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Récemment, la pyro-gazéification de déchets ménagers solides (DMS) a suscité une plus grande attention, en raison de ses bénéfices potentiels en matière d’émissions polluantes et d’efficacité énergique. Afin de développer un système de traitement de ces déchets, durable et intégré, ce manuscrit s’intéresse plus spécifiquement au développement de la technique de pyro-gazéification des DMS, à la fois sur l’aspect technologique (expérimentations) et sur son évaluation globale (modélisation). Pour cette étude, quatre composants principaux représentatifs des DMS (déchet alimentaire, papier, bois et plastique) ont été pyro-gazéifiés dans un lit fluidisé sous atmosphère N2, CO2 ou vapeur d’eau. Les expériences ont été menées avec les composés seuls ou en mélanges afin de comprendre les interactions mises en jeu et leurs impacts sur la qualité du syngas produit. La présence de plastique améliore significativement la quantité et la qualité du syngas (concentration de H2). La qualité du syngas est améliorée plus particulièrement en présence de vapeur d’eau, ou, dans une moindre mesure, en présence de CO2. Les résultats obtenus ont été ensuite intégrés dans un modèle prédictif de pyro-gazéification basé sur un réseau de neurones artificiels (ANN). Ce modèle prédictif s’avère efficace pour prédire les performances de pyro-gazéification des DMS, quelle que soit leur composition (provenance géographique). Pour améliorer la qualité du syngas et abaisser la température du traitement, la gazéification catalytique in-situ, en présence de CaO, a été menée. L’impact du débit de vapeur d’eau, du ratio massique d’oxyde de calcium, ainsi que de la température de réaction a été étudié en regard de la production (quantité et pourcentage molaire dans le gaz) d’hydrogène. La présence de CaO a permis d’abaisser de 100 oC la température de gazéification, à qualité de syngas équivalente. Pour envisager une application industrielle, l’activité du catalyseur a aussi été évaluée du point de vue de sa désactivation et régénération. Ainsi, les températures de carbonatation et de calcination de 650 oC et 800 oC permettent de prévenir la désactivation du catalyseur, tandis que l’hydratation sous vapeur d’eau permet la régénération. Ensuite, une étude a été dédiée à l’évaluation et à l’optimisation de la technologie de pyro-gazéification par la méthode d’analyse de cycle de vie (ACV). Le système de gazéification permet d’améliorer les indicateurs de performances environnementales comparativement à l’incinération conventionnelle. De plus, des systèmes combinant à la fois la transformation des déchets en vecteur énergétique et la mise en œuvre de ce vecteur ont été modélisés. La pyro-gazéification combinée à une turbine à gaz permettrait de maximiser l’efficacité énergétique et de diminuer l’impact environnemental du traitement. Ainsi, les résultats permettent d’optimiser les voies actuelles de valorisation énergétique, et de d’optimiser les techniques de pyro-gazéification. / Due to the potential benefits in achieving lower environmental emissions and higher energy efficiency, municipal solid waste (MSW) pyro-gasification has gained increasing attentions in the last years. To develop such an integrated and sustainable MSW treatment system, this dissertation mainly focuses on developing MSW pyro-gasification technique, including both experimental-based technological investigation and assessment modeling. Four of the most typical MSW components (wood, paper, food waste and plastic) are pyro-gasified in a fluidized bed reactor under N2, steam or CO2 atmosphere. Single-component and multi-components mixture have been investigated to characterize interactions regarding the high-quality syngas production. The presence of plastic in MSW positively impacts the volume of gas produced as well as its H2 content. Steam clearly increased the syngas quality rather than the CO2 atmosphere. The data acquired have been further applied to establish an artificial neural network (ANN)-based pyro-gasification prediction model. Although MSW composition varies significantly due to geographic differences, the model is robust enough to predict MSW pyro-gasification performance with different waste sources. To further enhance syngas properties and reduce gasification temperature as optimization of pyro-gasification process, MSW steam catalytic gasification is studied using calcium oxide (CaO) as an in-situ catalyst. The influence of CaO addition, steam flowrate and reaction temperature on H2-rich gas production is also investigated. The catalytic gasification using CaO allows a decrease of more than 100 oC in the reaction operating temperature in order to reach the same syngas properties, as compared with non-catalyst high-temperature gasification. Besides, the catalyst activity (de-activation and re-generation mechanisms) is also evaluated in order to facilitate an industrial application. 650 oC and 800 oC are proven to be the most suitable temperature for carbonation and calcination respectively, while steam hydration is shown to be an effective CaO re-generation method. Afterwards, a systematic and comprehensive life cycle assessment (LCA) study is conducted. Environmental benefits have been achieved by MSW gasification compared with conventional incineration technology. Besides, pyrolysis and gasification processes coupled with various energy utilization cycles are also modeled, with a gasification-gas turbine cycle system exhibits the highest energy conversion efficiency and lowest environmental burden. The results are applied to optimize the current waste-to-energy route, and to develop better pyro-gasification techniques.

