abstract: The continued reliance on fossil fuel for energy resources has proven to be unsustainable, leading to depletion of world reserves and emission of greenhouse gases during their combustion. Therefore, research initiatives to develop potentially carbon-neutral biofuels were given the highest importance. Hydrothermal liquefaction (HTL, a thermochemical conversion process) of microalgae is recognized as a favorable and efficient technique to produce liquid biofuels from wet feedstocks. In this work, three different microalgae (Kirchneriella sp., Galdieria sulphuraria, Micractinium sp.) grown and harvested at Arizona State University were hydrothermally liquefied to optimize their process conditions under different temperatures (200-375 °C), residence times (15-60 min), solids loadings (10-20 wt.%), and process pressures (9-24 MPa). A one-factor-at-a-time approach was employed, and comprehensive experiments were conducted at 10 % solid loadings and a residence time of 30 min. Co-liquefaction of Salicornia bigelovii Torr. (SL), Swine manure (SM) with Cyanidioschyzon merolae (CM) was tested for the presence of synergy. A positive synergistic effect was observed during the co-liquefaction of biomasses, where the experimental yield (32.95 wt.%) of biocrude oil was higher than the expected value (29.23 wt.% ). Co-liquefaction also led to an increase in the energy content of the co-liquefied biocrude oil and a higher energy recovery rate ( 88.55 %). The HTL biocrude was measured for energy content, elemental, and chemical composition using GC-MS. HTL aqueous phase was analyzed for potential co-products by spectrophotometric techniques and is rich in soluble carbohydrates, dissolved ammoniacal nitrogen, and phosphates. HTL biochar was studied for its nutrient content (nitrogen and phosphorous) and viability of its recovery to cultivate algae without any inhibition using the nutrient leaching. HTL biochar was also studied to produce hydrogen via pyrolysis using a membrane reactor at 500 °C, 1 atm, for 24 h to produce 5.93 wt.% gas. The gaseous product contains 45.7 mol % H2, 44.05 ml % CH4, and 10.25 mol % of CO. The versatile applications of HTL biochar were proposed from a detailed physicochemical characterization. The metal impurities in the algae, bio-oil, and biochar were quantified by ICP-OES where algae and biochar contain a large proportion of phosphorous and magnesium. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2020

Current global demands for energy resources along with continuous global population growth have placed natural environments and societies under great stress to fulfill such a need without disrupting economic and social structures. Policy and decision-making processes hold some of the most important keys to allow safe paths for societies towards energy security and safeguard of the environment. Brazil has played a lead role within renewable energy production and use during the last decades, becoming one of the world’s leading producer of sugarcane based ethanol and adapting policies to support renewable energy generation and use. Although it is true that Brazil has historic experience with managing development of renewables and its further integration into the consumer market, there is still a lot to do to impulse new technologies that could further reduce emissions, increase economic stability and social welfare. Throughout this thesis project a sustainability assessment of hydrogen production technologies in Brazil is conducted through Multi-Criteria Analysis. After defining an initial framework for decision-making, options for hydrogen production were reviewed and selected. Options were evaluated and weighted against selected sustainability indicators that fitted the established framework within a weighting matrix. An overall score was obtained after the assessment, which ranked hydrogen production techniques based on renewable energy sources in first place. Final scoring of options was analyzed and concluded that several approaches could be taken in interpreting results and their further integration into policy making. Concluding that selection of the right approach is dependent on the time scale targeted for implementation amongst other multi-disciplinary factors, the use of MCA as an evaluation tool along with overarching sustainability indicators can aid in narrowing uncertainties and providing a clear understanding of the variables surrounding the problem at hand.

Dual-broadband and dual-pump nanosecond CARS experiments were performed to investigate the pure rotational transitions of the nitric oxide molecule. The former experiment was initially utilized to determine the pure rotational structure while the latter focused on polarization suppression of the pure rotational transitions of nitric oxide. A polarization calculation and analysis were conducted on the rotational and vibrational transitions of nitrogen, and the pure rotational transitions of nitric oxide were subjected to a similar polarization scheme. The electronic transitions that arise due to the spin-split nature of nitric oxide ground electronic energy levels were suppressed by the polarization scheme in a similar manner to the rotational S branch transitions. Results have been compared with a spectral simulation developed by Dr. Lucht, and the theory is partially presented. Comparison between simulation and experimental data yielded favorable agreement for the pure rotational transitions of nitric oxide.

