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Quick-EXAFS and hydrotreating catalysts : chemometrics contribution / Quick-EXAFS et catalyseurs d’hydrotraitement : apports de la chimiométrieOliveira De Souza, Danilo 15 July 2015 (has links)
L’hydrodésulfuration (HDS) est un procédé catalytique utilisé pour éliminer le soufre des carburants. La demande mondiale de carburants propres a stimulé les recherches sur autour de ce procédé afin de mieux comprendre les mécanismes réactionnels et de produire des catalyseurs plus efficaces. Deux axes de recherches peuvent être dégagés : d’une part la formulation de nouvelles voies de synthèse permettant la production des catalyseurs plus efficaces et d’autre part la compréhension du processus catalytique au niveau moléculaire. La compréhension des transformations structurales du catalyseur au niveau moléculaire pendant la réaction ainsi que pendant la genèse de la phase active est une nécessité pour améliorer les propriétés des catalyseurs. Dans ce contexte, ce travail propose deux objectifs. En premier lieu, il présente nouvelle méthode de synthèse de catalyseurs d’HDS à base de CoMo supporté dans TiO2 par voie sol-gel. Dans un deuxième temps, le travail présente la mise-en-œuvre de la chimiometrie pour traiter des données in situ de spectroscopie d’absorption de rayons-X (XAS) qui permet d’obtenir des informations sur la structure moléculaire du catalyseur pendant son activation. Les installations synchrotron de dernière génération permettent en effet d’enregistrer des données expérimentales avec résolution temporelle de l’ordre de la seconde (Quick-EXAFS) et la chimiometrie fournit des outils d’analyse et d’interprétation pour extraire des informations sur les cinétiques de réaction et sur les transformations structurales menant à la formation de la phase active du catalyseur. / Hydrodesulfurization (HDS) is catalytic process used to remove sulfur from petroleum feedstock. The world claim for clean fuel boosted scientists to get new insights on the catalytic reaction in order to understand the mechanisms of the process and, thus, produce catalysts that are more efficient. Such researches are based mainly in to lines: by one hand, in the formulation of new routes that lead to tailored catalysts and, by the other hand, in a better understanding of the catalytic process at the molecular and atomic level. Particularly, the later leads to an optimization of the formulation and better catalytic performance, for which is required further understanding of the molecular structure, its transformations during the reaction, the nature of active species and its genesis. In this picture, the goal of this work is twofold. First, to present a new route for produce HDS CoMo-based catalysts via one-pot sol-gel method, which revealed to have suitable macro- and microscopic properties making promising solids for further applications. Second, to adapt and use chemometrics method to treat in situ measurements, particularly, X-ray absorption spectra (XAS), to get new insights on the genesis of the catalytic active phase at the molecular level. XAS techniques is suitable to probe local atomic structure, and last generation synchrotron facilities provide conditions to perform such in situ experiments with very fast acquisition (Quick-EXAFS). Chemometrics provide a brand new scope on data analysis and interpretation for extract information on the kinetics of reaction and structure transformation that leads to the active phase of the catalysts.
