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1
Hellgardt, Klaus. "Coprecipitated iron based catalysts for hydrotreating." Thesis, Imperial College London, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243566.
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Kouyionas, Vassilos. "Interactions of competing catalytic hydrotreating reactions." Thesis, Imperial College London, 1990. http://hdl.handle.net/10044/1/46398.
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Oliveira, De Souza Danilo. "Quick-EXAFS and hydrotreating catalysts : chemometrics contribution." Thesis, Lille 1, 2015. http://www.theses.fr/2015LIL10061/document.
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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<br>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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Schwartz, Viviane. "Preparation and Reactivity of Niobium-Containing Hydrotreating Catalysts." Diss., Virginia Tech, 2000. http://hdl.handle.net/10919/26368.
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A series of niobium-containing nitride and carbides were prepared by a temperature-programmed synthesis method. The catalysts synthesized comprised a monometallic niobium oxynitride and a new bimetallic oxycarbide supported system, Nb-Mo-O-C/Al₂O₃ (Mo/Nb = 1.2; 1.6; 2.0).
In the case of the niobium oxynitride, the progress of formation was analyzed by interrupting the synthesis at various stages. The effect of the heating rate on product properties was also investigated. The solid intermediates and the final niobium oxynitride were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), elemental analysis (CHNS), and gas adsorption techniques. The solid state transformation occurred directly from Nb₂O₅ to NbN<sub>x</sub>O<sub>y</sub> without any suboxide intermediates.
The bimetallic supported oxycarbide materials were also characterized by X-ray diffraction (XRD), gas adsorption techniques, X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS). It was found that the electronic properties of the oxycarbide were modified by the interaction with the Al₂O₃ support, and that most of the oxygen atoms were associated with the niobium rather than the molybdenum atom. All of the niobium-containing catalysts were tested in a three-phase trickle-bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene. The niobium oxynitride presented low HDS activity and moderate HDN activity, whereas the supported bimetallic oxycarbide was found to be highly active for both, HDN and HDS, demonstrating higher activities than the commercial sulfided Ni-Mo/Al₂O₃ when compared on the basis of active sites.
In addition to these studies a comprehensive investigation of the HDN reaction mechanism was carried out over bulk unsupported Mo₂C, NbC, NbMo₂-O-C, and compared with the mechanism over a sulfide catalyst, MoS₂/SiO₂. For this purpose, a comparison of the HDN rate of a series of isomeric amines was performed, and the reaction occurred mainly through a β-elimination mechanism for all catalysts. Temperature programmed desorption of ethylamine was used to investigate the acid properties of the catalytic surfaces, and a good agreement between the specific rate of reaction and the number of Brønsted acid-sites was obtained. Infrared spectroscopy showed that the amines interacted with acidic centers to form adsorbed quartenary ammonium species. The deamination reaction over the carbide and sulfide catalysts probably occurs by a concerted push-pull mechanism involving basic sulfur species and Brønsted-acidic centers. In order to obtain more insight into the mechanism a study of the pyridine HDN network was carried out.All of the catalysts showed the same activity trend: the reactivity of n-pentylamine was high, while those of piperidine and pyridine were relatively low. The carbide catalysts showed higher selectivity towards HDN products than the sulfide catalyst at the same conversion levels. The higher selectivity was related to the higher ratio (r = k₂/k₁) between the rate constants of the two consecutive reactions, hydrogenation of pyridine (k₁) and ring opening of piperidine (k₂). The order of activity of the carbides and sulfide differed considerably depending on the substrate. However, for the pyridine reaction network the similarity in product distribution suggested that a similar surface composition, a carbosulfide, was attained during the reaction.<br>Ph. D.
5
Patel, Jayeskumar Pravinzhai. "Characterisation study of nitrogen detection on coked hydrotreating catalyst." Thesis, Imperial College London, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.271715.
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Ahmad, Muhammad Imran. "Integrated and multi-period design of diesel hydrotreating process." Thesis, University of Manchester, 2009. http://www.manchester.ac.uk/escholar/uk-ac-man-scw:228852.
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Hydrotreating processes play a vital role in petroleum refineries to meet the increasing demand of transportation fuels. The recent trends in processing of heavier crudes with higher sulphur contents and more stringent product specifications for cleaner transportation fuels, such as ultra-low sulphur diesel, are resulting in more severe operating conditions and higher hydrogen consumption of hydrotreating processes. In order to carry out any revamp or design projects for improving the performance and efficiency of hydrotreating units molecular kinetic models of hydrotreating reactions may be required to provide detailed and accurate information of the composition and properties of hydrotreating products. The overall hydrotreating process consisting of the hydrotreater, the separation system and the associated heat recovery system need to be modelled on a consistent basis of detailed characterisation of petroleum fractions and the interactions of these individual subsystems with each other and with the refinery hydrogen network handled simultaneously for overall process optimisation. A molecular pathways level model of diesel hydrotreating reactions using the molecular type and homologous series matrix is employed for prediction of detailed molecular level information of composition and properties of diesel hydrotreating products. The molecular type and homologous series matrix representation of petroleum fractions is a detailed characterisation approach that represents the composition of a stream in a matrix in terms of the carbon number range and compound classes existing in the petroleum fraction. A new strategy is developed for estimation of physical properties of middle distillate and heavy petroleum fractions with molecular type and homologous series matrix representation using group contribution methods.
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Fulstow, A. N. "Some adsorption properties of molybdenum disulphide." Thesis, University of Hull, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375608.
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Bandyopadhyay, Rajarshi. "Comprehensive study on industrial diesel hydrotreating unit : new insights on design and optimization." Thesis, IIT Delhi, 2019. http://eprint.iitd.ac.in:80//handle/2074/8053.
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KAMYAB, ALI. "Preparation and evaluation of sulfided NiMo/γ-Al2O3 hydrotreating catalysts". Thesis, KTH, Skolan för kemivetenskap (CHE), 2016. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-190904.
