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Hydrodesulfurization and Hydrodenitrogenation of Model Compounds Using in-situ Hydrogen over Nano-Dispersed Mo Sulfide Based CatalystsLiu, Kun 06 November 2014 (has links)
Heavy oil derived from oil sands is becoming an important resource of energy and transportation fuels due to the depletion of conventional oil resources. However, bitumen and heavy oils have a low hydrogen/carbon ratio and contain a large percentage of sulfur and nitrogen heterocyclic compounds. At the level of deep desulfurization, aromatic poly-nuclear molecules, especially nitrogen-containing heterocyclic compounds, exhibit strong inhibitive effect on hydrodesulfurization (HDS) due to competitive adsorption on catalytically active sites with sulfur-containing molecules. Therefore, it is necessary to study the HDS of refractory sulfur-containing compounds and also the effect of nitrogen-containing species on the deep HDS for achieving the ultra low sulfur specifications for transportation fuels. Additionally, the cost of H2 increased in recent years and a bitumen emulsion upgrading technique using an alternative in-situ H2 generated via the water gas shift (WGS) reaction during the hydro-treating was developed in our group. In the present study, a kind of nano-dispersed unsupported MoSx based catalyst was developed and used for hydrodesulfurization, hydrodenitrogenation (HDN) and upgrading bitumen emulsions.
Objectives of this thesis were to (1) improve the catalytic activity of the nano-dispersed Mo based catalysts towards the HDS and HDN reactions of refractory sulfur-/nitrogen-containing compounds; and (2) compare the reactivity of in-situ hydrogen generated via the WGS reaction versus externally provided molecular hydrogen in HDS and HDN reactions to improve the efficiency of the bitumen emulsion upgrading technology developed by our group.
In the present study, to stimulate the reaction system of bitumen emulsion, water was added into the organic reaction system, so there are different phases in this reaction system. To investigate the activity of the catalyst, the catalyst particles dispersed in different phases were characterized separatedly via HRTEM-EDX. After HRTEM-EDX study, all phases were mixed up and dried for further characterizations, BET, SEM, and XRD. The catalyst prepared in in-situ hydrogen was found to have higher surface area and smaller particle size than the one made in molecular hydrogen. The presence of sulfur-/nitrogen-containing compounds in the preparation system caused significant changes in the morphology of dispersed Mo sulfide catalyst according to HRTEM observations.
Refractory sulfur-containing compounds of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) were used as model compounds in HDS studies. The simultaneous HDS of both model compounds was performed at different reaction temperatures from 330??C to 400??C. The effect of the reaction temperature on the WGS reaction in the presence of sulfur-containing model compounds was reported. A kinetic model for HDS reactions was proposed and used in discussing experiment results. The relative HDS reactivity of 4,6-DMDBT to DBT using dispersed Mo sulfide catalyst in in-situ hydrogen was found to be higher than the reported results which were obtained over supported catalysts. Nickel and potassium were introduced into Mo sulfide catalysts as promoters and their effect on the WGS reaction and the HDS reaction were discussed.
The simultaneous HDS was carried out in the two different hydrogen sources. The in-situ hydrogen reaction system showed higher conversion and desulfurization results of both sulfur model compounds. This observation has been found to be mainly contributed by the higher activity of the Mo sulfide catalyst prepared in in-situ H2.
Strong inhibitive effect of nitrogen-containing compounds, basic quinoline or non-basic carbazole, on the HDS of refractory sulfur model compounds was observed and discussed. Basic quinoline was a much stronger inhibitor than non-basic carbazole. The two HDS reaction pathways were affected by nitrogen-containing compounds to different extents.
The HDN of quinoline over the dispersed Mo sulfide catalyst using in-situ hydrogen had been studied extensively by a previous member in our group. In this thesis, the HDN of carbazole was studied. From the identification of HDN products of carbazole, a HDN reaction network was proposed. The HDN of carbazole was processed at different reaction temperatures. The WGS reaction was not inhibited in the presence of carbazole. Comparable reactivity of the two hydrogen sources towards the HDN of carbazole was observed. The presence of 4,6-DMDBT caused significant effect on the HDN of carbazole due to the competitive adsorption on the catalyst surface.
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Hydroconversion des résidus pétroliers par des catalyseurs dispersés / Hydroconversion of petroleum residues with dispersed catalystsJansen, Tim 21 October 2014 (has links)
Face à l'épuisement des pétroles bruts légers et à la demande en énergies fossiles toujours croissante, l'exploitation des pétroles lourds et le raffinage des résidus pétroliers devient une nécessité. Cependant, la nature de ces résidus pose de nombreuses difficultés aux procédés de raffinage existants. En conséquence, l'industrie pétrolière a actuellement un fort intérêt au développement d'un procédé de conversion profonde de ces résidus pétroliers en carburants valorisables. L'utilisation d'un catalyseur hautement dispersé dans la charge permettrait de minimiser ces difficultés. L'objectif de cette thèse est alors l'étude de quelques aspects du développement d'un procédé d'hydroconversion des résidus pétroliers avec des catalyseurs dispersés. La première partie est dédiée à la génération des données expérimentales de la conversion d'un résidu dans un micro-pilote continu en faisant varier les conditions opératoires. Ensuite, un modèle de cette unité a été développé en couplant la description des cinétiques chimiques déterminée dans un autre réacteur (dans une étude préalable), avec les modèles physiques (hydrodynamique et transfert de matière) et thermodynamiques. Le modèle a été validé en comparant les prédictions du modèle avec les résultats expérimentaux obtenus. La minimisation de la consommation de catalyseur et l'augmentation du rendement en produits désirables sont deux objectifs dans le développement d'un procédé industriel. Le recyclage du catalyseur et de la fraction non-convertie est une stratégie permettant d'atteindre ces objectifs. L'outil expérimental utilisé pour l'étude du fonctionnement en mode recyclage était un réacteur semi-continu. La caractérisation des produits issus d'expériences de la conversion avec un catalyseur recyclé est accompagnée d'une caractérisation de la phase active. De plus, l'étude de l'évolution de la réactivité de la charge recyclée fait partie de cette étude. Les résultats obtenus permettent d'évaluer la faisabilité du fonctionnement en recyclage / With the depletion of light petroleum crude oils and the demand in fossil energies still growing, the exploration of heavy oils and the refining of petroleum residues becomes a necessity. However, the nature of these feedstocks presents numerous difficulties for the existing refining processes. As a consequence, the petroleum industry is currently developing new processes for the deep conversion of these residues to more valuable fuels. The utilization of dispersed catalysts is a promising new strategy for minimizing these difficulties. The aim of this work was to study several aspects of the scale-up of a hydroconversion process of petroleum residues with dispersed catalysts. The first part of this work is dedicated to the generation of experimental data for the conversion of a residue in a continuous micro-pilot unit by varying the operating conditions. Afterwards, a model of the unit was developed by coupling the chemical kinetics determined in a previous batch reactor study with the physical characterization (hydrodynamics and mass transfer) of the continuous micro-pilot unit. The model was validated by comparing its predictions with the experimental data. Minimization of catalyst consummation and the increasing product yields are vital in the development of an industrial process. Recycling the non-converted fraction as well as the catalyst is is a strategy to achieve these two objectives. The second part was thus dedicated to the study of the recycling mode, which was carried out in a semi-continuous reactor. The product characterization of catalyst recycling experiments was accompanied with the characterization of the active phase to evaluate the performance of an aging catalyst. Additionally, the evolution of the reactivity of the recycled product was studied. The results obtained allow us to evaluate the feasibility of the recycling mode
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