In this dissertation a novel ZLC setup has been developed as part of a DOE-funded grant in collaboration with UOP, to provide rapid screening of novel adsorbent materials for carbon capture (CC). The key features of the new apparatus that was developed are: the use of 5-15 mg of sample and a dual detector system – a thermal conductivity detector (TCD) for single component measurements and a mass spectrometer for studying the influence of water and other impurities. Improvements over previous ZLC apparatuses include: 1. Extension to lower flowrates, i.e. < 3 cc/min, thereby reducing consumption of gases and allowing to run the system under equilibrium control conditions; 2. A new gas dosing system that allows the use of vapours without a chilled bath and bubbler system; 3. A new switching valve system, which prevents leakages; 4. Automated series of experiments, which are implemented using Labview. The new ZLC technique was first applied to provide rapid screening capacity ranking of more than 15 MOF materials from the open literature and three typical zeolites for carbon capture. At the point of interest for flue gas application (38°C, 0.1 bar CO2 partial pressure), Mg/DOBDC was found to outperform significantly all other MOFs and benchmark zeolites at the point of interest in low pressure physisorption of CO2. The ZLC was also used to investigate steaming on Ni/DOBDC as well as see the effect of forming powders into pellets. The new ZLC system also enables one to measure micropore and macropore diffusivity. Experiments were carried out on both powders and pellets of typical MOFs and zeolites. For Co/DOBDC crystals, since the system is close to equilibrium control even at the highest flow rate, a low limit of diffusivity can be estimated. For all the formed samples of Ni/DOBDC and 13X pellets, the results indicate that mass transfer is controlled by macropore diffusion. The ZLC technique can also estimate realistic void fraction and tortuosity values for the pellets. The new ZLC technique was applied to study the stability on the MOF M/DOBDC series. The preliminary water tests showed that all M/DOBDC samples are highly hydrophilic. Therefore in a process design using these MOFs, we conclude that there is a needs to use a guard bed layer to adsorb water or use a gas drying unit before the CO2 capture section of the plant. The ZLC system appears to be extremely useful to accelerate the deactivation of samples due to SOX and NOX impurities. The key advantages are based on the fact that the treatment can be repeated in situ, in a relatively simple way using a very small sample. The results show that in the presence of impurities and water the candidate MOFs undergo significant deactivation. The Ni based material shows the best resistance to degradation. This result indicates further that there would be a need for a drying unit prior to the carbon capture adsorption process.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / A profunda compreensÃo dos mecanismos difusivos em sÃlidos porosos à essencial para o desenvolvimento de vÃrios processos envolvendo catÃlise heterogÃnea. A impregnaÃÃo de metais em suporte poroso Ã, geralmente, uma forma eficaz de aumentar a eficiÃncia do catalisador. No entanto, os efeitos de tal procedimento sobre as propriedades de transporte ainda sÃo pouco conhecidos. ZeÃlitas, sÃlicas e aluminas sÃo os suportes mais frequentemente utilizados para catalisadores heterogÃneos. Atualmente, utilizam-se tambÃm carbonos ativados (AC) como suportes, porÃm, apesar das vÃrias vantagens potenciais (por exemplo, Ãreas de superfÃcie bastante especÃficas), pouco tem sido estudado em relaÃÃo ao comportamento difusivo nestes materiais. A SÃntese de Fischer-Tropsch (FTS) à um processo que pode ser beneficiado com a utilizaÃÃo de materiais à base de carbono impregnados. Dessa forma, o mÃtodo Zero Length Column (ZLC) foi aplicado neste estudo para avaliar a difusÃo de n-heptano e n-octano, produtos relevantes do FTS, em materiais à base de carbono antes e apÃs a impregnaÃÃo com Fe com o objetivo de investigar a cinÃtica sob as condiÃÃes normais de temperatura de FTS e determinar se os produtos do processo apresentam uma resistÃncia significativa para o processo. / A deep understanding of the diffusion mechanisms in porous solids is essential to the development of many processes involving heterogeneous catalysis. The impregnation of metals on porous supports is generally an effective way of increasing the catalyst efficiency, but the effects of such procedure on the transport properties are poorly known. Zeolite, silica and alumina are most frequently used as supports for heterogeneous catalysts. Despite the several potential advantages of using activated carbon (AC) as supports (e.g. high specific surface areas), little has been studied regarding diffusion behavior in these materials. The Fischer-Tropsch Synthesis (FTS) is a process which could benefit from the use of carbon-based impregnated materials. The Zero Length Column (ZLC) method was applied in this study to evaluate the diffusion of n-heptane and n-octane, relevant products of the FTS, in carbon-based materials before and after impregnation with Fe. The aim was to investigate the kinetics under the usual temperature conditions of the FTS and determine if the products diffusion poses a significant resistance for the process.

