Although current trends in global warming are of great concern, energy demand is still increasing, resulting in increasing pollutant emissions. To address this issue, we need reliable renewable energy sources, lowered pollutant emissions, and efficient and profitable processes for energy conversion. We also need to improve the use of the energy, produced by existing infrastructure. Consequently, the work presented in this thesis aims at investigating current scientific and technological challenges in energy conversion through biomass gasification and the alternative use of fossil fuels, such as diesel, in the generation of cleaner electricity through auxiliary power units in the transport sector. Production of chemicals, syngas, and renewable fuels is highly dependent on the development and innovation of catalytic processes within these applications. This thesis focuses on the development and optimization of catalytic technologies in these areas. One of the limitations in the commercialization of the biomass gasification technology is the effective catalytic conversion of tars, formed during gasification. Biomass contains high amounts of alkali impurities, which pass on to the producer gas. Therefore, a new material with alkali tolerance is needed. In the scope of this thesis, a new catalyst support, KxWO3 – ZrO2 with high alkali resistance was developed. The dynamic capability of KxWO3 – ZrO2 to store alkali metals in the crystal structure, enhances the capture of alkali metals "in situ". Alkali metals are also important electronic promoters for the active phase, which usually increases the catalysts activity and selectivity for certain products. Experimental results show that conversion of 1-methylnaphathalene over Ni/KxWO3 – ZrO2 increases in the presence of 2 ppm of gas-phase K (Paper I). This support is considered to contribute to the electronic equilibrium within the metal/support interface, when certain amounts of alkali metals are present. The potential use of this support can be extended to applications in which alkali "storage-release" properties are required, i.e. processes with high alkali content in the process flow, to enhance catalyst lifetime and regeneration. In addition, fundamental studies to understand the adsorption geometry of naphthalene with increasing temperature were performed in a single crystal of Ni(111) by STM analyses. Chapter 9 presents preliminary studies on the adsorption geometry of the molecule, as well as DFT calculations of the adsorption energy. In relation to the use of clean energy for transport applications, hydrogen generation through ATR for FC-APUs is presented in Papers II to V. Two promoted RhPt bimetallic catalysts were selected in a previous bench scale study, supported on La2O3:CeO2/d – Al2O3 and MgO : Y2O3/CeO2 – ZrO2. Catalyst evaluation was performed in a fullscale reformer under real operating conditions. Results showed increased catalyst activity after the second monolithic catalyst due to the effect of steam reforming, WGS reaction, and higher catalyst reducibility of the RhxOy species in the CeO2 – ZrO2 mixed oxide, as a result of the improved redox properties. The influence of sulfur and coke formation on diesel reforming was assessed after 40 h on stream. Sulfur poisoning was evaluated for the intrinsic activity related to the total Rh and Pt area observed after exposure to sulfur. Sulfur concentration in the aged catalyst washcoat was observed to decrease in the axial direction of the reformer. Estimations of the amount of sulfur adsorbed were found to be below the theoretical equilibrated coverage on Rh and Pt, thus showing a partial deactivation due to sulfur poisoning. / <p>QC 20150213</p>

The “Integrated Coal Gasification Combined Cycle” (IGCC) represents an advanced approach for green field projects for power generation. This process requires separation of carbon dioxide from the shifted-synthesis gas mixture (fuel gas). Treated fuel gas consists of approximately 40% CO2 and rest H2. Gas hydrate based separation technology for hydrate forming gas mixtures is one of the novel approaches for gas separation. The present study illustrates the gas hydrate-based separation process for the recovery of CO2 and H2 from the fuel gas mixture and discusses relevant issues from macro and molecular level perspectives. Propane (C3H8) is used as an additive to reduce the operating pressure for hydrate formation and hence the compression costs. Based on gas uptake measurement during hydrate formation, a hybrid conceptual process for pre-combustion capture of CO2 is presented. The result shows that it is possible to separate CO2 from hydrogen and obtain a hydrate phase with 98% CO2 in two stages starting from a mixture of 39.2% CO2. Molecular level work has also been performed on CO2/H2 and CO2/H2/C3H8 systems to understand the mechanism by which propane reduces the operating pressure without compromising the separation efficiency.

