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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Síntese e caracterização de catalisadores de Co-Mo e Ni-Mo para hidrodessulfurização suportados em sílica mesoporosa ordenada (SBA-15 e FDU-1) / Synthesis and characterization of Co-Mo and Ni-Mo catalysts supported on ordered mesoporous silica (SBA-15 and FDU-1) for hydrodessulfurization

Oliveira, Nara Andréa de 26 September 2013 (has links)
Este trabalho teve como objetivo a síntese e caracterização de catalisadores de Co-Mo e Ni-Mo para hidrodessulfurização suportados em sílica mesoporosa ordenada (SBA-15 e FDU-1). As amostras de SBA-15 and FDU-1 foram sintetizadas a partir de TEOS como fonte de sílica e copolímeros triblocos como agentes direcionadores de estrutura em meio ácido. Ni(NO3)2.6H2O, Co(NO3)2.6H2O, (NH4)6Mo7O24.4H2O foram utilizados como fontes de metais. A suspensão aquosa de sílica foi misturada com a solução do cátion metálico conforme a concentração desejada. Após evaporação da água o molde polimérico foi eliminado por calcinação sob atmosferas dinâmicas de N2/ar, produzindo os precursores na forma de óxidos. As técnicas de TG/DTG, DRX, MEV-EDS, ICP OES, isotermas de adsorção/dessorção de N2 e SAXRD foram empregadas para a caracterização destes materiais. A TG foi utilizada para verificar a composição dos sais de partida, para definir as melhores condições de calcinação e definir a estequiometria do produto final. Os resultados de DRX confirmaram as fases óxidos após a calcinação dos sais e dos catalisadores. Os resultados de SAXRD indicaram picos bem resolvidos e ótima estruturação para os catalisadores suportados em SBA-15. Entretanto, os catalisadores suportados em FDU-1 não apresentaram picos de difração bem definidos, mas apenas bandas de correlação que indicaram a formação de domínios de poros desordenados e domínios pouco ordenados. As isotermas de adsorção de N2 foram concordantes com a literatura para as amostras de SBA-15 puras e modificadas. Porém, as amostras de FDU-1 pura e modificadas apresentaram deformidades nos ramos das isotermas de dessorção. Os teores metálicos foram determinados por espectrometria de emissão atômica com fonte de plasma. Os valores de áreas superficiais foram superiores a 450 m2/g para os catalisadores suportados em SBA-15 e superiores a 290 m2/g para os catalisadores suportados em FDU-1, sugerindo que esses materiais são promissores para prosseguir com os estudos e efetivamente testá-los para hidrodessulfurização. / This work aimed at the synthesis and characterization of Co-Mo and Ni-Mo catalysts supported on ordered mesoporous silica (SBA-15 and FDU-1) for hydrodesulfurization. SBA-15 and FDU-1 samples were synthesized from TEOS as silica source and triblock copolymers as structure templating agents in acidic medium. Ni(NO3)2.6H2O, Co(NO3)2.6H2O, (NH4)6Mo7O24.4H2O were used as metal sources. The aqueous suspension of silica was mixed with the metallic cation solution according to desired concentration. After evaporation of water the polymeric template was removed by calcination under dynamic atmospheres of N2/air producing precursors in the oxide form. The TG/DTG, XRD, SEM-EDS, ICP OES, isotherm adsorption/desorption of N2 and SAXRD techniques were employed to characterize these materials. The TG was used to verify the composition of the starting salts, to define the best conditions of calcination and define the final product stoichiometry. The XRD results confirmed the oxide phase after calcination of salts and catalysts. The SAXRD results indicated well resolved peaks and great structure for catalysts supported on SBA-15. However, the catalysts supported on FDU-1 showed no well-defined diffraction peaks but only correlation bands which indicated the formation of areas of somewhat ordered pores and disordered domains. The nitrogen adsorption isotherms were according to literature for SBA-15 pure and modified samples but FDU-1 pure and modified samples presented deformed branches of desorption isotherms. The metallic contents were determined by emission spectrometry atomic plasma source. The values for surface areas were greater than 450m2/g for the catalysts supported on SBA-15 and larger than 290 m2/g for the catalysts supported on FDU-1, suggesting that these materials are promising for further studies and test them in the hydrodesulfurization reactions.
12