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.

As emissões veiculares constituem-se em uma das mais graves ameaças a qualidade de vida da população, principalmente nos grandes centros urbanos. Poluentes de origem veicular podem induzir alterações no material genético de organismos a eles expostos, pois nessas emissões, destacam-se entre outros, os hidrocarbonetos policíclicos aromáticos (HPAs), que são substâncias consideradas carcinogênicas e mutagênicas. A utilização de indicadores sensíveis a ação de agentes genotóxicos serve para avaliar a presença destes compostos no ambiente. Portanto, o objetivo deste trabalho foi avaliar comparativamente o risco mutagênico das emissões provenientes da combustão dos combustíveis fósseis (gasolina e diesel) e renováveis (álcool e biodiesel), utilizando o bioensaio Trad-SH. Os ensaios foram realizados utilizando veículos do ciclo Diesel (Citröen JUMPER 2.8 L, 2006) e do ciclo Otto (VW FOX 1.6 Flex, 2005 sem o conversor catalítico), em um dinamômetro de chassi, submetidos a um ciclo de condução urbano padronizado (FTP-75) modificado, para a coleta dos gases de escapamento. Os gases foram misturados com o ar ambiente e homogeneizados para simular o que ocorre no trânsito urbano. As inflorescências do clone KU-20 de Tradescantia foram expostas a mistura de poluentes, provenientes dos veículos, dentro de uma câmara de fumigação, por duas horas. Para a avaliação do efeito mutagênico foi feita uma comparação entre as inflorescências não expostas aos poluentes (grupo 1) e as inflorescências expostas as emissões do álcool (grupo 2), do biodiesel (grupo 3), da gasolina (grupo 4) e do diesel (grupo 5). Os dados obtidos dos experimentos foram analisados estatisticamente onde se observou que a freqüência média das mutações no grupo 1 (controle), foi significativamente mais baixa do que aquela dos grupos 2, 3, 4, e 5. Os resultados indicam que as emissões dos veículos abastecidos com combustíveis fósseis (gasolina e diesel), são mais mutagênicas do que as emissões provenientes da combustão dos combustíveis renováveis (álcool e biodiesel). / The vehicle emissions constitute a major serious threat to the population\'s quality of life, especially in the large urban areas. Pollutants from vehicle origin may lead to changes concerning the genetic material of some organisms that have been exposed to them, and within these emissions it is stood out among others the polycyclic aromatic hydrocarbons (PAH\'s), which are carcinogenic and mutagenic compounds. The use of sensitive indicators to the action of genotoxic agents is useful to prevent and to evaluate the presence of these compounds in the environment. Therefore, this work is aimed at evaluating comparatively the mutagenic risk of emissions from the burning of fossil fuel (gasoline and diesel) and renewable ones (ethanol and biodiesel) by the use of Trad-SH bioassay. The assays were carried out using vehicles from the diesel cycle (Citröen JUMPER 2.8 L, 2006) and the Otto cycle (VW FOX 1.6 Flex, 2005, without a catalytic converter), in a chassis dynamometer, submitled to a standard urban driving cycle (FTP-75) in order to collect the gases of exhaust. The gases were mixed up to the atmosphere air and homogenized to simulate what happens in urban traffic. The inflorescences of KU-20 clone of Tradescantia were exposed to a mixture of pollutants from vehicles, in a fumigation chamber for two hours. To evaluate the mutagenic effect it was necessary to establish a comparison between the inflorescences which were not exposed to pollutants (group 1) and inflorescences exposed to emissions of alcohol (group 2), biodiesel (group 3), gasoline (group 4) and diesel (group 5). Data obtained from experiments were statistically analyzed in which appears that the average frequency of mutations in group 1 (control) was significantly lower than that of groups 2, 3, 4 and 5. The results indicate that emissions from vehicles fueled by fossil fuels (petrol and diesel) are more mutagenic than emissions from the combustion of renewable fuels (ethanol and biodiesel).