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Four nickel-molybdenum catalysts were synthesized on gamma alumina with higher surface area and on NiMo catalyst was prepared using gamma alumina with lower surface area. Catalysts with higher-surface-area support were prepared by co-impregnation, sequential impregnation and adding phosphorous. Theses catalysts were calcined at 500 ͦC. Effect of higher calcination temperature was investigated by preparation of one catalyst calcined at 700 ͦC. Catalysts were thoroughly characterized via four characterization techniques. The hydrotreating activity of three catalysts was carried out in a micro reactor at high pressure and three different temperatures with Nynas vacuum middle distillate. Prior to the test, sulfiding was carried out to activate the catalysts. Hydrotreated-oil samples as products were analyzed to evaluate the activity and conversion of the catalyst. Also, the spent catalysts were characterized to evaluate the surface area characteristics and deactivation of catalysts. Addition of phosphorous to NiMo/gamma-Al2O3 improved the interaction between the metals and the support as well as reduced the coke formation as observed in scanning electron microscopy micrographs.
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Nikulshina, Kulikova Maria. "(Ni)MoWS alumina supported hydrotreating catalysts prepared from mixed H4SiMonW12-nO40 heteropolyacids." Thesis, Lille 1, 2018. http://www.theses.fr/2018LIL1R015/document.
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Le développement de catalyseurs HDS plus efficaces est un enjeu majeur pour répondre aux exigences environnementales concernant la teneur en soufre dans les carburants. L'une des approches pour améliorer l'activité catalytique est le développement de catalyseurs ternaires NiMoW. Cette étude se concentre sur la synthèse et la caractérisation de catalyseurs (Ni)MoW préparés à partir hétéropolyacides (HPA) mixtes SiMo1W11 et SiMo3W9 de structure de Keggin. Les catalyseurs basés sur les HPAs monométalliques SiMo12 et SiW12 et leurs mélanges ont été préparés et étudiés. Les solides ont été caractérisés par spectroscopie Raman, SPX et MET. Les propriétés catalytiques ont été évaluées dans des réactions d’HDS, d'HYD et d'HDN. Les propriétés physico-chimiques et l'activité catalytique dépendent de la nature des précurseurs initiaux. La genèse de la phase active des catalyseurs a été étudiée lors de la sulfuration in-situ sous H2S/H2 par SAX au synchrotron SOLEIL. La transformation du W dans les catalyseurs basés sur les précurseurs moléculaires mixtes, présentant une proximité nanométrique Mo-W, est plus rapide que celle observée dans le cas des catalyseurs préparés à partir du mélange de deux HPAs et conduit à la sulfuration simultanée des métaux et à la formation de la phase mixte MoWS2. La présence de feuillets mixtes (Ni)MoxW1-xS2 lorsque des HPA mixtes ont été utilisés a été mise en évidence par EXAFS et HAADF. La substitution d'un ou trois atomes de tungstène par du molybdène dans le cas des HPAs mixtes a entraîné une augmentation significative des activités en HDS et en HYD, par rapport à celles obtenues pour les catalyseurs préparés à partir du mélange de HPAs<br>Developing highly active HDS catalysts has been one of the most challenging and important subjects because of strengthening of environmental requirements for the sulfur content in fuels. One of the approaches to improve catalytic activity is the development of ternary NiMoW catalysts. This investigation focuses on the synthesis and characterization of (Ni)MoW catalysts prepared by using mixed SiMo1W11 and SiMo3W9 heteropolyacids (HPA) with Keggin structure. For comparison purposes, catalysts based on monometallic SiMo12 and SiW12 HPAs and their mixtures were also prepared and studied. The samples were characterized by Raman spectroscopy, X-ray Photoelectron Spectroscopy, HRTEM. The catalytic properties were evaluated in HDS, HYD and HDN reactions. The physical-chemical properties and catalytic activity depends on the nature of the initial precursors. Genesis of the active phase was studied during in situ H2S/H2 sulfidation of the catalysts by X-ray absorption at SOLEIL Synchrotron. It was found that W transformation from mixed molecular precursors with a Mo-W nanoscale proximity is faster than from mixture of two HPAs resulting in simultaneously sulfidation of metals and the formation of mixed MoWS2 phase. The presence of mixed (Ni)MoxW1-xS2 slabs when mixed HPAs were used for preparation of the catalyst was evidenced by EXAFS and High angle annular dark field scanning transmission electron microscopy. Substitution of one or three tungsten atoms by molybdenum ones in the case of mixed HPAs resulted in a significant increase in HDS as well as in HYD activity, compared to those obtained for catalysts prepared from mixture of monometallic HPAs
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Nikulshina, Kulikova Maria. "(Ni)MoWS alumina supported hydrotreating catalysts prepared from mixed H4SiMonW12-nO40 heteropolyacids." Electronic Thesis or Diss., Université de Lille (2018-2021), 2018. http://www.theses.fr/2018LILUR015.