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Förbättringsåtgärder för en ökad talloljeproduktion vid Smurfit Kappa PiteåIsaksson, Jonas January 2017 (has links)
Sodapannan hos Smurfit Kappa Piteå är en av flaskhalsarna i produktionsflödet. Detta har till följd att tjockluten ackumulerar medan resterande lutar minskar, på grund av detta måste övriga enheter tidvis minska produktionen. Sodapannan har dessutom gett en varierad ångproduktion per ts (torrsubstans) lut vilket tros vara relaterat till lutens såpinnehåll, tidigare analyser påvisat stora variationer i avsåpning. Eftersom såpa har högre energivärde än svartlut ligger detta som grund till kopplingen mellan variationen i ångproduktion per ts lut och avsåpningen. Avskild såpa vidareförädlas till tallolja i hartskokeriet, Smurfit Kappa Piteå använder en HDS (hydrodynamisk separator) för att avskilja tallolja från spjälkvätska. Tallolja används bland annat för framställning av biodiesel och de senaste årens intresse för biobränslen har även bidragit med större fokus på talloljetillverkningen vid pappersbruken. Smurfit Kappa Piteå har på senare tid gjort två större förändringar som har en direkt påverkan på talloljeproduktionen. Avsåpningsparken har byggts ut och flödet av spjälkvätska har lagts om till efter avsåpning istället för före avsåpning. Företaget är därför intresserade av en djupare analys för att undersöka hur förändringarna påverkat talloljeproduktionen och vad som kan göras för att ytterligare förbättra den. I detta projekt undersöks förluster av såpa och tallolja till sodapannan, hur förlusterna påverkar ångproduktionen per ts lut samt möjliga förbättringsåtgärder för en ökad talloljeproduktion. För att utreda förlusterna genomfördes en kartering vid tio olika tillfällen där talloljeinnehåll i svartlut samt såpans talloljeinnehåll fastställdes. Från detta erhölls följande resultat; avsåpningens verkningsgrad var cirka 94 % i blandlutssteget och 0 % i mellanlutssteget. Medelutbytet av tallolja i hartskokeriet var 70 %. Resultatet från karteringen analyserades med SIMCA tillsammans med tillgängliga variabler som påverkar avsåpningen, ingen specifik variabel visades påverka avsåpningen i betydande grad. Via en sammanställning av tallolje- och såpförlusterna visades en förbättringspotential för ökad talloljeproduktion på 42 % över HDS:en och 4 % över blandlutssteget vid hypotetiska utbyten på 100 % för vardera enhet. Ur förlusterna beräknades även den extra belastning som erläggs sodapannan och hur ångproduktionen per ts lut varierade med avseende på detta. Variationen i ångproduktion per ts lut gick inte att korrelera till förlorad såpa och tallolja. Vid drift av HDS:en, bidrog dess talloljeförluster med 1,1 % ökning av medelenergi på brännluten samtidigt som förlusten av såpa vid avsåpning bidrog med en medelenergiökning på 0,3 %. Utöver detta undersöktes även talloljeproduktionen med avseende på massaproduktionen för perioden 2010-2016. Från detta kunde en tydlig årstidsvariation urskiljas. Totalutbytet av tallolja från massa hade stigit samtidigt som kvoten löv/barr minskat. De senaste månaderna påvisade ett minskat totalutbyte av tallolja från massan vilket kopplades till omläggning av spjälkvätska till efter avsåpning från att tidigare återinförts före avsåpning.
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Model Predictive Control of Traffic Flow Based on Hybrid System ModelingOKUMA, Shigeru, SUZUKI, Tatsuya, KIM, YoungWoo, KATO, Tatsuya 01 February 2005 (has links)
No description available.
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Compréhension de la relation entre la structure physico-chimique et l’activité des catalyseurs d’HDS vieillis / Understanding of the relation between physico-chemical structure and activity of aged HDS catalystsSaturnino, David 28 April 2014 (has links)
L'hydrodésulfuration (HDS) est un procédé majeur du raffinage pétrolier pour enlever le soufre des charges, typiquement avec un catalyseur CoMoS/Al2O3. Pendant un cycle du procédé d'HDS, la désactivation du catalyseur est due à trois causes principales : dépôt de coke, dépôt de métaux et ségrégation de la phase active. L'objectif de ce travail a été l'étude de l'effet du cokage et modifications de la phase active sur la désactivation du catalyseur d'HDS (de type CoMoS/Al2O3) appliqué à l'HDS des gazoles et la recherche des paramètres clés pour l'obtention d'un catalyseur usé comparable à celui issu de raffinerie. Des tests de vieillissement accéléré ont été réalisés avec différentes charges (différentes teneurs en aromatiques), couverture en hydrogène, durée et un pré-traitement de réduction. Après chaque test, les catalyseurs ont été caractérisés en termes de texture (méthodes BET et BJH), coke (Raman, IR, TPO, RPE, ToF-SIMS) et phase active (MET/EDX, XPS, TPR). En termes de texture et