Susidarantys nuotekų dumblo kiekiai ateityje didės, kadangi šalyje panaudojant ES paramą plėtojamas vandentiekio ir nuotekų surinkimo tinklas. Nuotekų dumblas yra neišvengiamas nuotekų valymo proceso produktas, kuriame yra labai daug kenksmingų medţiagų. Dumblo perdirbimo ir panaudojimo galimybės Europoje pastaruoju metu intensyviau plėtojamos. Naujausios nuotekų dumblo panaudojimo galimybės, turinčios labai didelį mokslininkų susidomėjimą yra šios: deginimas (išgaunant energiją), drėgnas oksidavimas, pirolizė, dujinimas, deginimas kartu su kuru, kuris yra naudojamas energijai išgauti (pvz. biokuras). Darbo metu nagrinėtos dvi dumblo panaudojimo galimybės energetikoje: dumblas, kaip trąša energetinių ţeldinių plantacijose ir dumblo dujinimas maišant su medienos biomase. Pirmoje darbo dalyje atliktas prieš 19 metų pasodintos energetinių ţeldinių plantacijos tyrimas. Tyrimo metu nustatytas medienos masės prieaugis ir sunkiųjų metalų pasisavinimas. Antroje darbo dalyje nustatyti dumblo ir jo mišinių su medienos biomase pagrindiniai kuro parametrai: drėgmė, šilumingumas, CHNS-O kiekiai, peleningumas, sunkieji metalai. Atlikta termogravimetrinė dumblo ir jo mišinių su medienos biomase analizė pagal pasirinktus dujinimo parametrus, kai pastoviai keliama temperatūrą 20 ˚C /min iki 995˚C, o oro padavimas yra 5 %, 10 % ir 17,5 %. / The amount of formed sewage sludge will be on the increase because of development of plumbing and wastewater accumulation network when using EU support in the country. Sewage sludge is inevitable product of the process when cleaning the wasterwater, there are a lot of harmful materials in it. The opportunities to reprocess and use sewage sludge in Europe are increasing more intensively recently. Scientists are interested in those newest opportunities to use sewage sludge: combustion (extracting energy), wet oxidation, pyrolisis, gasification, combustion with fuel, which is used to obtain energy (e. g. biofuels). During the work there were pending two opportunities how to resort sewage sludge in energetics: sewage sludge as a fertiliser in energetic plantations and the gasification of sewage sludge mixing it with biomass of wood. There was done the analysis of the 19 years old plantation of power afforests in the first part of work. During the analysis the increase of wood-pulp and the assimilation of hevy metals were found. During the second part of work there were established the main fuel parameters of sewage sludge and its compounds with wood-pulp: moisture, calorific value, amounts of CHNS-O, ash-content, heavy metals. Thermogravimetric analysis of sewage sludge and its compounds with wood-pulp was done by the selected gasification parameters, when the temperature is constantly raising to 995 ˚C every 20 ˚C /min, and the innings of air is 5 %, 10 % and 17,5 %.

No description available.

Hydrogen can be produced from biomass; this hydrogen is called biohydrogen. Biohydrogen produced in Western Canada can partially contribute to meeting the demand for hydrogen needed for bitumen upgrading. Gasification and pyrolysis are two promising pathways for producing biohydrogen in a large-scale plant. Syngas, produced from the gasification of biomass, and bio-oil, produced from fast pyrolysis of biomass, can be steam reformed to produce biohydrogen. The cost of biohydrogen delivered by pipeline to a distance of 500 km is $2.20 per kg of H2, assuming that a plant utilizes 2000 dry tonnes of whole-tree biomass per day processing it in a Battelle Columbus Laboratory (BCL) gasifier. For forest residue- and straw-based biohydrogen plants the values are similar: $2.19 and $2.31 per kg of H2, respectively. Maximum economy of scale benefits are realized for biohydrogen production plants capable of processing 2000 and 3000 dry tonnes per day using BCL and GTI (Gas Technology Institute) gasification technology, respectively. The cost of biohydrogen from fast pyrolysis ($2.47 per kg of H2 from a 2000 dry tonne per day plant), using forest residue as the feedstock, is higher than the cost of biohydrogen produced by gasification. Carbon credits of about $120-$140 per tonne of CO2 are required to make biohydrogen competitive with natural-gas-based hydrogen.