Submitted by Mauricio José de Oliveira Junior (mauriciooj@gmail.com) on 2011-12-12T19:55:27Z No. of bitstreams: 1 Oliveira Junior, Mauricio José de. Dissertação (MPAgro).pdf: 1664245 bytes, checksum: 7aa3a3c6e3d394c55abfc105128e5550 (MD5) / Approved for entry into archive by Gisele Isaura Hannickel (gisele.hannickel@fgv.br) on 2011-12-13T14:31:52Z (GMT) No. of bitstreams: 1 Oliveira Junior, Mauricio José de. Dissertação (MPAgro).pdf: 1664245 bytes, checksum: 7aa3a3c6e3d394c55abfc105128e5550 (MD5) / Made available in DSpace on 2011-12-13T16:10:00Z (GMT). No. of bitstreams: 1 Oliveira Junior, Mauricio José de. Dissertação (MPAgro).pdf: 1664245 bytes, checksum: 7aa3a3c6e3d394c55abfc105128e5550 (MD5) Previous issue date: 2011-11-21 / This work aims to study and present the analysis of technical and economic feasibility of use of the biomass of Pistia stratiotes (water lettuce) as a solid fuel in the furnace industry. For this we present the case study in a unit of Valley Fertilizer in the city of Cajati in the state of Sao Paulo. The technical feasibility analysis builds on the results of the analysis performed on the biomass composition, in search of the collection system and preparation, the calculations made to find productivity, such as biomass can be consumed and the study of the efficiency of industrial furnace the case. To demonstrate the economic feasibility, this study uses the classical model of economic engineering with the observation of rates and charges such as: Minimum Rate of Appeal (EBA), Net Present Value (NPV), Internal Rate of Return (IRR), Recovery Period Capital Investment (Payback) and Sensitivity Analysis. It was observed on the technical results that the characteristics of the biomass of water lettuce help in the steps of ignition and combustion of fuel, however this biomass has a low net calorific value for use without mixing fuel in industrial furnaces. The economic results were positive in the biomass, and the project was consistent and rapid recovery of invested capital. This case study demonstrates that the study of the use of water lettuce biomass as fuel solid to industrial furnace is technically and economically feasible. And beyond this, shows that such studies should be developed in the quest to diversify sources of energy through renewable energy. / Este trabalho tem como objetivo estudar e apresentar a análise de viabilidade técnica e econômica no projeto de utilização da biomassa de Pistia Stratiotes (Alface d’água) como combustível sólido em fornalha industrial. Para isto apresenta-se o estudo de caso em uma unidade da Vale Fertilizantes, no município de Cajati, no estado de São Paulo. A análise de viabilidade técnica baseia-se nos resultados encontrados pelas análises de composição realizadas na biomassa, na pesquisa do sistema de coleta e preparação, nos cálculos desenvolvidos para encontrar a produtividade, como a biomassa poderia ser consumida e no estudo da eficiência da fornalha industrial do caso. Para demonstrar a viabilidade econômica, este estudo recorre ao modelo clássico de Engenharia Econômica com a observação dos índices e taxas como: Taxa Mínima de Atratividade (TMA), Valor Presente Líquido (VPL), Taxa Interna de Retorno (TIR), Período de Recuperação do Capital Investido (Payback) e na Análise de Sensibilidade. Observou-se nos resultados técnicos que as características da biomassa de alface d’água ajudam nas etapas de ignição e combustão do combustível, no entanto esta biomassa apresenta baixo poder calorífico inferior para sua utilização sem mistura combustível em fornalhas industriais. Os resultados econômicos apresentaram-se positivos à utilização da biomassa, e o projeto mostrou-se consistente e de rápida recuperação do capital investido. Este estudo de caso demonstra que o estudo da utilização da biomassa de alface d’água como combustível sólido em fornalha industrial é viável tecnicamente e economicamente. E muito além disto, mostra que estudos deste tipo devem ser desenvolvidos na busca pela diversificação da matriz energética através de energia renovável.