coke, une teneur élevée en aromatiques dans la charge et une couverture en hydrogène faible favorisent la formation de coke. Pour augmenter l'organisation du coke par rapport au catalyseur industriel, nous avons proposé un test plus long. En termes de phase active, une longue durée, couverture en hydrogène élevée et une pré-réduction favorisent plus d'hétérogénéité des teneurs en soufre et cobalt de la phase active et la formation d'agglomérats de sulfure de cobalt. La pré-réduction semble être efficace pour simuler l'exposition à des températures élevées pendant un cycle d'HDS, ce qui conduit à la ségrégation de la phase active, une caractéristique d'un catalyseur usé industriellement / Hydrodesulfurization (HDS) is a major process of petroleum refining for sulphur removal, where CoMoS/Al2O3 is the typical catalyst. During the cycle of a HDS process, deactivation of the catalyst is attributed to three main causes: coke deposition (with loss of pore volume), metals deposition and segregation of the active phase. The aim of this work was to study the effect of coking and active phase changes on the deactivation of the HDS catalyst (of CoMoS/Al2O3 type) applied to the HDS of a diesel feed and find the key operating conditions to obtain a spent catalyst comparable to the industrial one. Accelerated aging tests have been performed with different feedstocks (different amounts of aromatics), hydrogen to oil ratio, duration and a pre-reduction treatment. After each test, catalysts have been characterized in terms of texture (BET and BJH methods), coke (Raman, IR, TPO, EPR, ToF-SIMS) and active phase (TEM/EDX, XPS, TPR). In terms of texture and coke, a high amount of aromatics on the feedstock and low hydrogen to oil ratio favor the formation of coke. In order to increase the organization of graphitic coke, we have proposed a longer test. In terms of active phase, a long duration, high hydrogen to oil ratio and a pre-reduction treatment favor loss of dispersion of sulphur and cobalt contents of the active phase and formation of cobalt sulfide agglomerates. Pre-reduction seems to be an effective treatment to simulate the exposure to high temperatures during a HDS cycle which results in segregation of the active phase, a fingerprint of an industrial spent HDS catalyst
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Influence de la morphologie 2D de la phase active sur la sélectivité des catalyseurs sulfures en HDS des essences / Influence of 2D morphology of active phase on selectivity of sulfide catalysts in HDS of gasolineBaubet, Bertrand 24 April 2013 (has links)
Ce travail de thèse étudie l’influence de la morphologie des feuillets de sulfure de molybdène sur la sélectivité des catalyseurs d’hydrotraitement. Les feuillets de phase active présentent en effet deux types de bords appelés « M-edge » et « S-edge » susceptibles de conduire à des réactivités différentes. Le changement de la morphologie 2D des feuillets pourrait modifier les proportions de bords M et S exposés et ainsi les propriétés catalytiques des catalyseurs sulfures. Pour cela, des catalyseurs non promus (Mo) et promus (CoMo), supportés sur alumine ont été préparés par imprégnation à sec puis sulfurés dans des conditions variées (gaz et température). Des tests catalytiques en hydrodésulfuration (HDS) sélective des essences de FCC (sélectivité HDS/HYD) ont ensuite permis d’évaluer l’impact de la morphologie en s’appuyant sur des modèles géométriques construits à partir de calculs DFT et de caractérisations expérimentales (TEM, IR (CO), TPR, XPS). Les résultats obtenus pour les catalyseurs de type Mo semblent ainsi confirmer l’influence de la morphologie 2D sur la sélectivité HDS/HYD, le bord M paraissant être le plus sélectif pour les catalyseurs non promus. Ils mettent également en évidence l’importance de la réductibilité plus ou moins marquée des bords sur les propriétés catalytiques, notamment sur le bord M. Le changement des conditions de sulfuration semble donc affecter la morphologie des particules mais également les propriétés chimiques propres à chaque bord. En ce qui concerne les catalyseurs promus, la variation des conditions de sulfuration semble agir essentiellement au niveau de la répartition du promoteur entre les bords M et S. Cependant, les interactions avec le support paraissent constituer un frein aux effets de promotion. Dans ce contexte, les sulfurations à haute température sous H2S pur permettent d’obtenir des gains significatifs en activité et sélectivité. Ces résultats semblent dus à de faibles interactions avec le support et une décoration privilégiée du bord S qui pourrait favoriser la réaction d’HDS et limiter la réaction d’HYD. Au final, les interprétations effectuées en terme de morphologie 2D tendent à confirmer que ce paramètre peut constituer un axe de développement