Thesis (MScEng)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: In light of the rapid depletion of the world’s oil reserves, concerns about energy security prompted the exploration of alternative sources of liquid fuels for transportation. One such alternative is the production of synthetic fuels with the indirect coal liquefaction process or Coal-To-Liquids (CTL) process. In this process, coal is burned in a gasifier in the presence of steam and oxygen to produce a synthesis gas or syngas, consisting mainly of hydrogen and carbon monoxide. The syngas is then converted to liquid fuels and a variety of useful chemicals in a Fischer Tropsch synthesis reactor. However, the traditional process for syngas production also produces substantial amounts of carbon dioxide. In fact, only about one third of the carbon in the coal feedstock ends up in the liquid fuel product using traditional CTL technology. If additional hydrogen was available, the carbon utilisation of the process could be improved significantly. The high temperature reactor (HTR) is a gas cooled Generation IV nuclear reactor ideally suited to provide electrical power and high temperature heat for the production of carbon neutral hydrogen via high temperature electrolysis. The integration of an HTR into a CTL process therefore provides an opportunity to improve the thermal and carbon efficiency of the CTL process significantly. This thesis presents a possible process flow scheme for a nuclear assisted CTL process. The system is evaluated in terms of its thermal or syngas production efficiency (defined as the ratio of the heating value of the produced syngas to the sum of the heating value of the coal plus the HTR heat input) as well as its carbon utilisation. If the hydrogen production plant is sized to produce only enough associated oxygen to supply in the needs of the gasification plant, syngas is produced at about 63% thermal efficiency, while 71.5% of the carbon is utilised in this process. It was found that the optimum HTR outlet temperature to produce hydrogen with a high temperature steam electrolysis process is 850°C. If enough process heat and electrical power are available and process equipment capacities are sufficient, the carbon utilisation of the process could be improved even further to values in excess of 90%. / AFRIKAANSE OPSOMMING: Die uitputting van die wêreld se olie-reserwes, asook kommer oor energiesekuriteit het daartoe gelei dat alternatiewe bronne van vloeibare brandstowwe vir vervoer ondersoek moes word. Een so 'n alternatief is die produksie van sintetiese brandstof d.m.v. die indirekte steenkool vervloeiing proses of sogenaamde Coal-To-Liquids (CTL) proses. In hierdie proses word steenkool in die teenwoordigheid van stoom en suurstof in 'n vergasser gebrand om 'n sintesegas of singas te produseer, wat hoofsaaklik uit waterstof en koolstofmonoksied bestaan. Die sintesegas word daarna omgeskakel na vloeibare brandstowwe en 'n verskeidenheid van nuttige chemikalieë in 'n Fischer-Tropsch-sintese reaktor. Ongelukkig produseer die tradisionele proses vir sintesegas produksie ook 'n beduidende hoeveelheid koolstofdioksied. Trouens, slegs sowat een derde van die koolstof in die steenkool roumateriaal eindig in die vloeibare brandstof produk indien van tradisionele CTL-tegnologie gebruik gemaak word. Indien addisionele waterstof beskikbaar was, kon die koolstofbenutting van die proses aansienlik verbeter word. Die hoë temperatuur reaktor (HTR) is 'n gas-verkoelde Generasie IV kernreaktor wat by uitstek geskik is om elektrisiteit en hoë temperatuur hitte te verskaf vir die produksie van koolstofneutrale waterstof d.m.v. hoë temperatuur elektrolise. Die integrasie van 'n HTR in 'n CTL-proses bied dus 'n geleentheid om die termiese- en koolstofdoeltreffendheid van die CTL-proses aansienlik te verbeter. In hierdie ondersoek word 'n moontlike proses vloeidiagram vir 'n kern-gesteunde CTL-proses voorgestel. Die stelsel is geëvalueer in terme van sy termiese- of sintesegas produksie doeltreffendheid (gedefinieer as die verhouding van die hittewaarde van die geproduseerde sintesegas gedeel deur die som van die hittewaarde