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Le développement de catalyseurs HDS plus efficaces est un enjeu majeur pour répondre aux exigences environnementales concernant la teneur en soufre dans les carburants. L'une des approches pour améliorer l'activité catalytique est le développement de catalyseurs ternaires NiMoW. Cette étude se concentre sur la synthèse et la caractérisation de catalyseurs (Ni)MoW préparés à partir hétéropolyacides (HPA) mixtes SiMo1W11 et SiMo3W9 de structure de Keggin. Les catalyseurs basés sur les HPAs monométalliques SiMo12 et SiW12 et leurs mélanges ont été préparés et étudiés. Les solides ont été caractérisés par spectroscopie Raman, SPX et MET. Les propriétés catalytiques ont été évaluées dans des réactions d’HDS, d'HYD et d'HDN. Les propriétés physico-chimiques et l'activité catalytique dépendent de la nature des précurseurs initiaux. La genèse de la phase active des catalyseurs a été étudiée lors de la sulfuration in-situ sous H2S/H2 par SAX au synchrotron SOLEIL. La transformation du W dans les catalyseurs basés sur les précurseurs moléculaires mixtes, présentant une proximité nanométrique Mo-W, est plus rapide que celle observée dans le cas des catalyseurs préparés à partir du mélange de deux HPAs et conduit à la sulfuration simultanée des métaux et à la formation de la phase mixte MoWS2. La présence de feuillets mixtes (Ni)MoxW1-xS2 lorsque des HPA mixtes ont été utilisés a été mise en évidence par EXAFS et HAADF. La substitution d'un ou trois atomes de tungstène par du molybdène dans le cas des HPAs mixtes a entraîné une augmentation significative des activités en HDS et en HYD, par rapport à celles obtenues pour les catalyseurs préparés à partir du mélange de HPAs<br>Developing highly active HDS catalysts has been one of the most challenging and important subjects because of strengthening of environmental requirements for the sulfur content in fuels. One of the approaches to improve catalytic activity is the development of ternary NiMoW catalysts. This investigation focuses on the synthesis and characterization of (Ni)MoW catalysts prepared by using mixed SiMo1W11 and SiMo3W9 heteropolyacids (HPA) with Keggin structure. For comparison purposes, catalysts based on monometallic SiMo12 and SiW12 HPAs and their mixtures were also prepared and studied. The samples were characterized by Raman spectroscopy, X-ray Photoelectron Spectroscopy, HRTEM. The catalytic properties were evaluated in HDS, HYD and HDN reactions. The physical-chemical properties and catalytic activity depends on the nature of the initial precursors. Genesis of the active phase was studied during in situ H2S/H2 sulfidation of the catalysts by X-ray absorption at SOLEIL Synchrotron. It was found that W transformation from mixed molecular precursors with a Mo-W nanoscale proximity is faster than from mixture of two HPAs resulting in simultaneously sulfidation of metals and the formation of mixed MoWS2 phase. The presence of mixed (Ni)MoxW1-xS2 slabs when mixed HPAs were used for preparation of the catalyst was evidenced by EXAFS and High angle annular dark field scanning transmission electron microscopy. Substitution of one or three tungsten atoms by molybdenum ones in the case of mixed HPAs resulted in a significant increase in HDS as well as in HYD activity, compared to those obtained for catalysts prepared from mixture of monometallic HPAs
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Berrigan, John Daniel. "Nanopowder nickel aluminate for benzothiophene adsorption from dodecane." Thesis, Atlanta, Ga. : Georgia Institute of Technology, 2008. http://hdl.handle.net/1853/26580.
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Thesis (M. S.)--Materials Science and Engineering, Georgia Institute of Technology, 2009.<br>Committee Chair: Carter, W.B.; Committee Member: Cochran, Joseph; Committee Member: Venugopal, Ganesh. Part of the SMARTech Electronic Thesis and Dissertation Collection.
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Trinh, Thi Kim Hoang. "Prediction of Phase Equilibria Associated with Hydrotreating Process of Biomass by GC-PPC-SAFT Equation of State." Thesis, Sorbonne Paris Cité, 2015. http://www.theses.fr/2015USPCD074/document.
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L'objectif de cette thèse est de développer un outil prédictif pour calculer les équilibres vapeur-liquide (VLE) associé à l'opération d'hydrotraitement à partir de biomasse pour la simulation de processus. La construction d'une base de données de solubilité fiables d'hydrogène et d'autres gaz d'hydrotraitement ont été réalisées. Le modèle utilisé a pour base l’équation Groupe Contribution- Polar Perturbed Chain - statistique Associer Fluid Theory (GC-PPC-SAFT), qui est version de PC-SAFT combiné avec la contribution de groupes proposé par Tamouza et un terme polaire développé par Nguyen Huynh. Des tests systématiques ont été effectué pour différents mélanges gaz + d'alcools, aldéhydes, esters, éthers, cétones, ... Une nouvelle contribution non-additif a été proposé sur la base des réflexions sur les interactions répulsives et l’effet de volume libre. Le modèle a été validé notamment par des simulations Monte Carlo. Ce terme non additif a été intégré dans GC-PPC-SAFT et testé pour les systèmes contenant de l'hydrogène. La méthode de contribution de groupes a été étendue au paramètre de ce nouveau terme. Des écarts moyens sur la constante de Henry sont en accord avec l'incertitude expérimentale (~ 10%). Nous avons également examiné la prédiction d’ autres gaz i.e. CO, H₂ S, NH₃ en utilisant GC-PPC-SAFT. Un paramètre associatif transversale a été utilisé pour des systèmes contenant H₂ S et NH₃. Les résultats sont tout à fait acceptable et cohérent avec l'incertitude expérimentale (~20%)<br>The main objective of this thesis is to develop a predictive tool to compute the vapor-liquid equilibria (VLE) associated with hydrotreating operation from biomass for process simulation. The construction of a reliable database of hydrogen and the other hydrotreating gases solubilities have been done. The model used based on the Group Contribution – Polar Perturbed Chain – Statistical Associating Fluid Theory (GC-PPC-SAFT), which is PC-SAFT combined with the group contribution proposed by Tamouza and a polar term developed by Nguyen Huynh. The systematic tests have been perform for mixtures of alcohols, aldehydes, esters, ethers, ketones,… A new non-additive contribution has also been proposed based on the reflections on the repulsive interactions and the free volume effect. The model development are validated by Monte Carlo simulations. This non-additive term has been integrated in GC-PPC-SAFT Equation of state and tested for systems containing hydrogen. Group contribution method has been extended to its parameter. Average deviations on Henry’s constant are within the experimental uncertainty (~10%). We also have performed the prediction of the other gases i.e. CO, H₂S, NH₃ solubility using GC-PPC-SAFT. A cross associative parameter has been used for systems containing H₂S and NH₃. The results are quite acceptable and within the experimental uncertainty (~20%)
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Torres, Escobar Brenda. "Transition metal catalysts for hydrodesulphurization reactions applied to petroleum industry." To access this resource online via ProQuest Dissertations and Theses @ UTEP, 2009. http://0-proquest.umi.com.lib.utep.edu/login?COPT=REJTPTU0YmImSU5UPTAmVkVSPTI=&clientId=2515.
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Jarullah, Aysar Talib. "Kinetic Modelling Simulation and Optimal Operation of Trickle Bed Reactor for Hydrotreating of Crude Oil. Kinetic Parameters Estimation of Hydrotreating Reactions in Trickle Bed Reactor (TBR) via Pilot Plant Experiments; Optimal Design and Operation of an Industrial TBR with Heat Integration and Economic Evaluation." Thesis, University of Bradford, 2011. http://hdl.handle.net/10454/5363.