As emissões veiculares constituem-se em uma das mais graves ameaças a qualidade de vida da população, principalmente nos grandes centros urbanos. Poluentes de origem veicular podem induzir alterações no material genético de organismos a eles expostos, pois nessas emissões, destacam-se entre outros, os hidrocarbonetos policíclicos aromáticos (HPAs), que são substâncias consideradas carcinogênicas e mutagênicas. A utilização de indicadores sensíveis a ação de agentes genotóxicos serve para avaliar a presença destes compostos no ambiente. Portanto, o objetivo deste trabalho foi avaliar comparativamente o risco mutagênico das emissões provenientes da combustão dos combustíveis fósseis (gasolina e diesel) e renováveis (álcool e biodiesel), utilizando o bioensaio Trad-SH. Os ensaios foram realizados utilizando veículos do ciclo Diesel (Citröen JUMPER 2.8 L, 2006) e do ciclo Otto (VW FOX 1.6 Flex, 2005 sem o conversor catalítico), em um dinamômetro de chassi, submetidos a um ciclo de condução urbano padronizado (FTP-75) modificado, para a coleta dos gases de escapamento. Os gases foram misturados com o ar ambiente e homogeneizados para simular o que ocorre no trânsito urbano. As inflorescências do clone KU-20 de Tradescantia foram expostas a mistura de poluentes, provenientes dos veículos, dentro de uma câmara de fumigação, por duas horas. Para a avaliação do efeito mutagênico foi feita uma comparação entre as inflorescências não expostas aos poluentes (grupo 1) e as inflorescências expostas as emissões do álcool (grupo 2), do biodiesel (grupo 3), da gasolina (grupo 4) e do diesel (grupo 5). Os dados obtidos dos experimentos foram analisados estatisticamente onde se observou que a freqüência média das mutações no grupo 1 (controle), foi significativamente mais baixa do que aquela dos grupos 2, 3, 4, e 5. Os resultados indicam que as emissões dos veículos abastecidos com combustíveis fósseis (gasolina e diesel), são mais mutagênicas do que as emissões provenientes da combustão dos combustíveis renováveis (álcool e biodiesel). / The vehicle emissions constitute a major serious threat to the population\'s quality of life, especially in the large urban areas. Pollutants from vehicle origin may lead to changes concerning the genetic material of some organisms that have been exposed to them, and within these emissions it is stood out among others the polycyclic aromatic hydrocarbons (PAH\'s), which are carcinogenic and mutagenic compounds. The use of sensitive indicators to the action of genotoxic agents is useful to prevent and to evaluate the presence of these compounds in the environment. Therefore, this work is aimed at evaluating comparatively the mutagenic risk of emissions from the burning of fossil fuel (gasoline and diesel) and renewable ones (ethanol and biodiesel) by the use of Trad-SH bioassay. The assays were carried out using vehicles from the diesel cycle (Citröen JUMPER 2.8 L, 2006) and the Otto cycle (VW FOX 1.6 Flex, 2005, without a catalytic converter), in a chassis dynamometer, submitled to a standard urban driving cycle (FTP-75) in order to collect the gases of exhaust. The gases were mixed up to the atmosphere air and homogenized to simulate what happens in urban traffic. The inflorescences of KU-20 clone of Tradescantia were exposed to a mixture of pollutants from vehicles, in a fumigation chamber for two hours. To evaluate the mutagenic effect it was necessary to establish a comparison between the inflorescences which were not exposed to pollutants (group 1) and inflorescences exposed to emissions of alcohol (group 2), biodiesel (group 3), gasoline (group 4) and diesel (group 5). Data obtained from experiments were statistically analyzed in which appears that the average frequency of mutations in group 1 (control) was significantly lower than that of groups 2, 3, 4 and 5. The results indicate that emissions from vehicles fueled by fossil fuels (petrol and diesel) are more mutagenic than emissions from the combustion of renewable fuels (ethanol and biodiesel).

No description available.