intéressant pour les catalyseurs d’hydrotraitement. L'optimisation des conditions de sulfuration permettraient bien de faire varier la morphologie et le taux de décoration du promoteur des catalyseurs, améliorant ainsi significativement l'activité et la sélectivité / This thesis examines the influence of the morphology of particles of molybdenum sulfide on selectivity of hydrotreating catalysts. Nanoparticles of active phase present two types of edges called “M-edge” and “S-edge” which may lead to different reactivities. The change in morphology of the 2D sheets could change the proportions of M and S edges exposed and thus the catalytic properties of sulfide catalysts. For this, non-promoted (Mo) and promoted (CoMo) catalysts, supported on alumina were prepared by dry impregnation and sulfide in various conditions (gas and temperature). Catalytic tests in selective hydrodesulfurization (HDS) of FCC gasoline (selectivity HDS /HYD) were then used to assess the impact of the morphology based on geometrical models which were constructed with DFT calculations and experimental characterizations (TEM, IR (CO), TPR, XPS). The results for Mo catalysts seem to confirm the influence of the 2D morphology selectivity HDS / HYD, M-edge appearing to be the most selective for non-promoted catalysts. They also highlight the importance of the reducibility more or less pronounced of the edges on the catalytic properties, especially on the M-edge. The different conditions of sulfidation seem to affect the morphology of the particles but also the specific chemical properties at each edge. Regarding to the promoted catalysts, the different conditions of sulfidation appear to act primarily at the distribution of the promoter between the M and S edges. However, interactions with the carrier appear to constitute an obstacle to promoting effects. In this context, sulfidations at high temperature in pure H2S lead to obtain significant gains in activity and selectivity. These results appear to be due to weak interactions with the carrier and to the presence of the promoter on the S-edge which could promote the HDS reaction and limit the HYD reaction. Finally, the interpretations made in terms of 2D morphology tend to confirm that this parameter can be an interesting line of development for hydrotreating catalysts. Optimization of the sulfidation conditions could effectively allow to vary the morphology and the rate of decoration of promoted catalysts which significantly improve the activity and selectivity
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EditorialMitterauer, Lukas 29 October 2020 (has links)
Unter dem Titel „Regeneration Hochschullehre“ fand die Jahrestagung der dghd 2019 in Leipzig statt. Regeneration kann hier zumindest auf drei Arten interpretiert werden:
Der Hochschullehre wird in den letzten Jahren wieder ein höherer Stellenwert zugeordnet und sie erscheint wieder nach Jahren der Konzentration auf Forschung regeneriert auf der Bildfläche.
Auf der organisatorischen und institutionellen Ebene sind vor allem die Entwicklungen seit dem Start des Bolognaprozesses und dem Qualitätspakt Lehre zu nennen, durch die in der Hochschullehre – neben ihrer Aufwertung – neue Ansätze generiert wurden.
Gleichzeitig kam es mit der Schaffung von Stellen für young professionals zu einem Generationenwechsel in der Hochschuldidaktik, was automatisch auch zur Entwicklung von und Öffnung hin zu neuen Ansätzen führt.
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Spectroscopic and Kinetic Studies of Hydrodenitrogenation and Hydrodesulfurization over Supported Nickel Phosphide (Ni₂P)Gott, Travis Matthew 20 November 2008 (has links)
This dissertation describes preparation and characterization of Ni₂P catalysts and their application in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN). The work carried out includes synthesis of Ni₂P on different siliceous supports, SiO2 and MCM-41. It also includes characterization of these catalytic materials using X-ray diffraction (XRD), temperature-programmed reduction (TPR), Fourier transform infrared (FTIR) spectroscopy and X-ray absorbance fine structure (XAFS) spectroscopy. In situ FTIR was employed to study the acidity of Ni₂P/SiO₂ and probe the catalytic sites involved in the HDN of pyridine. Transient and steady-state kinetics of a surface intermediate that is formed upon pyridine adsorption and reaction was studied to elucidate the mechanism of HDN over Ni₂P/SiO₂. Additionally, in situ FTIR and X-ray absorption near edge structure (XANES) spectroscopy was utilized to probe the bonding, mechanism and kinetics of thiophene HDS over a novel MCM-41-supported Ni₂P catalyst. The use of these techniques allowed for better understanding of the surface intermediates, mechanisms and the nature of the active sites involved in HDN and HDS. / Ph. D.
