Sol-gel (solution-gelation) method was used to prepare Ni-Ti and Ni-Ti-Al catalysts for reforming of methane with carbon dioxide. This method, after optimizing the parameters such as hydrolysis and acid/alkoxide ratio, is able to make a Ni-Ti catalyst with a surface area as high as 426m2/g when calcined at 473K; but calcination at higher temperature lead to dramatic decrease in surface area. XRD, XPS, TEM and SEM were used to understand this change. Using a packed bed reactor, the catalysts were evaluated with the reforming reaction. It was found that the activity of the Ni-Ti catalyst increases with the Ni loading in the range of 1-10wt%. The reduction temperature has strong effect on activity of the reduced catalyst. Up to 973K, the activity increases with the reduction temperature; but after 973K, the activity decreases and become 0 when the temperature is over 1023K. The Ni-Ti catalyst also deactivated as 15% after 4h of time on stream. The XRD analysis shows that Ti3O5 formed in the catalyst after higher-temperature reduction as well as after the reaction for a period of time. The formation of Ti3O5 may render the catalyst to loss its activity. However, further study is expected to understand the mechanism. TG/DTA analysis shows that both Ni-Ti and Ni-Ti-Al catalysts had carbon deposition; but the latter maintained higher activity in a longer period of time.

Sol-gel (solution-gelation) method was used to prepare Ni-Ti and Ni-Ti-Al catalysts for reforming of methane with carbon dioxide. This method, after optimizing the parameters such as hydrolysis and acid/alkoxide ratio, is able to make a Ni-Ti catalyst with a surface area as high as 426m2/g when calcined at 473K; but calcination at higher temperature lead to dramatic decrease in surface area. XRD, XPS, TEM and SEM were used to understand this change. Using a packed bed reactor, the catalysts were evaluated with the reforming reaction. It was found that the activity of the Ni-Ti catalyst increases with the Ni loading in the range of 1-10wt%. The reduction temperature has strong effect on activity of the reduced catalyst. Up to 973K, the activity increases with the reduction temperature; but after 973K, the activity decreases and become 0 when the temperature is over 1023K. The Ni-Ti catalyst also deactivated as 15% after 4h of time on stream. The XRD analysis shows that Ti3O5 formed in the catalyst after higher-temperature reduction as well as after the reaction for a period of time. The formation of Ti3O5 may render the catalyst to loss its activity. However, further study is expected to understand the mechanism. TG/DTA analysis shows that both Ni-Ti and Ni-Ti-Al catalysts had carbon deposition; but the latter maintained higher activity in a longer period of time.

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Numerical simulations of coal gasification process inside a generic 2-stage entrainedflow gasifier are carried out using the commercial CFD solver ANSYS/FLUENT. The 3-D Navier-Stokes equations and eight species transport equations are solved with three heterogeneous global reactions, three homogeneous reactions, and one thermal cracking equation of volatiles. Finite rates are used for the heterogeneous solid-gas reactions. Both finite rate and eddy-breakup combustion models are calculated for each homogeneous gas-gas reaction, and the smaller of the two rates is used. Lagrangian-Eulerian method is employed. The Eulerian method calculates the continuous phase while the Lagrangian method tracks each coal particle. Fundamental study is carried out to investigate effects of five turbulence models (standard k-ε, k-ω, RSM, k-ω SST, and k-ε RNG) and four devolatilization models (Kobayashi, single rate, constant rate, and CPD) on gasification simulation. A study is also conducted to investigate the effects of different operation parameters on gasification process including coal mixture (dry vs. slurry), oxidant (oxygen-blown vs. air-blown), and different coal distributions between two stages. Finite-rate model and instantaneous gasification model are compared. It is revealed that the instantaneous gasification approach can provide an overall evaluation of relative changes of gasifier performance in terms of temperature, heating value, and gasification efficiency corresponding to parametric variations, but not adequately capture the local gasification process predicted by the finite rate model in most part of the gasifier. Simulations are performed to help with design modifications of a small industrial demonstration entrained-flow gasifier. It is discovered that the benefit of opening the slag tap on the quench-type gasifier wider by allowing slag to move successfully without clogging is compromised by increased heat losses, reduced gasification performance, downgraded syngas heating value, and increased unburned volatiles. The investigation of heat transfer on fuel injectors shows that blunt tip fuel injector is less likely to fail compared to conical tip fuel injector because the maximum high temperature on the injector is scattered. Two concentric fuel/oxidant injections provide better fuel-oxidant mixing and higher syngas heating value than four separate fuel and oxidant injections.