van die steenkool en die HTR hitte-insette) sowel as sy koolstof-effektiwiteit. Indien die waterstof produksie-aanleg ontwerp word om net genoeg geassosieerde suurstof te voorsien om in die behoeftes van die vergassing-aanleg te voorsien, word sintesegas teen ongeveer 63% termiese doeltreffendheid vervaardig, terwyl 71.5% van die koolstof in hierdie proses benut word. Daar is bevind dat 850°C die optimum HTR uitlaat temperatuur is om waterstof d.m.v. hoë temperatuur stoom-elektrolise te vervaardig. Indien daar genoeg proses hitte en elektrisiteit beskikbaar is en die proses toerusting kapasiteite voldoende is, sou die koolstof-benutting van die proses tot meer as 90% verbeter kon word.

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.

Parmi les biocarburants de deuxième génération, la chaîne "biomass to liquid" vise à convertir les résidus agricoles en carburant. Cette voie suppose une première étape de gazéification de la biomasse en un gaz de synthèse, mélange de CO et de H2. Ce gaz doit ensuite être désulfuré, afin de ne pas endommager le catalyseur Fischer-Tropsch, à l'aide d'oxydes métalliques tel que l'oxyde de zinc, qui se sulfure selon la réaction suivante : ZnO(s) + H2S(g) → ZnS(s) + H2O(g) a l'heure actuelle, aucune étude ne décrit les mécanismes de la réaction. le but de ce travail a donc été d'identifier les différentes étapes du mécanisme de sulfuration puis d'établir une loi de vitesse de réaction. L'étude cinétique a été réalisée par thermogravimétrie. La formation de cavités au cœur des particules sulfurées a été observée par MEB et MET, mettant en évidence une croissance externe de la phase de ZnS. Un mécanisme de sulfuration en huit étapes élémentaires a été proposé avec diffusion des atomes de zinc et d'oxygène de l'interface interne ZnO/ZnS vers la surface externe du ZnS formé. Le régime limitant de la réaction a été déterminé via l'étude de l'influence des pressions partielles de H2S et de H2O sur la vitesse de réaction. Un régime mixte sur la base de deux étapes élémentaires a été envisagé : une réaction d'interface externe avec désorption des molécules d'eau et la diffusion des atomes d'oxygène. la formation de cavités à l'interface interne ZnO/ZnS entraînant une diminution de la surface de contact entre les phases ZnO et ZnS a été mise en évidence, phénomène probablement à l'origine du ralentissement de la réaction observé sur les courbes cinétiques. / Among the second generation biofuels processes, the "biomass to liquid" process aims at turning agricultural wastes into fuels. This process comprises a first step of feed gasification into a synthesis gas, composed of CO and H2. Sulfur compounds such as H2S are also present in the synthesis gas and must be removed, in order to prevent Fischer-Tropsch catalyst poisoning. deep desulfurization is achieved with metal oxides such as zinc oxide, which reacts with H2S according to the reaction: ZnO(s) + H2S(g) → ZnS(s) + H2O(g) nevertheless to our knowledge, most of the studies found in the literature do not describe accurately the mechanism involved at a crystal scale. The aim of this work was to determine the elementary steps of the ZnO sulfidation reaction, and in fine to establish a kinetic rate model in agreement with the proposed mechanism. The sulfidation reaction has been studied through thermogravimetric experiments. SEM and TEM characterizations of sulfided ZnO have revealed the presence of voids inside particles, that is evidence an external growth of ZnS phase. A sulfidation mechanism with eight elementary steps has been proposed, based on zinc and oxygen diffusion through the ZnS layer from the internal ZnO/ZnS interface to the ZnS surface. The rate determining step of the reaction was determined from the study of the influence of H2S and H2O partial pressures on the reaction rate. A "mixed kinetics" based on two elementary steps was considered: external interface reaction with H2O desorption and oxygen diffusion. Cavities formation at the internal ZnO/ZnS interface leading to a decreasing contact zone between ZnO and ZnS phases might be responsible for the reaction rate blocking observed on the kinetic curves.