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Catalytic Hydrogenation and Hydrodesulfurization of Model CompoundsZhao, Haiyan 06 May 2009 (has links)
This dissertation describes two related studies on hydrogenation and hydrodesulfurization of heterocyclic S-containing compounds.
Alkyl substituted thiophenes are promising candidates for hydrogen carriers as the dehydrogenation reactions are known to occur under mild conditions. Four types of catalysts including supported noble metals, bimetallic noble metals, transition metal phosphides and transition metal sulfides have been investigated for 2-methylthiophene (2MT) hydrogenation and ring opening. The major products were tetrahydro-2-methylthiophene (TH2MT), pentenes and pentane, with very little C5-thiols observed. The selectivity towards the desired product TH2MT follows the order: noble metals > bimetallics > phosphides > sulfides. The best hydrogenation catalyst was 2% Pt/Al2O3 which exhibited relatively high reactivity and selectivity towards TH2MT at moderate temperatures. Temperature-programmed desorption (TPD) of hydrogen indicated that the H2 desorption amount was inversely related to the rate of TH2MT formation. Temperature programmed reaction (TPR) experiments revealed that pentanethiol became the major product, especially with HDS catalysts like CoMoS/Al2O3 and WP/SiO2, which indicates that poisoned or modified conventional HDS catalysts would be good candidates for further 2MT hydrogenation studies.
The role of tetrahedral Ni(1) sites and square pyramidal Ni(2) sites in Ni2P hydrotreating catalysts was studied by substitution of Ni with Fe. The Fe component was deemed as a good probe because Ni2P and Fe2P adopt the same hexagonal crystal structure, yet Fe2P is completely inactive for hydrodesulfurization (HDS). For this purpose a series of NiFeP/SiO2 catalysts were prepared with different Ni:Fe molar ratios (1:0, 3:1, 1:1, 1:3, and 0:1) and investigated in the HDS of 4,6-dimethyldibenzothiophene at 300 and 340 oC. The uniformity of the NiFe series was demonstrated by x-ray diffraction analysis and by Fourier transform infrared (FTIR) spectroscopy of adsorbed CO. The position of substitution of Fe was determined by extended X-ray absorption fine structure (EXAFS) analysis. It was found that at 300 oC the HDS activity of the catalysts decreased with increasing Fe content and that this could be explained by the substitution of Fe at the more active Ni(2) sites. As temperature was raised to 340 oC, the activity of the Fe-containing samples increased, although not to the level of Ni2P, and this could be understood from a reconstruction of the NiFe phase to expose more Ni(2) sites. This was likely driven by the formation of surface Ni-S bonds, which could be observed by EXAFS in spent samples. / Ph. D.
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Reactivity and Structure of Supported Nickel Phosphides (Ni₂P) in Deep Hydrodesulfurization CatalysisLee, Yong-Kul 26 January 2005 (has links)
This dissertation describes preparation and characterization of Ni₂P catalysts and their application in deep hydrodesulfurization (HDS) of a model sulfur compound, 4,6-dimethyldibenzothiophene (4,6-DMDBT), one of the most refractory S-compounds. This topic is of great importance in addressing recently enacted environmental regulations limiting the sulfur content in fuels. The work carried out includes synthesis of Ni₂P on different siliceous supports, SiO₂, MCM-41, and ultra-stable Y zeolite (USY). It also includes determining the characteristics of the supported Ni₂P catalysts with a wide range of techniques: X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and X-ray absorption fine structure (XAFS) spectroscopy. The use of these techniques allowed better understanding of the nature of the active sites as well as the effect of supports. Activity tests were conducted in the HDS of 4,6-DMDBT and the HDN of quinoline. The performance of the catalysts will be compared to that of a conventional sulfide hydrotreating catalyst, Ni-Mo-S/Al₂O₃. Investigation of the reaction mechanism in the hydrodenitrogenation (HDN) of 2-methylpiperidine together with in situ FT-IR measurements were conducted to understand how catalyst properties affect activity and selectivity. / Ph. D.