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Catalytic hydrotreating (HDT) is a mature process technology practiced in the
petroleum refining industries to treat oil fractions for the removal of impurities (such as
sulfur, nitrogen, metals, asphaltene). Hydrotreating of whole crude oil is a new
technology and is regarded as one of the more difficult tasks that have not been reported
widely in the literature. In order to obtain useful models for the HDT process that can
be confidently applied to reactor design, operation and control, the accurate estimation
of kinetic parameters of the relevant reaction scheme are required. This thesis aims to
develop a crude oil hydrotreating process (based on hydrotreating of whole crude oil
followed by distillation) with high efficiency, selectivity and minimum energy
consumption via pilot plant experiments, mathematical modelling and optimization.
To estimate the kinetic parameters and to validate the kinetic models under different
operating conditions, a set of experiments were carried out in a continuous flow
isothermal trickle bed reactor using crude oil as a feedstock and commercial cobaltmolybdenum
on alumina (Co-Mo/¿-Al2O3) as a catalyst. The reactor temperature was
varied from 335°C to 400°C, the hydrogen pressure from 4 to10 MPa and the liquid
hourly space velocity (LHSV) from 0.5 to 1.5 hr-1, keeping constant hydrogen to oil
ratio (H2/Oil) at 250 L/L. The main hydrotreating reactions were hydrodesulfurization
(HDS), hydrodenitrogenation (HDN), hydrodeasphaltenization (HDAs) and
hydrodemetallization (HDM) that includes hydrodevanadization (HDV) and
hydrodenickelation (HDNi).
An optimization technique is used to evaluate the best kinetic models of a trickle-bed
reactor (TBR) process utilized for HDS, HDAs, HDN, HDV and HDNi of crude oil
based on pilot plant experiments. The minimization of the sum of the squared errors
(SSE) between the experimental and estimated concentrations of sulfur (S), nitrogen
(N), asphaltene (Asph), vanadium (V) and nickel (Ni) compounds in the products, is
used as an objective function in the optimization problem using two approaches (linear
(LN) and non-linear (NLN) regression).
The growing demand for high-quality middle distillates is increasing worldwide
whereas the demand for low-value oil products, such as heavy oils and residues, is
decreasing. Thus, maximizing the production of more liquid distillates of very high
quality is of immediate interest to refiners. At the same time, environmental legislation
has led to more strict specifications of petroleum derivatives. Crude oil hydrotreatment
enhances the productivity of distillate fractions due to chemical reactions. The
hydrotreated crude oil was distilled into the following fractions (using distillation pilot
plant unit): light naphtha (L.N), heavy naphtha (H.N), heavy kerosene (H.K), light gas
oil (L.G.O) and reduced crude residue (R.C.R) in order to compare the yield of these
fractions produced by distillation after the HDT process with those produced by
conventional methods (i.e. HDT of each fraction separately after the distillation). The
yield of middle distillate showed greater yield compared to the middle distillate
produced by conventional methods in addition to improve the properties of R.C.R.
Kinetic models that enhance oil distillates productivity are also proposed based on the
experimental data obtained in a pilot plant at different operation conditions using the
discrete kinetic lumping approach. The kinetic models of crude oil hydrotreating are
assumed to include five lumps: gases (G), naphtha (N), heavy kerosene (H.K), light gas
oil (L.G.O) and reduced crude residue (R.C.R). For all experiments, the sum of the
squared errors (SSE) between the experimental product compositions and predicted
values of compositions is minimized using optimization technique.
The kinetic models developed are then used to describe and analyse the behaviour of an
industrial trickle bed reactor (TBR) used for crude oil hydrotreating with the optimal
quench system based on experiments in order to evaluate the viability of large-scale
processing of crude oil hydrotreating. The optimal distribution of the catalyst bed (in
terms of optimal reactor length to diameter) with the best quench position and quench
rate are investigated, based upon the total annual cost.
The energy consumption is very important for reducing environmental impact and
maximizing the profitability of operation. Since high temperatures are employed in
hydrotreating (HDT) processes, hot effluents can be used to heat other cold process
streams. It is noticed that the energy consumption and recovery issues may be ignored
for pilot plant experiments while these energies could not be ignored for large scale
operations. Here, the heat integration of the HDT process during hydrotreating of crude
oil in trickle bed reactor is addressed in order to recover most of the external energy.
Experimental information obtained from a pilot scale, kinetics and reactor modelling
tools, and commercial process data, are employed for the heat integration process
model. The optimization problem is formulated to optimize some of the design and
operating parameters of integrated process, and minimizing the overall annual cost is
used as an objective function.
The economic analysis of the continuous whole industrial refining process that involves
the developed hydrotreating (integrated hydrotreating process) unit with the other
complementary units (until the units that used to produce middle distillate fractions) is
also presented.
In all cases considered in this study, the gPROMS (general PROcess Modelling
System) package has been used for modelling, simulation and parameter estimation via
optimization process.<br>Tikrit University, Iraq
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Johansson, Johannes. "Inhibition Kinetics of Hydrogenation of Phenanthrene." Thesis, KTH, Skolan för kemi, bioteknologi och hälsa (CBH), 2019. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-279025.
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In this thesis work the hydrogenation kinetics of phenanthrene inhibited by the basic nitrogen compound acridine and the non-basic carbazole was investigated. Based on a transient reactor model a steady state plug flow model was developed and kinetic parameters were estimated through nonlinear regression to experimental data. The experimental data was previously collected from hydrotreating of phenanthrene in a bench-scale reactor packed with a commercial NiMo catalyst mixed with SiC. As a first two-step solution, the yields of the hydrogenation products of phenanthrene were predicted as a function of conversion, which subsequently was used to calculate concentration profiles as a function of position in reactor. As a second improved solution, the concentration profiles were calculated directly as a function of residence time, and these results were then used for further analysis. Reaction network 2 in figure 7 was considered sufficient to describe the product distribution of phenanthrene, with a pseudo-first-order rate law for the nitrogen compounds. Both solution methods provided similar results which gave good predictions of the experimental data, with a few exceptions. These cases could be improved by gathering more experimental data or by investigating the effect of some model assumptions. The two-step method thus proved useful in evaluating the phenanthrene reaction network and providing an initial estimate of the parameters, while the onestep method then could give a more precise solution by calculating all parameters simultaneously. As expected, acridine was shown to be more inhibiting than carbazole, both in the produced concentration profiles and estimated parameters. A possible saturation effect was also seen in the inhibition behavior, where adding more nitrogen compounds only had a small additional effect on the phenanthrene conversion. The Mears and Weisz-Prater criteria were found to be inversely proportional to the concentrations of the nitrogen compounds and otherwise only depend on rate constants, with values well below limits for diffusion controlled processes. Sensitivity analyses also supported that the global minimum had been found in the nonlinear regression solution.