In this work the experimental results from the rapid screening and ranking of a wide range of novel adsorbents for carbon capture are presented. The samples were tested using the Zero Length Column (ZLC) method which has proved to be an essential tool for the rapid investigation of the equilibrium and kinetic properties of prototype adsorbents. The study was performed on different classes of nanoporous materials developed as part of the EPSRC-funded “Innovative Gas Separations for Carbon Capture” (IGSCC) project. More than 120 novel adsorbents with different key features for post-combustion carbon capture were tested. The classes of materials investigated were: • PIMs (Polymers of Intrinsic Microporosity) • MOFs (Metal - Organic Frameworks) • Mesoporous Silica • Zeolites • Carbons All the samples were tested at experimental conditions close to the ones of a typical flue gas of a fossil fuel power plant: 35 ºC and 0.1 bar of partial pressure of CO2. The results from the ranking of the CO2 capacity of the materials, at the conditions of interest, indicate the Mg and Ni-based MOF samples as the adsorbents with the highest uptake among all the candidates. The best sample shows a CO2 capacity almost double than the benchmark adsorbent, zeolite 13X (provided by UOP). The ranking also shows some of the zeolite adsorbents synthesised as promising materials for carbon capture: uptakes comparable or slightly higher than 13X were obtained for several samples of Rho and Chabazite zeolite. Water stability tests were also performed on the best MOFs and showed a deactivation rate considerably faster for the Mg-based MOFs, proving an expected higher resistance to degradation for the Ni based materials. A focused investigation was also carried out on the diffusion of CO2 in different ionexchanged zeolites Rho samples. The study of these samples, characterised by extremely slow kinetics, extended the use of the ZLC method to very slow diffusional time constants which are very difficult to extract from the traditional long time asymptotic analysis. The results show how the combination of the full saturation and partial loading experiment can provide un-ambiguous diffusional time constants. The diffusivity of CO2 in zeolite Rho samples shows to be strongly influenced by the framework structure as well as the nature and the position of the different cations in the framework. The kinetics of the Na-Cs Rho sample was also measured by the use of the Quantachrome Autosorb-iQ™ volumetric system. To correctly interpret the dynamic response of the instrument modifications were applied to the theoretical model developed by Brandani in 1998 for the analysis of the piezometric method. The analytical solution of the model introduces parameters which allow to account for the real experimental conditions. The results confirm the validity of the methodology in the analysis of slow diffusion processes. In conclusion the advantages offered by the small size of the column and the small amount of sample required proved the ZLC method to be a very useful tool for the rapid ranking of the CO2 capacity of prototype adsorbents. Equilibrium and kinetic measurements were performed on a very wide range of novel nanoporous materials. The most promising and interesting samples were further investigated through the use of the water stability test, the partial loading experiment and the volumetric system. The ZLC technique was also extended to the measurements of systems with very slow kinetics, for which is very difficult to extract reliable diffusional time constants. An improved model for the interpretation of dynamic response curves from a non-ideal piezometric system was developed.

nÃo hà / O presente trabalho tem como principal objetivo investigar as condiÃÃes mais adequadas para o estudo da difusividade de n-parafinas em um catalisador tÃpico para a sÃntese de Fischer-Tropsch (SFT), utilizando o mÃtodo cromatogrÃfico ZLC (coluna de comprimento zero), e avaliando-se a repetitividade e a reprodutibilidade desta metodologia. Objetiva, ainda, verificar o desempenho do catalisador em um reator de leito fixo, em escala piloto, e observar o efeito da difusÃo na seletividade a hidrocarbonetos de alta massa molar. O catalisador foi caracterizado, com Ãnfase nos ensaios de microscopia e anÃlise textural. Quanto à difusividade dos n-alcanos (n-C7, n-C9, n-C12, n-C16), foram utilizados dois sistemas ZLC, sendo um na Universidade Federal do Cearà (UFC) e o outro na Universidade de Edimburgo, empregando-se amostras de diferentes granulometrias (forma pà e pellet). Investigou-se, tambÃm, a influÃncia da temperatura, da vazÃo do gÃs de purga, da massa de catalisador e da concentraÃÃo do sorbato no gÃs de purga. Quanto à etapa reacional, esta ocorreu em uma unidade piloto para a SFT a 20 bar, nas temperaturas de 210 ÂC e 230 ÂC e em diferentes velocidades espaciais. O catalisador apresentou-se como mesoporoso, com um pouco de microporosidade, e com a fase ativa (Co) bem distribuÃda. Em relaÃÃo à difusividade efetiva, o diÃmetro de partÃcula mais adequado para o uso na coluna ZLC, dentre os testados, foi de 214 Âm para o catalisador na forma pÃ, com 5 mg de amostra. Comparando-se os experimentos realizados nas duas universidades, percebeu-se uma boa repetitividade, porÃm a reprodutibilidade, nÃo foi satisfatÃria. Observou-se ainda, a influÃncia da constante de Henry nos resultados obtidos para difusividade efetiva, em diferentes tamanhos de catalisador, entretanto, nÃo se perceberam mudanÃas significativas na difusividade efetiva