Die Arbeit befasst sich mit der thermodynamischen Modellierung des British Gas-Lurgi-Vergasungsprozesses (BGL). Es werden auftretende Schwachstellen des Prozesses analysiert und auf das Verhalten der Mineralstoffkomponenten zurückgeführt. Auf Grundlage einer Stoffbilanz sowie zahlreicher Prozessdaten (BGL-Vergaser der SVZ Schwarze Pumpe GmbH) wurde das in SimuSage erstellte Stufenmodell an Nichtgleichgewichtszustände und Transportvorgänge angepasst. Das Modell erlaubt die qualitative und quantitative Beschreibung eines Alkalikreislaufes, welcher durch KCl geprägt ist. Mit dem Modell werden wirksame Maßnahmen abgebildet, um die Anreicherung von KCl und die damit verbundenen technischen Störungen zu vermeiden.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Submitted by JOSÉ RAMON COPA REY null (jcoparey@gmail.com) on 2018-09-14T03:34:23Z No. of bitstreams: 1 Tesis José R. Copa Rey.pdf: 5579664 bytes, checksum: 29f9e65ff72c472b08614891d5361d0e (MD5) / Approved for entry into archive by Pamella Benevides Gonçalves null (pamella@feg.unesp.br) on 2018-09-14T12:35:08Z (GMT) No. of bitstreams: 1 coparey_jr_dr_guara.pdf: 5579664 bytes, checksum: 29f9e65ff72c472b08614891d5361d0e (MD5) / Made available in DSpace on 2018-09-14T12:35:08Z (GMT). No. of bitstreams: 1 coparey_jr_dr_guara.pdf: 5579664 bytes, checksum: 29f9e65ff72c472b08614891d5361d0e (MD5) Previous issue date: 2018-08-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O bagaço e a palha são resíduos do processamento industrial da cana-de-açúcar que constituem uma importante fonte de recurso para cogeração de energia no setor sucroalcooleiro. Os sistemas de cogeração neste setor geram potência mecânica ou elétrica e vapor, que são utilizados no próprio processo e o excedente é vendido as concessionárias de energia. Porém, estes sistemas encontram-se bem abaixo do potencial real. Uma alternativa tecnológica que poderá contribuir com a oferta de excedentes de energia elétrica é a introdução da tecnologia BIG-GT (gaseificadores de biomassa associados a turbina a gás e caldeira de recuperação). O presente trabalho, tem como objetivo o estudo termoeconômico da incorporação desta tecnologia em usinas sucroalcooleiras como alternativa para o aumento de geração de eletricidade. As análises energéticas e exergéticas foram realizadas para quatro possíveis configurações de uma usina sucroalcooleira com a integração da tecnologia BIG-GT com o objetivo de avaliar a eficiência de geração de eletricidade e vapor de processo, bem como o aproveitamento global de energia de cada uma delas. Na análise termoeconômica, é determinado o custo de produção de gás de gaseificação, eletricidade e vapor do processo no sistema proposto, assim como, tempo de recuperação do investimento. Na parte final do trabalho foi realizada a otimização multiobjetiva do sistema considerando três funções objetivo: tecnológica, econômica e ambiental, para identificar a configuração com melhor comportamento. De acordo com os resultados obtidos no estudo conclui-se que o caso III que estuda a gaseificação em leito fluidizado circulante pressurizado e mistura de oxigênio-vapor de gaseificação e o caso IV que além da gaseificação em leito fluidizado circulante pressurizado com mistura de oxigênio-vapor estuda a queima suplementar de palha na caldeira de recuperação, apresentam-se como as melhores das opções propostas. / Bagasse and straw are residues from the industrial processing of sugarcane that constitute an important source for cogeneration of energy in the sugar-alcohol sector. The cogeneration systems in this sector generate mechanical or electrical power and steam, which are used in the process itself and the surplus is sold to energy distribution companies. However, these systems are well below real potential. One of the technological alternatives that may improve the supply of surplus electricity is the introduction of BIG-GT technology (biomass gasifier associated