Régénération et réactivation de catalyseurs d'hydrotraitement : vers la compréhension des paramètres de réjuvenation / Regeneration and reactivation of hydrotreatment catalysts : towards understanding the parameters of rejuvenation

Pedraza Parra, Camila- Andrea 13 December 2018 (has links)
La régénération et la réactivation des catalyseurs industriels d'hydrodésulfuration (HDS) CoMo/Al2O3 usés permettent leur réutilisation. Étant donné que ces catalyseurs sont considérés comme toxiques et polluants, la régénération/réactivation est une procédure intéressante dans un cadre écologique et économique. La régénération permet d'éliminer les dépôts de carbone mais ne permet pas de restaurer complètement l'activité des catalyseurs de HDS des nouvelles générations. En conséquence, une deuxième étape appelée « réjuvenation », impliquant l’ajout de composés organiques, a été mise en œuvre. L’étude de l’impact des additifs est d’un grand intérêt mais de nombreuses observations restent inexpliquées. En outre, certains brevets ont décrit une procédure de pré-activation permettant d'activer des catalyseurs ex situ afin d'éviter le contact avec des composés soufrés, ainsi que de manipuler et de charger en toute sécurité les catalyseurs dans des unités de HDS. De plus, il est de notoriété publique que la sulfuration est une étape critique ayant un impact important sur les performances catalytiques. En ce sens, cette étude vise à étudier l’effet de différentes conditions de rajeunissement, de pré-activation et de sulfuration ultérieure sur les caractéristiques finales des catalyseurs. Dans ce travail, trois catalyseurs régénérés et pré-activés ont été étudiés après différents protocoles de sulfuration. Les catalyseurs ont été testés et comparés dans la HDS de thiophène et SRGO. Aussi, l’influence des composés organiques ajoutés lors de la réjuvenation a été étudiée par différentes techniques (XPS, CO / IR, TEM…). Les résultats ont permis de déterminer les différences d'activité catalytique et d'établir une corrélation entre l'activité en HDS du thiophène et la concentration de sites CoMoS. Aucune divergence morphologique n'a été détectée dans les systèmes et les différences de performances catalytiques sont attribuées à un degré de promotion inégal. / Regeneration and reactivation of used industrial CoMo/Al2O3 hydrodesulfurization (HDS) catalysts allows reusing them. Since these catalysts are considered toxic and pollutant, regeneration/reactivation is an interesting procedure from an economical and ecological point of view. The regeneration allows removing carbon deposits but, by itself, does not restore completely the activity of new generations of HDS catalysts. Consequently, a second stage named rejuvenation, involving addition of organic compounds has been implemented. The study of the impact of additives is of great interest but many observations remain unexplained. Furthermore, some patents have described a pre-activation procedure that allows activating catalysts ex situ in order to avoid contact with sulfur compounds and a safe handling and loading of the catalysts in HDS units. In addition, it is common knowledge that sulfidation is a critical stage that impacts strongly the catalytic performance. In this sense, this study aims to study the effect of different rejuvenation, pre-activation and subsequent sulfidation conditions on final characteristics of catalysts. In this work three rejuvenated and pre-activated catalysts were studied after different sulfidation protocols. Catalysts were tested and compared in thiophene and SRGO HDS. Additionally, the influence of the organic compounds added during rejuvenation was studied by different techniques (XPS, CO/IR, TEM…). Results allowed determining differences in catalytic activity and establishing a correlation between thiophene HDS activity and CoMoS concentration. No morphological divergences were detected in the systems, instead, differences in catalytic performances are attributed to an unequal promotion degree
13

Efeitos da substituição de átomos de molibdênio em catalisadores empregados nos processos de hidrodessulfurização