Catalisadores ativos e estáveis, preparados a partir dos hidróxidos duplos lamelares (HDLs) contendo os cátions Ni2+, Zn2+, Al3+ e Zr4+(NiZn-Al, NiZn-AlZr e NiZn-Zr), foram avaliados na reação de reforma seca do metano. Os precursores foram caracterizados por difração de raios X, confirmando a formação das fases para as amostras de NiZn-Al e NiZn-AlZr. As espectroscopias no infravermelho/Raman elucidaram a ocorrência dos ânions (CO32-) e das moléculas de água na intercamada. A Fisissorção de nitrogênio ( método de BET) determinou a presença de poros e a área superficial específica. As formas das isotermas foram do tipo IV, de acordo com a IUPAC, e representa uma estrutura mesoporosa. A análise termogravimétrica foi utilizada para determinar a temperatura de calcinação dos precursores para obtenção dos catalisadores e as temperaturas utilizadas foram 550 °C, 650 °C e 750 °C. Os resultados de difração de raios X dos catalisadores apresentaram uma mistura de óxidos binários (NiO, ZnO, ZrO2 e Al2O3) e óxidos ternários (NiAl2O4 e ZnAl2O4). As fases de espinélios foram observadas nos catalisadores obtidos a 650°C (Ni/ZnAl-6 e Ni/ZnAlZr-6) e 750°C (Ni/ZnAl-7 e Ni/ZnAlZr-7). A redução a temperatura programada de hidrogênio (TPR-H2) forneceu informações sobre a redução do catalisador. Os resultados exibiram interações entre a fase ativa com as outras fases presentes no intervalo entre 350 - 800 °C, enquanto que a dessorção àtemperatura programada de CO2 (DTP-CO2) mostrou que os catalisadores possuem sítios básicos fracos. Ademais, os catalisadores foram caracterizados por fisissorção de nitrogênio, microscopia eletrônica de varredura (MEV), espectroscopia Raman e basicidade usando um indicador de Hammett. O desempenho dos catalisadores foi avaliado na reação de reforma seca do metano utilizando uma razão molar de alimentação de CH4: CO2 = 1,5:1,0; a fim de simular a composição do biogás. Os resultados mostraram uma maior conversão para o CO2 em todos os catalisadores investigados, o que pode ser atribuído ao maior teor de CH4 alimentado. Além disso, é importante ressaltar a contribuição dos sítios básicos presentes nas amostras, o que pode também contribuir para a conversão do CO2. A maior conversão de CH4 foi observada para os catalisadores tratados a 750 °C. Após as reações, foi observada a formação de carbono grafite sobre todos os catalisadores, com menor percentual para a amostra Ni/ZnAl, calcinadas a 550 °C e 650 °C, e Ni/ZnZr-7, calcinada a 750 °C. Finalmente, os catalisadores calcinados a 650 °C e 750 °C também foram ativados na temperatura de 750°C e os resultados reacionais mostraram que essa temperatura favoreceu o processo de aglomeração e, portanto, promoveu baixas conversões para o CH4 e CO2. / Active and stable catalysts, prepared from the lamellar double hydroxides (HDLs) containing the cations Ni2 +, Zn2 +, Al3 + and Zr4 + (NiZn-Al, NiZn-AlZr and NiZn-Zr) were evaluated in the dry reforming reaction of methane. The precursors were characterized by X-ray diffraction method, confirming the formation of phases for NiZn-Al and NiZn-AlZr samples. Infrared / Raman spectroscopies elucidated the occurrence of anions (CO32-) and water molecules in the interlayer. Nitrogen physisorption (BET method) determined the presence of pores and the specific surface area. The shape of the isotherms were type IV, according to the IUPAC, representing a mesoporous structure. The thermogravimetric analysis was used to determine the calcination temperature of the precursors to obtain the catalysts and the temperatures used were 550 ° C, 650 ° C and 750 ° C. The X-ray diffraction results of the catalysts showed a mixture of binary oxides (NiO, ZnO, ZrO2 and Al2O3) and ternary oxides (NiAl2O4 and ZnAl2O4). The spinel phases were observed in the catalysts obtained at 650 °C (Ni/ZnAl-6 and Ni/ZnAlZr-6) and 750°C (Ni/ZnAl-7 and Ni/ZnAlZr-7) Temperature- programmed reduction with hydrogen (H2-TPR) provided information on catalyst reduction. The results showed interactions between the active phase and the other phases present in the range of 350 - 800 ° C, while temperature- programmed desorption of CO2 (CO2-TPD) showed that the catalysts have weak basic sites. In addition, the catalysts were characterized by Nitrogen physisorption, scanning electron microscopy (SEM), Raman spectroscopy and basicity using a Hammett indicator. The performance of the catalysts was evaluated in the dry reforming reaction of the methane using a CH4: CO2 molar feed ratio = 1.5: 1.0; In order to simulate the biogas composition. The results showed a higher