Monte Carlo based methods applied to heterogeneous catalysis and gas separation
The research work presented in this thesis is divided in two main topics: gas separation and heterogeneous catalysis. Although the systems studied in one part and another are quite different, they share two fundamental features: both topics have a special industrial interest and they have been studi...
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| Tipo de recurso: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2019 |
| País: | España |
| Institución: | CBUC, CESCA |
| Repositorio: | TDR. Tesis Doctorales en Red |
| OAI Identifier: | oai:www.tdx.cat:10803/666583 |
| Acceso en línea: | http://hdl.handle.net/10803/666583 |
| Access Level: | acceso abierto |
| Palabra clave: | Gasos Gases Separació (Tecnologia) Separación (Tecnología) Separation (Technology) Catàlisi heterogènia Catálisis heterogénea Heterogeneus catalysis Zeolites Zeolitas Mètode de Montecarlo Método de Montecarlo Monte Carlo method Ciències Experimentals i Matemàtiques 54 |
| Sumario: | The research work presented in this thesis is divided in two main topics: gas separation and heterogeneous catalysis. Although the systems studied in one part and another are quite different, they share two fundamental features: both topics have a special industrial interest and they have been studied through stochastic Monte Carlo based methods. The present work on gas separation aims to assess the performance of several faujasite structures, a well-known family of zeolites, in CO2 capture processes. Concretely, ten faujasite structures with different Al content have been evaluated in the separation of post-combustion CO2 mixtures via simulation of swing adsorption processes. Through GCMC simulations performed on a wide range of pressures and temperatures, the pure and mixture adsorption isotherms and isobars for the different structures are obtained. This data is used to calculate several performance criteria such as purity, working capacity, selectivity and energy required per ton of CO2 captured. The results show that high Al content structures are suitable for operating under a TSA unit, while intermediate and low Al content structures show better performance in PSA and VSA units, respectively. On the other hand, the research work on chemical reactivity focus on the study of the water-gas shift reaction (WGSR) on copper surfaces both from a thermodynamic and from a kinetic point of view. First, a kMC study is performed on the flat Cu(111) surface. The lattice model is quite simple, consisting on an hexagonal periodic grid of points. All sites are considered equivalent, and only repulsive lateral interactions between neighboring CO adsorbed species are included. However, even with this simple model, the kMC results agree quite well to the available experimental data, and demonstrate that the dominant reaction mechanism is the COOH mediated associative mechanism. The effect of van der Waals interactions is then studied, by performing DFT calculations of the WGSR on Cu(321) using the Grimme D2 correction accounting for the dispersion forces. The results obtained are compared with previous DFT results published in the literature where no van der Waals corrections were included. The comparison shows big differences on the adsorption energies of some gas species, as well as important differences in some energy barriers, hence demonstrating the importance of including dispersion terms in order to obtain a meaningful description of the energetics of the WGSR. New kMC simulations are then performed for the WGSR on Cu(321) surface to study the effect of step sites on the WGSR activity. The recently developed graph- theoretical kMC framework is used, coupled with cluster expansion Hamiltonians to account for the lateral interactions between neighboring species. The simulation results show that the activity is much lower on the stepped Cu(321) surface. Analysis of the kMC simulations suggests that the reason in the poisoning of step sites by CO species, as well as the presence of low energy barriers for some key steps on the reverse direction (e.g. water dissociation and COOH formation). Finally, the thesis ends with a brief tutorial on kMC simulations where several issues are discussed, like the importance of including diffusion processes of the effect of lateral interactions. |
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