Martins, Claudinei January 2014 (has links)
Orientadora: Profa. Dra. Paula Homem de Mello / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Ciência & Tecnologia - Química, 2014. / Métodos computacionais foram empregados para avaliar os efeitos da substituição de átomos de molibdênio por cobalto, ou níquel, em catalisadores de sulfeto de molibdênio, utilizados nos processos de hidrodessulfurização. O estudo foi feito utilizando duas diferentes abordagens. O método de Monte Carlo para determinar as estrutura mais prováveis envolvidas no processo de adsorção de tiofeno e sulfeto de dimetila, enquanto métodos baseados na teoria do funcional da densidade foram utilizados para otimizar as estruturas obtidas por Monte Carlo e determinar as energias de adsorção. A validação dos clusters utilizados foi feita pela avaliação das distâncias das ligações entre os átomos, principalmente dos átomos localizados nas bordas e encontrado como cluster mínimo a ser utilizado nas simulações o Mo16S32. Foi, em seguida, estudada a adsorção de tiofeno, e a possibilidade de transferência de carga foi avaliada a partir das cargas atômicas, juntamente com os orbitais HOMO-LUMO. Essas propriedades permitiram mostrar que a substituição de átomos de molibdênio por átomos de cobalto, resultam em maior transferência de carga do adsorbato ocorrendo ampliação dos sítios ácidos. / Computational methods were used to evaluate the effect of substitution of atoms of molybdenum by cobalt or nickel in the molybdenum sulfide catalyst used in hydrodesulfurization process. The study was conducted using two different approaches. Monte Carlo method was employed to determine the most probable structures involved in the thiophene and dimethyl sulfide adsorption process. Density functional theory-based methods were used to optimize the structures obtained by Monte Carlo and determine the adsorption energies. Validation of clusters employed in this study was performed by evaluating the bond distances between atoms, particularly atoms from the edges. The results presented herein demonstrate that Mo16S32 cluster can be used to represent the catalyst. Atomic charges analysis and frontier molecular orbitals were employed to evaluate the acidity of the different sites. These properties showed also that the replacement of molibidenium atoms by cobalt atoms results in increasing charge transfer and promotes new acidic sites.
14

Hydrodesulfurization and Hydrodenitrogenation of Model Compounds Using in-situ Hydrogen over Nano-Dispersed Mo Sulfide Based Catalysts

Liu, 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.
15

Supercritical fluids synthesis, characterization and test of HDS catalysts : Assessment of criticality of metals contained in HDS catalysts / Synthèse en milieux supercritiques, caractérisation et tests de catalyseurs d´hydrodésulfuration (HDS) : Evaluation de la criticité des éléments contenus dans les catalyseurs HDS