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Hein, Jennifer [Verfasser], Johannes A. [Akademischer Betreuer] Lercher, and Moniek [Akademischer Betreuer] Tromp. "Investigation and Understanding of Unsupported Ni-Mo-W Sulfides for Hydrotreating / Jennifer Hein. Betreuer: Johannes A. Lercher. Gutachter: Johannes A. Lercher ; Moniek Tromp." München : Universitätsbibliothek der TU München, 2015. http://d-nb.info/1078112622/34.
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Wagenhofer, Manuel Florian [Verfasser], Johannes A. [Akademischer Betreuer] Lercher, Johannes A. [Gutachter] Lercher, Klaus [Gutachter] Köhler, and Roel [Gutachter] Prins. "Unsupported transition metal sulfides for hydrotreating of conventional and renewable feedstock / Manuel Florian Wagenhofer ; Gutachter: Johannes A. Lercher, Klaus Köhler, Roel Prins ; Betreuer: Johannes A. Lercher." München : Universitätsbibliothek der TU München, 2020. http://d-nb.info/1220423718/34.
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Ferreira, Junior Ary Rodrigues. "Estudo teórico da adsorção de siloxanos sobre superfícies da gama-alumina." Universidade Federal de Juiz de Fora, 2013. https://repositorio.ufjf.br/jspui/handle/ufjf/2308.
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Previous issue date: 2013-11-28<br>CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico<br>A alumina, Al2O3, é um material largamente utilizado na indústria. A fase é o α produto mais estável da calcinação de hidróxidos e oxihidróxidos como a boehmita, γ AlO(OH), a bayerita, Al(OH) α 3, e a gibbsita Al(OH) γ 3, acima de 1.000°C. Em temperaturas intermediárias, diferentes fases da alumina podem ser observadas, as quais são denominadas aluminas de transição ( , , , , e ). A fase deste óxido é reconhecida como um material η γ χ δ κ θ γ extremamente importante em vários processos industriais atuando como adsorvente, catalisador ou suporte. Esta alumina de transição é muito utilizada na indústria petroquímica como suporte para catalisadores a base de sulfetos de metais de transição Co(Ni)MoS no processo de hidrotratamento (HDT).
O polidimetilsiloxano (PDMS) é um polímero de fórmula geral [(CH3)2SiO]n, empregado como fluído de perfuração na indústria do petróleo, porém a sua aplicação como agente antiespumante em processos de transformação e tratamento nas refinarias merece maior atenção, devido ao problema da contaminação de catalisadores utilizados no processo de HDT. A sua degradação pode ocorrer a temperaturas superiores a 400°C alcançadas nos processos térmicos não catalíticos. Logo, as frações do petróleo que seguem para o processo de HDT, como a nafta leve e pesada ou o óleo diesel, já podem estar carregando para o reator oligômeros em concentrações suficientes para a desativação do catalisador.
Neste trabalho, a Teoria do Funcional da Densidade (DFT) foi utilizada na modelagem das superfícies (100) e (110) da alumina e também da fase ativa do catalisador γ MoS/ Al γ 2O3. Foi possível realizar a simulação de propriedades como os parâmetros espectrais de Ressonância Magnética Nuclear de Estado Sólido de 27Al e 29Si bem como as frequências vibracionais dos modos normais associados aos grupos hidroxila superficiais. Este conjunto de simulações permitiu que uma série de trabalhos experimentais relevantes relacionados à caracterização das superfícies do óxido e do catalisador envenenado fossem revisitados. Com a termodinâmica estatística foi possível discutir a presença de sítios ácidos de Lewis tricoordenados AlIII em amostras do suporte submetidas a tratamento térmico. Uma análise de energias livres dos primeiros estágios do envenenamento do catalisador sugeriu que os sítios ácidos de Brønsted do suporte são consumidos preferencialmente.<br>Alumina, Al2O3, is a material widely used in the industry. The phase is the most α stable product in the calcination of boehmite, AlO(OH), bayerite Al(OH) γ α 3, and gibbsite Al(OH)γ 3, at temperatures above 1.000°C. At intermediate temperatures, different phases of alumina can be observed, which are termed transition aluminas ( , , , , e ). The phase η γ χ δ κ θ γ of this oxide is known as an extremely important material in a number of industrial processes acting as an adsorbent, a catalyst or a catalyst support. This transition alumina is extensively used in petroleum and petrochemical industries as a support for transitionmetal sulfides Co(Ni)MoS in hydrotreatment (HDT) process.
Polydimethylsiloxane (PDMS) is a polymer with chemical formula [(CH3)2SiO]n applied in the oil industry as a drilling fluid, but its application as an antifoaming agent in oil refineries deserves attention, because of the problem associated with catalyst deactivation in the HDT process. Its degradation can occur at temperatures exceeding 400°C in noncatalytic thermal processes. So, some oil fractions which follows to the HDT process, as naphtha or diesel, may already be carrying to the reactor some oligomers like siloxanes, silanes, and silanols, in very low concentrations, but enough for catalyst deactivation due to the accumulation of silicon over the surfaces.
In the present work, the Densidty Functional Theory (DFT) was used for the modeling of the (100) and (110) surfaces of alumina as well as of the active phase of MoS/ Al γ γ 2O3 catalyst. With the structural models it was possible to perform simulations of properties like the 27Al and 29Si SolidState Nuclear Magnetic Resonance spectral parameters as well as the vibrational frequencies of the normal modes associated with the surfaces hydroxyl groups. With this set of simulated data, it was possible to reassess a number of experimental works related to the characterization of the oxide surfaces and the catalyst poisoning. From statistical thermodynamics, the presence of tricoordinated Lewis acid sites AlIII in samples subjected to thermal treatment was discussed and a free energy analysis considering the first steps of the catlyst poisoning process suggested that the Brønsted acid sites of the support are consumed preferentially.
