic liquid fraction), water fraction, solid fraction and gas fraction, showing a high fuel potential. This paper aims to evaluate the pyrolysis process applied to domestic sludge as an alternative source of energy and identify the process conditions that resulted in better efficiency of the biooil produced.