Quilfen, Cyril 15 December 2016 (has links)
Dans un contexte environnemental où les législations concernant la teneur ensoufre présent dans les coupes pétrolières sont de plus en plus drastiques, le développementde nouveaux catalyseurs toujours plus actifs est donc nécessaire. Cette augmentation del´activité catalytique est possible à plusieurs niveaux dont, par exemple, par l´utilisation denouveaux procédés de synthèse tel que l´emploi de la voie fluides supercritiques. Dans unpremier temps, l´objectif est d´étudier les éléments utilisés pour préparer ces catalyseurs afind´avoir une vision plus large des réserves, des utilisations, des possibilités de substitutions…La criticité de ces éléments a donc été évaluée par le biais de plusieurs indicateurs. Dans unsecond temps, la compréhension de la synthèse de catalyseurs d´hydrodésulfuration (HDS) aété étudiée. Pour cela des expériences utilisant différents solvants et précurseurs métalliquesont été suivies via des analyses in situ Raman. Après avoir défini les résultats les plusprobants, le procédé de préparation de catalyseurs HDS assisté par le CO2 supercritique(scCO2) a été optimisé à travers une étude paramétrique. Pour cela, la température, lapression, le solvant d´imprégnation, le ratio entre CO2 et solvant d´imprégnation, le temps deréaction et le chargement en métaux ont été variés. Les matériaux obtenus ont ensuite étéfinement caractérisés (microscopie, DRX, Raman, ICP, microsonde) avant d´être activés parsulfuration et testés dans différentes réactions catalytiques (hydrogénation du toluène,hydrodésulfuration du dibenzothiophène et du 4,6-diméthyldibenzothiophène). / In an environmental context where legislations concerning the sulfur content in oilare increasingly drastic, the research for new and ever more active catalysts is necessary. Thisincrease of the catalytic activity is possible at several levels, for example, with the use of novelsynthetic processes such as the use of the supercritical fluids route. In a first stage, theobjective is to study the elements used to prepare these catalysts in order to have a broaderview of the reserves, the uses, the possibility of substitutions ... The criticality of these elementshas therefore been evaluated by means of several indicators. In a second stage, theunderstanding of the synthesis of hydrodesulfurization catalysts (HDS) was studied. For thispurpose, experiments using different solvents and metallic precursors were followed by in situRaman analyses. After defining the most convincing results, the process for preparing HDScatalysts assisted by supercritical CO2 medium (scCO2) was optimized through a parametricstudy. For this, temperature, pressure, impregnation solvent, ratio of CO2 to impregnationsolvent, reaction time and metal loading were varied. The materials obtained were thencharacterized (microscopy, DRX, Raman, ICP, microprobe) before being activated bysulfidation and tested in various catalytic reactions (hydrogenation of toluene,hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene).
16

Síntese e caracterização de catalisadores de Co-Mo e Ni-Mo para hidrodessulfurização suportados em sílica mesoporosa ordenada (SBA-15 e FDU-1) / Synthesis and characterization of Co-Mo and Ni-Mo catalysts supported on ordered mesoporous silica (SBA-15 and FDU-1) for hydrodessulfurization

Nara Andréa de Oliveira 26 September 2013 (has links)
Este trabalho teve como objetivo a síntese e caracterização de catalisadores de Co-Mo e Ni-Mo para hidrodessulfurização suportados em sílica mesoporosa ordenada (SBA-15 e FDU-1). As amostras de SBA-15 and FDU-1 foram sintetizadas a partir de TEOS como fonte de sílica e copolímeros triblocos como agentes direcionadores de estrutura em meio ácido. Ni(NO3)2.6H2O, Co(NO3)2.6H2O, (NH4)6Mo7O24.4H2O foram utilizados como fontes de metais. A suspensão aquosa de sílica foi misturada com a solução do cátion metálico conforme a concentração desejada. Após evaporação da água o molde polimérico foi eliminado por calcinação sob atmosferas dinâmicas de N2/ar, produzindo os precursores na forma de óxidos. As técnicas de TG/DTG, DRX, MEV-EDS, ICP OES, isotermas de adsorção/dessorção de N2 e SAXRD foram empregadas para a caracterização destes materiais. A TG foi utilizada para verificar a composição dos sais de partida, para definir as melhores condições de calcinação e definir a estequiometria do produto final. Os resultados de DRX confirmaram as fases óxidos após a calcinação dos sais e dos catalisadores. Os resultados de SAXRD indicaram picos bem resolvidos e ótima estruturação para os catalisadores suportados em SBA-15. Entretanto, os catalisadores suportados em FDU-1 não apresentaram picos de difração bem definidos, mas apenas bandas de correlação que indicaram a formação de domínios de poros desordenados e domínios pouco ordenados. As isotermas de adsorção de N2 foram concordantes com a literatura para as amostras de SBA-15 puras e modificadas. Porém, as amostras de FDU-1 pura e modificadas apresentaram deformidades nos ramos das isotermas de dessorção. Os teores metálicos foram determinados por espectrometria de emissão atômica com fonte de plasma. Os valores de áreas superficiais foram superiores a 450 m2/g para os catalisadores suportados em SBA-15 e superiores a 290 m2/g para os catalisadores suportados em FDU-1, sugerindo que esses materiais são promissores para prosseguir com os estudos e efetivamente testá-los para hidrodessulfurização. / This work aimed at the synthesis and characterization of Co-Mo and Ni-Mo catalysts supported on ordered mesoporous silica (SBA-15 and FDU-1) for hydrodesulfurization. SBA-15 and FDU-1 samples were synthesized from TEOS as silica source and triblock copolymers as structure templating agents in acidic medium. Ni(NO3)2.6H2O, Co(NO3)2.6H2O, (NH4)6Mo7O24.4H2O were used as metal sources. The aqueous suspension of silica was mixed with the metallic cation solution according to desired concentration. After evaporation of water the polymeric template was removed by calcination under dynamic atmospheres of N2/air producing precursors in the oxide form. The TG/DTG, XRD, SEM-EDS, ICP OES, isotherm adsorption/desorption of N2 and SAXRD techniques were employed to characterize these materials. The TG was used to verify the composition of the starting salts, to define the best conditions of calcination and define the final product stoichiometry. The XRD results confirmed the oxide phase after calcination of salts and catalysts. The SAXRD results indicated well resolved peaks and great structure for catalysts supported on SBA-15. However, the catalysts supported on FDU-1 showed no well-defined diffraction peaks but only correlation bands which indicated the formation of areas of somewhat ordered pores and disordered domains. The nitrogen adsorption isotherms were according to literature for SBA-15 pure and modified samples but FDU-1 pure and modified samples presented deformed branches of desorption isotherms. The metallic contents were determined by emission spectrometry atomic plasma source. The values for surface areas were greater than 450m2/g for the catalysts supported on SBA-15 and larger than 290 m2/g for the catalysts supported on FDU-1, suggesting that these materials are promising for further studies and test them in the hydrodesulfurization reactions.
17