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Da, Costa Soares Jean-Jérôme. "Compréhension moléculaire et prédiction des propriétés physicochimiques dans les produits pétroliers." Thesis, Lyon, 2017. http://www.theses.fr/2017LYSE1310/document.
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La diminution en pétrole brut léger nécessite de convertir les fractions lourdes en produits valorisables (essences, gazoles, huiles, etc.). Dans ce contexte, l'hydrocraquage (HCK) fournit des produits de très haute qualité à partir de distillats sous vide (DSV) du pétrole brut. La qualité des coupes obtenues est caractérisée par des propriétés physico-chimiques qui sont soumises à des spécifications. L'optimisation du procédé nécessite des expérimentations longues et coûteuses. IFPEN a donc de plus en plus recours à des tests sur unité d'expérimentation haut débit (EHD). Ces derniers posent cependant un problème d'accessibilité aux coupes d'intérêt. Par ailleurs, pour comprendre et prédire l'impact des conditions opératoires sur la qualité des produits, des simulateurs sont développés. Certaines propriétés de produits sont cependant complexes et difficiles à modéliser voire mal comprises. Ce travail de thèse a porté sur l'amélioration de la compréhension moléculaire des propriétés produits pour une meilleure prédiction. Dans cette étude, nous nous sommes focalisés sur le point de trouble (PT) de la coupe gazole et l'indice de viscosité (VI) de l'huile obtenue lors de l'hydrocraquage de DSV. Deux techniques d'analyse moléculaire ont été utilisées : la chromatographie en phase gazeuse bidimensionnelle (GC×GC) qui permet de déterminer la composition par famille chimique des différentes coupes et la résonance magnétique nucléaire (RMN) du 13C qui fournit des informations sur la structure chimique des hydrocarbures présents dans ces mélanges. Nous présentons les résultats obtenus par une régression multivariée parcimonieuse (sparse Partial Least Squares) appliquée aux données GC×GC et 13C RMN. Il s'agit d'une variante de la PLS classique qui permet de réduire le nombre de facteurs tout en privilégiant ceux qui sont les plus corrélés à une propriété d'intérêt donnée. Globalement, cette étude a notamment permis de mieux comprendre l'impact des différents hydrocarbures (n-paraffines, isoparaffines, aromatiques,…) et de leur structure moléculaire (longueur de chaînes, degrés de branchements,…) sur le PT des gazoles et le VI des huiles. La bonne qualité des modèles obtenus par sparse PLS montre par ailleurs la possibilité d'accéder à la qualité des produits lors de l'utilisation d'EHD. Des modèles de prédiction par krigeage ont également été développés. Cette méthode d'interpolation permet de prédire une propriété en un point donné en effectuant une moyenne pondérée des observations au voisinage de ce point. Les modèles de krigeage sont des modèles locaux adaptés aux structures de données complexes. Ce sont des approches probabilistes qui permettent d'estimer les incertitudes de prédiction. Aussi bien dans le cas du PT de la coupe gazole que dans celui du VI de la coupe huile, les résultats montrent une amélioration des performances. Cette approche est tout à fait novatrice dans le domaine des produits pétroliers. Lors de l'utilisation d'unités EHD, elle permet d'accéder au VI des huiles de base plus aisément que via des données chromatographiques ou spectroscopiques, qui sont de plus non accessibles en raffinerie<br>The rapid decline in light crude oils requires to convert heavy petroleum fractions into more valuable products (naphtha, diesel, lubricants, etc.). In this context, hydrocracking process (HCK) consists on upgrading vaccum gas oil (VGO) into high quality products. The quality of petroleum products is based on some chemical and physical properties that should fulfill prerequisite specifications. The hydrocracking process optimization requires to set up time consuming and costly experiments for developing catalysts and setting operating conditions. High throughput experimentation (HTE) units are then increasingly used at IFPEN. However, these units do not enable to obtain end products. Otherwise, predictive models were developed in order to understand and predict the impact of operating conditions about products quality. However, some complex properties are very difficult to model and require a better understanding. This work is mainly concerned with the understanding of diesel cloud point (CP) and viscosity index (VI) of base oils. Two analytical techniques were used: the two-dimensional gas chromatography (GC×GC) that enables to identify hydrocarbons compounds in petroleum products and the 13C nuclear magnetic resonance (NMR) spectroscopy which provides structural characteristics of these compounds. A sparse multivariate regression (sparse Partial Least Squares) was performed using chromatographic and spectroscopic data. The sparse PLS is derived from classical PLS. It allows to reduce the number of factors by performing a variable selection. The selected factors are the most correlated to the property to model. Globally, this approach enabled to better understand how hydrocarbon compounds (nparaffins, isoparaffins, aromatics,…) and their molecular characteristics (carbon number, degree of branching,…) affect the diesel CP and the VI of base oil. Furthermore, the good performances of developed sparse PLS models show that it is possible to access to the products quality when using HTE units. Kriging models were also developed. Kriging is an interpolation method that predicts the value of a function at a given point by computing a weighted average of the known values of the function in the neighborhood of the point. Kriging models have local aspect which is well adapted to complex data. Its probabilistic approach enables to provide an estimate of predicted value uncertainty. Results show that kriging improves predictive performances for both diesel CP and VI of base oil. This approach is quite innovative in modelling of petroleum products properties. When using HTE units, it allows to estimate the VI of base oil more easily than from chromatographic or spectroscopic data which are not available for the refiners
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Strutzel, Flávio Augusto Martins. "Controle IHMPC de um processo industrial de hidrotratamento de diesel." Universidade de São Paulo, 2014. http://www.teses.usp.br/teses/disponiveis/3/3137/tde-24062014-102335/.