with gas turbine and Heat recovery steam generator). In this work, it is proposed to conduct thermoeconomic studies of the incorporation of this technology in the sugarcane ethanol plants as an alternative to increasing the supply of electricity generation. The energetic and exergetic analyses were performed for four possible configurations of a sugarcane ethanol plant with the integration of BIG-GT technology with the objective of evaluating the efficiency of electricity generation and process steam as well as the global energy utilization of each one of them. In the thermoeconomic analysis, it is determined the cost of production of producer gas, electricity and steam of the process in the proposed system, as well as the investment payback period. In the final part of the work, it is developed the multiobjective optimization of the system considering three objective functions: technological, thermoeconomic and environmental, for identifying the configuration with better behavior. According to the results obtained in the study, it is concluded that case III and case IV are presented as the best of the proposed options. / 1450304

La conversion thermochimique de la biomasse en lit fluidisé circulant permet la production d’un gaz à haute valeur ajoutée, utilisable dans de nombreuses applications. L’objectif de ces travaux est de mieux comprendre et modéliser les phénomènes couplés, hydrodynamiques et réactifs, se déroulant en lit fluidisé circulant. Dans un premier temps, un pilote de pyrogazéification de 20 kg/h de biomasse en lit fluidisé circulant a été conçu. L’étude hydrodynamique de ce pilote a ensuite été réalisée entre 20 et 950 °C. Les résultats ont permis d’établir des règles de design et de fonctionnement de réacteurs de gazéification en lit fluidisé circulant. Dans un second temps, une étude de la pyrogazéification de la biomasse a été réalisée en lit fluidisé dense ainsi qu’en lit fluidisé circulant, entre 750 et 850 °C. L’étude de l’influence de nombreux paramètres opératoires (températures, pression partielle de la vapeur d’eau, débit de biomasse, débit de circulation, inventaire et nature du média, forme de la biomasse) sur les performances de la gazéification a permis d’identifier les paramètres clés permettant de contrôler la composition ainsi que le volume de gaz de synthèse produit. Par ailleurs, à partir des résultats expérimentaux, un schéma réactionnel est proposé pour la pyrolyse de la biomasse étudiée. Enfin, un outil de modélisation du réacteur de gazéification de la biomasse en lit fluidisé dense et circulant, intégrant les réactions de pyrolyse, de gazéification, de water-gas shift et de reformage des goudrons a été développé et validé sur les résultats expérimentaux. / The biomass thermochemical conversion in fast internally circulating fluidized bed (FICFB) allows producing a high-added value syngas that can be used in many end-use applications. This work aims to better understand and model the coupled phenomena, hydrodynamic and reactive, occurring in FICFB processes. In a first time, a 20 kg/h FICFB biomass pyrogasification pilot was designed and erected. Then, the hydrodynamic study of this pilot was carried out between 20 and 950 °C. Results led to propose some design and operation rules for FICFB gasifiers. In a second time, biomass pyrogasification was studied in a dense fluidized bed (DFB) as in a FICFB, between 750 and 850 °C. From the survey of the effect of numerous operating parameters (temperatures, steam partial pressure, biomass feeding rate, circulation flow rate, bed material inventory and nature, biomass shape) on the gasification performances, the key parameters for the control of produced syngas volume and composition were identified. Finally, a modelling tool of DFB and FICFB biomass gasifiers, integrating pyrolysis, gasification, water-gas shift and tars reforming reactions was developed and validated on the experimental results.