conversion to CO2 in all the catalysts investigated, which can be attributed to the higher content of CH4 fed. In addition, it is important to restate the contribution of the basic sites present in the samples, which may also contribute to the conversion of CO2.The higher conversion of CH4 was observed for the catalysts treated at 750 ° C. After the reactions, the formation of graphite carbon was observed on all the catalysts, with a lower percentage for Ni / ZnAl samples, calcined at 550 ° C and 650 ° C, and Ni / ZnZr-7, calcined at 750 ° C. Finally, the catalysts calcined at 650 ° C and 750 ° C were also activated at the temperature of 750 ° C. and the reaction results showed that this temperature favored the agglomeration process and, therefore, promoted low conversions for CH4 and CO2.

Environmentally friendly and efficiently produced energy from sustainable and renewable resources is of great importance. Carbon dioxide (CO2) and nitric oxides (NOx) are the main emissions of air-breathing gas turbines in power plants. Gas turbines of the power generation industry are normally fueled with liquid fuels, natural gas or syngas in changing qualities. Syngas can be produced by gasification processes in IGCC power plants and consist of varying percentages of the main fractions hydrogen (H2) and carbon monoxide (CO). CO2 emissions can be reduced by a decrease of the CO-share and an increase of the hydrogen-share in the syngas fuel, and by using pre-combustion carbon capture and sequestration (CCS) technology. For low NOx, current gas turbine combustion chamber technologies require diluents, a rather low H2 content and modifications of the combustor hardware. A feasible solution for low NOx hydrogen and syngas combustion in gas turbines is the Micromix principle developed at Aachen University of Applied Sciences. The goal of this doctoral thesis is the research on a Micromix combustor with increased power densities fueled with hydrogen-rich syngas with about 90% by volume hydrogen, and going up to 100% hydrogen in the fuel. Test burner experiments are used to characterize the combustion and emission properties of a multitude of key drivers. Based on this optimization with a variety of scaled model test burners, a prototype dual-fuel hydrogen/syngas Micromix combustor is designed and integrated into the annular combustion chamber of an industrial gas turbine. In the gas turbine, the performance characteristics of the prototype-combustor are investigated under real operational conditions with hydrogen-rich syngas and pure hydrogen. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Reduction of the pollutant emissions is a challenge for the gas turbine industry. A solution to this problem is to employ the low swirl burner which can operate at lower equivalence ratios than a conventional swirl burner. However, flames in the lean regime of combustion are susceptible to flow perturbations and combustion instability. Combustion instability is the coupling between unsteady heat release and combustor acoustic modes where one amplifies the other in a feedback loop. The other method for significantly reducing NOx and CO2 is increasing fuel reactivity, typically done through the addition of hydrogen. This helps to improve the flammability limit and also reduces the pollutants in products by decreasing thermal NOx and reducing CO2 by displacing carbon. In this work, the flammability limits of a low swirl burner at various operating conditions, is studied and the effect of pressure, bulk velocity, burner shape and percent of hydrogen (added to the fuel) is investigated. Also, the flame structure for these test conditions is measured using OH planar laser induced fluorescence and assessed. Also, the OH PLIF data is used to calculate Rayleigh index maps and to construct averaged OH PLIF intensity fields at different acoustic excitation frequencies (45-155, and 195Hz). Based on the Rayleigh index maps, two different modes of coupling between the heat release and the pressure fluctuation were observed: the first mode, which occurs at 44Hz and 55Hz, shows coupling to the flame base (due to the bulk velocity) while the second mode shows coupling to the sides of the flame. In the first mode, the flame becomes wider and the flame base moves with the acoustic frequency. In the second mode, imposed pressure oscillations induce vortex shedding in the flame shear layer. These vortices distort the flame front and generate locally compact and sparse flame areas. The local flame structure resulting from these two distinct modes was markedly different.