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Neste trabalho é abordado o problema de controle e de otimização de unidades industriais de hidrotratamento de diesel (UHDT) por controladores MPC (Model Predictive Control). É apresentado um breve histórico dos controladores MPC convencionais e de horizonte infinito (IHMPC), bem como uma breve descrição do processo de Hidrotratamento de Diesel e das particularidades da aplicação do controle de processos a este tipo de planta industrial. Em seguida foi gerado, passo a passo, um algoritmo de controle que sumarizou e agregou características de vários controladores MPC disponíveis na literatura aberta, em especial os que foram desenvolvidos ao longo dos últimos anos pelo laboratório de simulação e controle da USP (LSCP), a fim de se obter um algoritmo adequado para a solução do problema de controle abordado. Em ambiente computacional de simulação, o algoritmo resultante possibilitou controlar e otimizar simultaneamente processos contínuos, sendo capaz de estabilizar a planta industrial de forma robusta e, ao mesmo tempo, aumentar a lucratividade de sua operação. Para tanto, foi desenvolvida uma função objetivo econômica que aumentou a conversão da carga bruta em produtos hidrotratados e minimizou o consumo de insumos, sendo que essa correlação foi agregada ao algoritmo de controle. As simulações permitiram que as estratégias de controle previamente discutidas pudessem ser testadas e seus resultados apresentados e debatidos.<br>This work addresses the control and optimization problem of industrial diesel hydrotreating units (UHDT) by MPC controllers (Model Predictive Control). It is presented a brief historical of conventional MPC controllers and infinite horizon controllers (IHMPC), as well as a brief description of the Diesel Hydrotreating process and the particulars of the application of process control for this type of industrial plant. It was then generated, step by step, one algorithm that summarized and aggregated control characteristics of various MPC controllers available in the open literature, in particular those that have been developed over the past few years by USPs laboratory of simulation and control of (LSCP), in order to obtain an algorithm suitable for solving the addressed control problem. In a computational simulation environment, the resulting algorithm allowed to simultaneously control and optimize continuous processes, being able to robustly stabilize the industrial plant and at the same time increase the profitability of its operation. For this purpose, an \"objective function\" was developed which increased the economic conversion of crude feed to hydrotreated product and minimized the consumption of raw materials, and this correlation was added to the control algorithm. The simulations allowed that the previously discussed control strategies could be tested and the results presented and discussed.
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Junior, Marcelo Ramalho Amora. "AvaliaÃÃo em unidade piloto da desativaÃÃo de catalisadores industriais de hidrotratamento." Universidade Federal do CearÃ, 2015. http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=18393.
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PetrÃleo Brasileiro S/A<br>O objetivo principal à determinar a atividade catalÃtica residual e as causas da desativaÃÃo de amostras de catalisadores de uma unidade de HDT de lubrificantes.
Foram realizadas corridas em unidade piloto, caracterizaÃÃo dos catalisadores e coletados dados do histÃrico operacional da unidade industrial. A atividade catalÃtica foi determinada atravÃs das conversÃes das reaÃÃes de HDA, HDS e HDN bem como pelos parÃmetros cinÃticos aparentes de um modelo de lei das potÃncias e lei de Arrhenius.
Os catalisadores dos leitos principais de entrada e saÃda dos reatores industrial foram os mais desativados e o menos desativado o do leito intermediÃrio sendo estabelecida a seguinte ordem de atividade catalÃtica residual: R1L3 (meio) > R1L2 (topo)  R2L2 (fundo).
Os resultados de teor e caracterÃsticas do coque, contaminantes e propriedades texturais sugerem que mecanismos distintos tenham causado a desativaÃÃo desses catalisadores: deposiÃÃo de metais e deposiÃÃo de coque.
Os mecanismos de desativaÃÃo foram fortemente influenciados pelo posicionamento das amostras no interior do leito catalÃtico. No inÃcio do leito, a contaminaÃÃo por metais (notadamente Si e As) revelou-se o principal mecanismo de desativaÃÃo. JÃ no final do leito, a deposiÃÃo de coque foi o mecanismo preponderante e a temperatura de reaÃÃo identificada como a principal causa para o maior envelhecimento do coque.<br>The main objective of this work is to study the residual catalyst activity and the mechanisms of deactivation of catalyst from a lube-oil hydroprocessing industrial unit.
In order to accomplish this, pilot plant tests were carried out followed by spent catalysts characterization. The residual catalytic activity was determined by HDA, HDS and HDN conversions and adjusted by a power law apparent kinetic model.
Pilot plant tests revealed different levels of residual activity for spent catalyst samples. Catalyst samples taken from the first and last of the five catalytic beds showed higher deactivation than others.
Catalyst characterization results pointed out two mechanisms as the main reason for the catalytic deactivation through the industrial reactor: poisoning by metal deposition (mainly Si and As) and coke deposition. Poisoning was the main deactivation mechanism for the first bed spent catalyst sample, while coke deposition was predominant at the last catalytic bed sample. Reactor temperature was identified as the most important operational parameter considering coke aging.
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Calheiros, Cleyla Janey Peixoto. "Estudo do processo de hidrotratamento de diesel através de simuladores comerciais e redes neurais artificiais." Universidade Federal de Alagoas, 2014. http://www.repositorio.ufal.br/handle/riufal/1190.