Le dioxyde de carbone, principal gaz à effet de serre lié aux activités humaines, est considéré comme l’un des gaz les plus problématiques pour notre environnement ces dernières années, principalement à cause du réchauffement climatique qu’il engendre. C’est pour cette raison que l’augmentation de sa teneur dans l’atmosphère nous concerne tous quant aux conséquences futures pour notre planète. Afin de limiter l’émission de CO2, sa conversion en composés à valeur ajoutée présente un grand intérêt et est possible notamment via des procédés plasmas. Plus particulièrement, les décharges à barrière diélectrique (DBD) sont utilisées depuis quelques années pour générer des plasmas froids opérant à pression atmosphérique, principalement pour des applications en traitement de surface, mais également pour le traitement d’effluents gazeux.Lors de cette thèse, nous nous sommes focalisés sur le processus de dissociation du CO2 en CO et O2 via un réacteur DBD à flux continu et avons analysé sa conversion et son efficacité énergétique via différentes études. Celles-ci ont été réalisées grâce à plusieurs méthodes de diagnostic, comme par exemple la spectrométrie de masse utilisée pour déterminer la conversion et l’efficacité du processus, la spectroscopie d’émission optique, l’oscilloscope pour une caractérisation électrique, etc. afin d’avoir une meilleure compréhension du comportement des décharges CO2.Dans un premier temps, nous avons réalisé une étude détaillée d’un plasma CO2 pur où nous avons fait varier différents paramètres, tels que le temps de résidence, la fréquence, la puissance, la pulsation de la haute tension et l’épaisseur et la nature du diélectrique. Le CO2 donne lieu généralement à une décharge filamentaire, consistant en de nombreuses microdécharges réparties au niveau de la zone du plasma. Celles-ci constituent la principale source de réactivité dans une DBD. Un aperçu détaillé de l’aspect physique de ces microdécharges a été réalisé grâce à la caractérisation électrique, permettant de mieux comprendre les propriétés électriques de la décharge et des microdécharges. En effet, nous avons pu déterminer l’importance de la tension présente au niveau du plasma, de l’intensité du courant plasma, du nombre de microdécharges et de leur temps de vie sur l’efficacité du processus de dissociation de CO2.Ensuite, nous avons conclu ce travail avec des études combinant le CO2 en phase plasma avec de l’eau ou du méthane afin de produire des molécules à valeur ajoutée telles que les syngas (CO et H2), mais aussi des hydrocarbures (C2H6, C2H4, C2H2 et CH2O) dans le cas de l’ajout du méthane. A travers ces études, nous avons obtenu une meilleure connaissance de la chimie et de la physique qui ont lieu dans ce type de plasma. / Carbon dioxide appears as one of the most problematic gases for the environment, mostly because it is responsible for global warming. This is why its increasing concentration into the atmosphere, mainly due to anthropogenic activities, is a real concern for planet Earth. In order to prevent the release of large amounts of CO2, its conversion into value-added products is of great interest. In this context, plasma-based treatments using dielectric barrier discharges (DBDs) are nowadays more and more used for the conversion of this gas. In this thesis, we investigated the CO2 splitting process into CO and O2 via a flowing cylindrical DBD and we studied its conversion and energy efficiency by means of several diagnostic methods, such as mass spectrometry to determine the conversion and energy efficiency of the process, optical emission spectroscopy for gas temperature measurements, and an oscilloscope for electrical characterization, in order to obtain a better understanding of the CO2 discharge itself.First, we focused on an extensive experimental study of a pure CO2 plasma where different parameters were varied, such as the gas residence time, the operating frequency, the applied power, the pulsation of the AC signal, the thickness and the nature of the dielectric. CO2 discharges typically exhibit a filamentary behavior, consisting of many microdischarges, which act as the main source of reactivity in a DBD. A detailed insight in the physical aspects was achieved by means of an in-depth electrical characterization, allowing more insight in the electrical properties of the discharge and more specifically in the microdischarges, which are spread out throughout the active zone of the plasma. It was found throughout this work that the plasma voltage, which reflects the electric field and thus determines how the charged particles are accelerated, the plasma current, which reflects the electron density, but also the number of microdischarges and their average lifetime, play an important role in the efficiency of the CO2 dissociation process. It was revealed that the microdischarge number is important as it represents the repartition of the locations of reactivity. Indeed, as the microfilaments are more spread out in the same discharge volume, the probability for the CO2 molecules to pass through the reactor and interact with at least one microdischarge filament becomes more important at a larger number of microfilaments.The second part of the thesis was dedicated to discharges combining CO2 and H2O or CH4, both being hydrogen source molecules. The combined CO2/H2O or CO2/CH4 conversion allows forming value-added products like syngas (CO and H2), but also hydrocarbons (C2H6, C2H4, C2H2 and CH2O), at least in the presence of methane. Throughout this study, we tried to obtain a better knowledge of the chemistry and physic behind these conversion processes. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

In the effort to introduce fuel cell technology in the field of decentralized and mobile power generators, a hydrocarbon reformer to syngas seems to be the way for the market uptake. In this thesis, a potential technology is developed and investigated, in order to convert commercial liquid fuel (diesel, kerosene and biodiesel) to syngas. The fundamental concept is to oxidise the fuel in a oxygen depleted environment, obtaining hydrogen and carbon monoxide as main products of the reaction. In order to extend the flammability limit of hydrocarbon/air mixtures, the rich combustion experiments have been carried out in a two-layer porous medium combustor, which stabilises a flame at the matrix interface and recirculates the enthalpy of the hot products in order to enhance the reaction rates at ultra-rich equivalence ratio. This thesis demonstrates the feasibility of the concept, by exploring characteristic parameters for a compact, reliable and cost effective device. Specifically, a range of equivalence ratios, thermal loads and porous materials have been examined. n-heptane was successfully reformed up to an equivalence ratio of 3, reaching a conversion efficiency (based on the lower heating value of H2 and CO over the fuel input) up to 75% for a packed bed of alumina beads. Thermal loads from P=2 to 12 kW at phi=2.0 demonstrated that heat losses can be reduced to 10%.Similarly, diesel, kerosene and bio-diesel were reformed to syngas in a Zirconia foam burner with conversion efficiency over 60%. The effect of different burners, thermal loads and equivalence ratios have also been assessed for these commercial fuels, leading to equivalent conclusions. A preliminary attempt to reduce the content of CO and hydrocarbons in the reformate has been also performed using commercial steam reforming and water-gas shift reaction catalysts, obtaining encouraging results. Finally, soot emission has been assessed, demonstrating particle formation for all the fuels above phi=2.0, with biodiesel showingthe lowest soot formation tendency among all the fuels tested.

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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.

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