Coal derived synthetic gas (syngas) fuel is a promising solution for today s increasing demand for clean and reliable power. Syngas fuels are primarily mixtures of H2 and CO, often with large amounts of diluents such as N2, CO2, and H2O. The specific composition depends upon the fuel source and gasification technique. This requires gas turbine designers to develop fuel flexible combustors capable of operating with high conversion efficiency while maintaining low emissions for a wide range of syngas fuel mixtures. Design tools often used in combustor development require data on various fundamental gas combustion properties. For example, laminar flame speed is often an input as it has a significant impact upon the size and static stability of the combustor. Moreover it serves as a good validation parameter for leading kinetic models used for detailed combustion simulations. Thus the primary objective of this thesis is measurement of laminar flame speeds of syngas fuel mixtures at conditions relevant to ground-power gas turbines. To accomplish this goal, two flame speed measurement approaches were developed: a Bunsen flame approach modified to use the reaction zone area in order to reduce the influence of flame curvature on the measured flame speed and a stagnation flame approach employing a rounded bluff body. The modified Bunsen flame approach was validated against stretch-corrected approaches over a range of fuels and test conditions; the agreement is very good (less than 10% difference). Using the two measurement approaches, extensive flame speed information were obtained for lean syngas mixtures at a range of conditions: 1) 5 to 100% H2 in the H2/CO fuel mixture; 2) 300-700 K preheat temperature; 3) 1 to 15 atm pressure, and 4) 0-70% dilution with CO2 or N2. The second objective of this thesis is to use the flame speed data to validate leading kinetic mechanisms for syngas combustion. Comparisons of the experimental flame speeds to those predicted using detailed numerical simulations of strained and unstrained laminar flames indicate that all the current kinetic mechanisms tend to over predict the increase in flame speed with preheat temperature for medium and high H2 content fuel mixtures. A sensitivity analysis that includes reported uncertainties in rate constants reveals that the errors in the rate constants of the reactions involving HO2 seem to be the most likely cause for the observed higher preheat temperature dependence of the flame speeds. To enhance the accuracy of the current models, a more detailed sensitivity analysis based on temperature dependent reaction rate parameters should be considered as the problem seems to be in the intermediate temperature range (~800-1200 K).

Liquid transportation fuels can be produced by gasification of carbon containing biomass to syngas( a gaseous mixture of CO and H2) with subsequent conversion of the syngas to fuels. One possible process is the so called mixed alcohols synthesis, which produces a mixture of ethanol and higher alcohols. Another possible process is the reaction of syngas to Fischer-Tropsch liquids, mainly diesel fuel. This study examines the economics of syngas, ethanol and diesel fuel production from lignocellulosic biomass (southern pine residues). The process is modeled with Aspen Plus, a process simulation software package. The process is simulated for plant sizes between 715 and 2205 dry tons/day. The feedstock moisture content is varied between 20% and 50% and the feedstock costs are varied between $30/dry ton and $80/dry ton. The influences of the examined variables on the minimum product selling price are determined. The economic effects of an integration of the mixed alcohols and the FT diesel process with a kraft mill are also evaluated.