Nouvel additif pour l'activation de catalyseurs d'hydrotraitement régénérés / New additive for the activation of regenerated hydrotreating catalysts

Bui, Ngoc-Quynh 06 October 2011 (has links)
L'objectif de ce travail est d'améliorer l'activation de catalyseurs d'hydrotraitement CoMo/Al2O3 régénérés par l'emploi d'un nouvel additif organique, l'acide maléïque. En effet, le procédé de régénération permet la réutilisation d'un catalyseur d'hydrotraitement ayant subi une désactivation en éliminant les impuretés carbonées et en redispersant la phase active à la surface du catalyseur. Ce procédé ne permet cependant pas de retrouver l'activité initiale d'un catalyseur neuf. L'emploi d'additif organique lors de la préparation de catalyseurs régénérés permet alors d'améliorer l'activité catalytique. Au cours de ce travail, l'influence de l'acide maléïque a été étudiée à chaque étape du processus d'activation d'un catalyseur d'hydrotraitement régénéré. A l'état oxyde, l'acide maléïque n'influence pas la formation d'aluminate de cobalt tandis que cet additif consomme la phase CoMoO4 néfaste à l'activité finale dès maturation à 30°C. Cette consommation de la phase CoMoO4 s'accompagne de la formation de maléate de cobalt. Des études complémentaires menées par extraction des espèces oxydes suite à l'interaction du catalyseur régénéré avec l'acide maléïque en solution aqueuse montrent également une redispersion du molybdène sous forme d'un sel d'Anderson, AlMo6. Cette redispersion permet de sulfurer rapidement le molybdène dès 150°C tandis que le cobalt tend à se sulfurer progressivement avant décomposition du maléate. La décomposition complète du maléate de cobalt à 350°C permet alors de libérer le cobalt afin que celui-ci interagisse efficacement avec le sulfure de molybdène déjà formé conduisant à une proportion élevée en phase promue / The objective of this study is to improve the activation of regenerated CoMo/Al2O3 hydrotreating catalysts through the use of a novel organic additive, maleic acid. The regeneration process allows to re-use hydrotreating catalysts that have been deactivated leading to the removal of carbon impurities and to the redispersion of the active at the catalyst surface. However, using this process, the regenerated catalyst cannot recover completely the activity of a fresh catalyst. The use of organic additives during the preparation of regenerated catalysts can improve the final catalytic activity. In this work, the influence of maleic acid has been studied at each step of the activation procedure of a regenerated hydrotreating catalyst. At the oxide state, maleic acid does not influence the formation of cobalt aluminate while after maturation at 30°C, this additive can consume the CoMoO4 phase known to be detrimental to the activity. This disappearance of the CoMoO4 phase is accompanied by the formation of cobalt maleate. Complementary studies based on the extraction of oxide species through the interaction of the regenerated catalyst with maleic acid in aqueous solution also evidence the redispersion of molybdenum as AlMo6 Anderson salt species. This redispersion allows to rapidly sulphide molybdenum as soon as 150°C while cobalt is progressively sulphided before the maleate decomposition. The complete decomposition of cobalt maleate at 350°C makes cobalt available to interact efficiently with the already formed molybdenum sulphide leading to a high proportion of promoted phase
18