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Adição de fósforo (P) em catalisadores NiMo, suportados em γ-Al2O3, Al2O3/TiO2 e TiO2 - efeito na hidrodessulfurização do tiofenoZanotello, Tatiane Cristina 18 February 2013 (has links)
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Previous issue date: 2013-02-18 / Universidade Federal de Sao Carlos / Mo, NiMo or NiMoP HDS catalysts were supported on Al2O3, Al2O3-TiO2 or TiO2. These supports were synthesized via sol-gel and in the case o TiO2 it was used a commercial sample. The active phases were introduced by impregnation. Supports and catalysts in the oxide form were characterized by X-ray diffraction (XRD), diffuse reflectance UV-Vis spectroscopy (DRSUV-Vis), thermogravimetric analyses (TG), temperature-programmed reduction with H2 (TPR-H2), N2 adsorption/desorption, energy dispersive X-ray spectroscopy (EDS), X-ray fluorescence (XRF), temperature-programmed desorption of NH3 (TPD-NH3), high resolution transmission electron microscopy (HRTEM) and evaluated at 300°C in the HDS of thiophene, used as a model molecule. Alumina presented a high specific surface area and meso/macroprous characteristics, allowing a high dispersion of the active phases, as was evidenced by XRD and DRSUV-VIS data. A HRTEM image of a NiMo/Al2O3 catalyst showed the presence of crystalline MoS2 whose activity was substantially promoted by the presence of Ni. The NiMo catalysts were active in the HDS of thiophene, however, the activity was enhanced significantly by the incorporation of P. This result corroborates the positive influence of P in the preparation of HDS catalysts. It was suggested that P must participate as promoter in the formation of the NiMoS phase during the sulfidation process of the Ni and Mo oxides. The supported NiMoP catalysts prepared in this work were more active than a commercial NiMoP/ Al2O3 catalyst, with this result validating the preparation procedures used here. The titania addition in the alumina framework led to NiMo catalysts possessing lower activity. That behavior was attributed to the formation of Ni and Mo sulfides without interaction diminishing the generation NiMoS phase, which is highly active in the HDS of sulfured organic compounds. / Catalisadores para hidrodessulfurização (HDS) contendo Mo, NiMo ou NiMo e o aditivo fósforo (P), foram suportados sobre Al2O3, Al2O3-TiO2 ou TiO2. A alumina e a alumina-titânia foram sintetizadas via sol-gel e, no caso da titânia pura, utilizada uma amostra comercial. A introdução dos sais precursores da fase ativa foi realizada via impregnação. Suportes e catalisadores na forma de óxidos foram caracterizados através de difração de raios X (DRX), espectroscopia por refletância difusa no ultravioleta visível (DRSUV-VIS), termogravimetria (TG), redução com hidrogênio à temperatura programada (RTP-H2), adsorção/dessorção de N2, espectroscopia de energia dispersiva de raios X (EDX), fluorescência de raios X (FRX), dessorção de amônia a temperatura programada (TPD-NH3), microscopia eletrônica de transmissão de alta resolução (HRTEM) e avaliados a 300⁰C na HDS do tiofeno. A alumina apresentou uma alta área superficial específica e características meso/macroporosa, possibilitando alta dispersão das fases ativas, conforme evidenciado por DRX e dados de DRSUV-VIS. A imagem de HRTEM do catalisador NiMo/Al2O3 mostrou a presença de MoS2 cuja atividade foi promovida substancialmente pela presença de Ni. Os catalisadores NiMo sobre os suportes utilizados foram ativos no HDS do tiofeno, entretanto, essa atividade foi melhorada pela incorporação de P. Esse resultado ratifica a influência positiva da utilização desse aditivo na preparação de catalisadores de HDS. O fósforo deve atuar como um promotor na formação de espécies NiMoS durante o processo de sulfetação dos óxidos de Mo e Ni. Os catalisadores NiMoP preparados neste trabalho apresentaram atividade específica superior à de um catalisador NiMoP/Al2O3 comercial, o que valida os procedimentos de preparação utilizados no trabalho. A adição de titânia na alumina durante a síntese sol-gel conduziu a catalisadores com menor atividade. Esse resultado foi atribuído à formação de sulfetos de Ni e Mo não interativos, com a consequente diminuição da formação da fase NiMoS de alta atividade no HDS de compostos organo-sulfurados.
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