Growing prices, limited supply, and public concern about greenhouse gases associated with crude-derived jet fuels have led to development of renewable alternatives which must be compatible with the worldwide civilian and military aviation infrastructure, which were designed for operation with Jet-A/JP-8. Any alternative fuel should not have negative effects on the aircraft engines and fuel systems, especially from a thermal stability perspective, since any adverse effect of the physical properties, and chemical composition, including existence of trace elements, of those fuels may only be revealed after extensive operation, resulting in higher life-cycle maintenance and operation costs. This study considered four types of alternative fuels: two derived by Fischer-Tropsch (FT) process, and two types of Hydro-processing Esters and Fatty acids (HEFA). For each of these types, both raw and 50:50 blends in volume with Jet-A samples have been prepared, thus resulting in eight different fuel blends. Fit-for-purpose ability of these alternative fuels is first investigated by studying the effects of the fuel properties and composition effects on elastomer materials, and micro-turbine performance. When elastomer o-rings, similar to those used in aircraft fuel systems were immersed in renewable fuels, smaller volume change or swelling was detected (lower than 2%), contrary to a 14% swelling observed for baseline Jet-A. Lower swelling may result into leaks during aircraft operation. This trend was reversed when renewable fuels were blended with aromatics containing Jet-A. Lower energetic content per unit volume of the renewable fuels, resulted in a thrust reduction around 10% when compared to baseline Jet-A at full throttle settings, but other than this, no other significant effect on the engine combustion temperature or other parameters were found for short iv duration testing. On the other hand at the end of the alternative fuel testing an injector issue was detected, which caused a localized heat zone at the turbine stator, and subsequent damage. The investigation of the causes of this nozzle fouling, which may be related to fuel contamination, turbine manufacture defects, or operation conditions is left for future studies. Primary focus of this study is coking behavior of 8 different alternative fuel blends over 4 different metallic surfaces, as compared against baseline Jet-A. A specialized single tube heat exchanger apparatus was used where each fuel sample was allowed to flow through a metal tube placed inside a tube furnace. Thermal stresses caused by the break-down of hydrocarbon molecules and the catalytic effects of the tube surfaces affect thermal stability of the fuel, leading to coking deposits under the auto-oxidation and pyrolysis mechanisms. In the results reported in this study, physical methods such as gravimetric measurements were used to obtain the deposits, while UV/VIS absorption, and GC/MS were used to study chemical changes in fuel composition and their relation with coking deposits. Thermal depositions between 16 and 46 μg/cm2 were measured at the tubes after 3 hours of testing, finding no significant differences between the baseline Jet-A and the renewable fuels blends, even when sulfur levels, which are linked to deposits formation, were lower for the renewable fuels. Fuel bulk constituents, such as paraffins and cycloalkanes, under thermal stressing and catalytic influence of the tube metals cracked into reactive intermediates leading to surface deposits formation, like aromatic compounds. These compounds were identified by the shift towards longer excitation wavelengths of the UV-Vis absorption measurements on stressed fuels.

<div>High speed laser diagnostics are performed in two vastly differing swirl combustors at conditions relevant for industrial gas turbines. This high quality data can not only be used to elucidate key features of the flow field but also for validation of computational models simulating turbulence, chemistry, and their interactions. The first combustor is a piloted lean premixed prevaporized arrangement common in aviation applications. Fueling parameters are varied and sensitivity towards the pilot flame is observed. Conditioning to the stagnation line demonstrates increased fluctuations of shear and rotation in the inner shear layer when the pilot fueling is reduced.</div><div><br></div><div>The second flame has a simpler configuration with a single swirler and combusting natural gas. Thermoacoustic instability coupled to a helical precessing vortex core is found at certain conditions. Sparse Dynamic Mode Decomposition and phase averaging is applied to the velocity fields to create a three dimensional reconstruction of the helical vortex core in a non-precessing reference frame. Heat release is found to be correlated to the interaction strength of the central recirculation bubble and the helical vortex core. </div><div><br></div><div> </div><div>Finally, intermittent phenomena within a thermoacoustic instability are examined. The most prominent deviation is that the flame is observed to randomly lift and reattach. In addition, a convolutional neural network is employed to extract the morphology from otherwise qualitative OH species imaging. The average characteristics of the lifted and attached flame are compared and dramatic differences are found. All of the flow structures have been altered such as the precessing vortex core being greatly intensified during flame lift-off. Evaluating the average events before flame lift-off revealed the importance of conditions at the combustor inlet. However, evidence for a future reattachment event was only found with a less spatially confined perspective. In addition, transition to lift-off was very sudden while reattachment was far slower.</div>