Design and Synthesis of Crystalline Dehydrobenzoannulene-Containing Covalent Organic Frameworks for Sustainable Applications

Haug, William Karl, IV January 2021 (has links)
No description available.
19

Kinetic parameter estimation and simulation of trickle-bed reactor for hydrodesulfurization of crude oil

Jarullah, Aysar Talib, Mujtaba, Iqbal M., Wood, Alastair S. January 2011 (has links)
No description available.
20

Novel, High Activity Hydroprocessing Catalysts: Iron Group Phosphides

Wang, Xianqin 27 March 2002 (has links)
A series of iron, cobalt and nickel transition metal phosphides was synthesized by means of temperature-programmed reduction (TPR) of the corresponding phosphates. The same materials, Fe₂P, CoP and Ni₂P, were also prepared on a silica (SiO₂) support. The phase purity of these catalysts was established by x-ray diffraction (XRD), and the surface properties were determined by N₂ BET specific surface area (Sg) measurements and CO chemisorption. The activities of the silica-supported catalysts were tested in a three-phase trickle bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene using a model liquid feed at realistic conditions (30 atm, 370 °C). The reactivity studies showed that the nickel phosphide (Ni₂P/SiO₂) was the most active of the catalysts. Compared with a commercial Ni-Mo-S/g-Al₂O₃ catalyst at the same conditions, Ni₂P/silica had a substantially higher HDS activity (100 % vs. 76 %) and HDN activity (82 % vs. 38 %). Because of their good hydrotreating activity, an extensive study of the preparation of silica supported nickel phosphides, Ni₂P/SiO₂, was carried out. The parameters investigated were the phosphorus content and the weight loading of the active phase. The most active composition was found to have a starting synthesis Ni/P ratio close to 1/2, and the best loading of this sample on silica was observed to be 18 wt.%. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES) measurements were employed to determine the structures of the supported samples. The main phase before and after reaction was found to be Ni₂P, but some sulfur was found to be retained after reaction. A comprehensive scrutiny of the HDN reaction mechanism was also made over the Ni₂P/SiO₂ sample (Ni/P = 1/2) by comparing the HDN activity of a series of piperidine derivatives of different structure. It was found that piperidine adsorption involved an a-H activation and nitrogen removal proceeded mainly by means of a b-H activation though an elimination (E2) mechanism. The relative elimination rates depended on the type and number of b-hydrogen atoms. Elimination of b-H atoms attached to tertiary carbon atoms occurred faster than those attached to secondary carbon atoms. Also, the greater the number of the b-H atoms, the higher the elimination rates. The nature of the adsorbed intermediates was probed by Fourier transform infrared spectroscopy (FTIR) and temperature-programmed desorption (TPD) of the probe molecule, ethylamine. This measurement allowed the determination of the likely steps in the hydrodenitrogenation reaction. / Ph. D.

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