em funÃÃo da variaÃÃo da temperatura e da concentraÃÃo de sorbato no gÃs de purga. Em se tratando da reaÃÃo, os resultados indicaram um forte efeito da temperatura na conversÃo de CO e na seletividade a C5+. O mecanismo difusivo à afetado pela difusividade de superfÃcie, e, a partir deste resultado, pode-se justificar o aumento da seletividade a metano com o incremento da relaÃÃo H2/CO. Com base nos resultados apresentados, o mÃtodo ZLC mostrou-se adequado para o estudo da difusividade efetiva de n-parafinas em um catalisador convencional para a SFT. / The main goal of the present research is to establish the most appropriate conditions for studying the diffusivity of n-paraffins in the presence of a typical catalyst for Fischer-Tropsch synthesis (FTS), by using the chromatographic method ZLC (zero length column) and evaluating the repeatability and reproducibility of this method. It also aims to verify the catalyst performance in a fixed bed reactor, at a pilot-scale, and observe the effect of diffusion in the selectivity of high molar mass hydrocarbons. At first, the catalyst characterization was done with emphasis on the microscopy studies and textural analysis with N2. Regarding the n-alkanes diffusivity (n-C7, n-C9, n-C12, n-C16), two ZLC equipments were used, one at the Federal University of Ceara (UFC) and the another one at the University of Edinburgh, with different particle size samples. This work has also evaluated the influence of temperature, the purge gas flow rate, the catalyst mass and sorbate concentration in the purge gas. The reaction step was done at a Fisher-Tropsch pilot-scale unit at 20 bar, with 210ÂC and 230ÂC in different space velocities. As a result, the catalyst was presented as mesoporous, with small microporosity, and with active phase (Co) well distributed. Concerning the effective diffusivity, the most appropriate particle diameter to be used at the ZLC column, among the tested diameters, is 214 Âm (dust form), with 5 mg of catalyst. Comparing the studies that were held at the two universities, it was noticed a good repeatability, however, the reproducibility was not satisfactory. It was observed a strong influence of the HenryÂs constant at the results of effective diffusivity, for different catalyst sizes; however, no significant changes at the effective diffusivity were noted due to temperature variation and sorbate concentration. Regarding the reaction, the results indicated a strong effect of temperature at the CO conversion and at the C5+ selectivity. The diffusive mechanism is strongly affected by the catalyst surface effects. Based on this result, the raise of methane selectivity by increasing H2/CO ratio can explained. As final result, the ZLC is found as a suitable method for surface diffusion estimation using typical Fischer-Tropsch catalyst.

De par leur morphologie, les cristaux creux de zéolithe permettent d’étudier les phénomènes de limitations diffusionnelles en catalyse et également d’encapsuler des particules métalliques ; les nano-réacteurs ainsi obtenus ont montré des activités catalytiques originales. Leur synthèse, qui nécessite des caractéristiques structurales particulières, a longtemps été limitée aux zéolithes de structure MFI. Le but de cette thèse était d’étudier différentes voies de synthèse pour préparer des cristaux creux de zéolithe Beta, une des zéolithes les plus utilisées dans l’industrie. Deux voies ont été suivies : l’utilisation d’un zincosilicate de même structure que la zéolithe Beta comme gabarit sacrificiel et une méthode plus classique de désilication sélective. L’encapsulation de nanoparticules de platine dans les cristaux obtenus selon la première voie a été confirmée par l’hydrogénation d’aromatiques substitués. L’’influence de la morphologie sur la diffusion de différentes molécules a été étudiée par ZLC : le temps caractéristique de diffusion a été réduit de 30 à 83 % par rapport à des cristaux conventionnels. Malgré cela, la présence d’une cavité dans les cristaux de zéolithe Beta n’a pas d’effets sur l’activité catalytique dans les réactions d’hydro-isomérisation du nC16 et du craquage du cyclohexane. La thèse discute de la présence/absence de limitations diffusionnelles / Hollow zeolite single crystals have received particular interest in catalysis. The presence of a large cavity in these model zeolites enables the study of diffusional limitation in Catalysis. The cavity also enables the encapsulation of metal nanoparticles. However, their synthesis requires specific structural characteristics and it has been limited for long to zeolites with the MFI structure. The objective of this PhD work was to investigate the synthesis of hollow Beta zeolites (*BEA framework type) and study the impact of the hollow morphology on molecular diffusion and catalysis. Two different strategies have been envisaged: a dissolution/recrystallization approach using CIT-6, a zincosilicate with the same *BEA topology and a selective desilication route. Pt nanoparticles encapsulated in hollow crystals obtained from CIT-6 showed remarkable size-selectivity in the hydrogenation of aromatics. The effect of the hollow morphology in molecular diffusion was studied using the ZLC technique; the characteristic diffusion time of the hollow morphology was reduced by 30-83% compared to the corresponding bulk zeolite. Despite that, the hollow structure had no influence on the catalytic activities for the hydroisomerization of n-C16 and for the cracking of cyclohexane. The presence/absence of diffusional limitation is discussed