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Diesel plays an important role to the Brazil’s energy matrix, because it is one of the most consumed fuel at country. This study describes the hydrotreating process for petroleum refining using commercial software, PRO/II®. In addition, the artificial neural networks (ANN), using MATLAB®, were evaluated as tool for the development of virtual sensors and fault detection in chemical processes. The theoretical and practical assessment carried out in relation to the suitability of the software is justified by having acceptability in the oil and gas industry. For the oil hydrotreating associated with sulfur, the Diesel was represented by weight oil features; similar those used in refinery Abreu e Lima (RNEST). The goal of this study was to modeling in stationary condition for the reactor section the diesel hydrotreating process getting operating conditions to keep the sulfur concentration below of the ANP (Agência Nacional do Petróleo) specification, which is 10 ppm. The RNA applied to evaluate the virtual sensors was the MLP (Multi-Layer Perceptron), however, using the Levenberg-Marquardt Backpropagation (LMB) training algorithm. The coefficient of correlation was close to 1, so it means the network was satisfactory for this study. In the binary classification stage, the performance of RNA-LMB was efficient since a percentage of success above 93% was observed. In data clustering stage, used to define faults detection from parameters like flow of diesel, contaminants, pressure and temperature, the RNA-Kohonen was evaluated to check the sensitivity of the network to cluster the data with similarity. In a second stage, were inserted errors in the network, the temperature was the parameter with the greatest susceptibility to measurement errors in the industry. The lack of similarity for the input data in the RNA was well represented by self-organizing map (SOM). The simulations, as well as network training, adequately represent the analyzed processes.<br>Coordenação de Aperfeiçoamento de Pessoal de Nível Superior<br>O presente trabalho aborda o estudo do processo de hidrotratamento no refino de petróleo utilizando e avaliando software comercial, PRO/II®, e investiga a utilização da aplicação das redes neurais artificiais (RNA), em ambiente Matlab®, como ferramenta para o desenvolvimento de sensores virtuais e detecção de falhas em processos químicos. A avaliação teórica e prática realizada em relação à adequabilidade do software são justificadas pela sua aceitabilidade na área de petróleo e gás. Para a representação do diesel, combustível de maior interesse por ser o mais consumido dentro da matriz energética brasileira, foram utilizados dados associados ao petróleo pesado, obtidos da literatura, com características semelhantes ao que será utilizado na refinaria Abreu e Lima (RNEST). Petróleos com maiores índices de contaminantes como enxofre e nitrogênio estão cada vez mais presentes nas cargas das unidades de refino o que aumenta o interesse nos estudos referentes ao hidrotratamento (HDT). A principal variável estudada neste trabalho foi a avaliação da remoção do enxofre via HDT. O trabalho propôs uma modelagem estacionária da seção de reatores do processo de hidrotratamento de diesel obtendo condições operacionais que possibilite a manutenção do teor de enxofre abaixo da concentração de especificação da ANP, 10 ppm de enxofre no diesel. A RNA utilizada para a avaliação dos sensores virtuais foi a MLP (Multi-Layer Perceptron) com algoritmo de treinamento Levenberg-Marquardt backpropagation. A rede mostrou-se satisfatória, pois obteve um coeficiente de regressão próximo de um. Na etapa de classificação, a RNA, usando o algoritmo Levenberg-Marquardt backpropagation, através de uma classe binária, obteve um percentual de acertos acima de 93%, o que o classifica como bastante eficiente. Na análise da RNA, na etapa de agrupamento de dados utilizada para possíveis detecções de falhas, a rede utilizada foi a Kohonen onde foi avaliada a sensibilidade da rede em agrupar os dados com similaridade. Os parâmetros utilizados foram as vazões de diesel e contaminantes, pressão e temperatura. Numa segunda etapa foram inseridos erros na rede. A temperatura foi o parâmetro escolhido por ter maior susceptibilidade a erros de medição na indústria. O resultado obtido é representado por um mapa auto-organizável (SOM Self-Organizing Map) que identificou de forma satisfatória, através de cores, a falta de similaridade entre os dados inseridos na rede. As simulações desenvolvidas neste trabalho, bem como o treinamento da rede conseguiram representar adequadamente os processos estudados.
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Kokliukhin, Aleksandr. "Catalyseurs sulfures (Ni)MoW massiques et supportés, préparés à partir d'hétéropolyacides mixtes de Keggin H4SiMonW12-nO40, pour l'hydrotraitement des coupes lourdes." Electronic Thesis or Diss., Université de Lille (2018-2021), 2021. http://www.theses.fr/2021LILUR024.
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Les raffineurs doivent faire face au renforcement des exigences environnementales relatives à la teneur en soufre des carburants ainsi qu'à l'utilisation de pétrole brut plus lourd pour la production de carburants à l'aide de procédés catalytiques d'hydrotraitement. Une des approches pour améliorer l'activité catalytique est le développement de sulfures trimétalliques NiMoW. Sur des catalyseurs supportés sur alumine, l'utilisation de précurseurs mixtes, les hétéropolyacides (HPA) de Keggin H4SiMo1W11O40 et H4SiMo3W9O40, s'est avérée plus favorable à la formation d'une phase MoWS mixte hautement active que le mélange de deux précurseurs monométalliques H4SiMo12O40 et H4SiW12O40. Dans cette étude, un nouveau protocole pour la synthèse de précurseurs mixtes H4SiMonW12-nO40 avec n = 6 et 9 a été développé. Ces nouveaux composés ont été caractérisés par spectroscopie IR et Raman, ainsi que par DRX sur monocristal. Des catalyseurs d'hydrotraitement massiques et supportés ont été synthétisés à partir de cette série d’HPA. Concernant les catalyseurs non promus supportés sur alumine, l'influence du rapport atomique Mo/(Mo+W) sur la composition de la phase active a été étudié ainsi que son effet sur l'activité catalytique dans des réactions d'hydrotraitement de composés modèles (hydrodésulfuration du dibenzothiophène et hydrogénation du naphtalène). Il a été observé par HAADF que pour un rapport atomique Mo/(Mo+W) égal à 0,25 et 0,5, la structure de la phase active après sulfuration en phase gaz est une structure core-shell. Une augmentation de la teneur en molybdène jusqu'à un ratio Mo/(Mo+W) de 0,75 conduit à une structure désordonnée de la phase active, correspondant à une diminution de l'activité catalytique. En revanche, pour les catalyseurs obtenus à partir d'un mélange des HPA monométalliques, la phase active s’est avérée principalement constituée de cristallites monométalliques MoS et WS, quel que soit le rapport atomique Mo/(Mo+W), avec une activité inférieure à celle des catalyseurs préparés à partir de HPA mixtes.L'influence du rapport atomique Mo/(Mo+W) pour les systèmes promus au nickel, après sulfuration en phase liquide afin de se rapprocher au maximum des conditions industrielles, a également été étudiée. L'introduction de Ni n'empêche pas la formation de la phase active mixte MoWS, ce qui a été confirmé par HAADF et EXAFS. De plus, l’effet d’inhibition dû à la présence de composés azotés dans la charge à hydrotraiter a été analysé. Il a été observé que les catalyseurs NiMoW/Al2O3 riches en tungstène sont plus résistants à la présence des composés azotés et que le choix de la composition du catalyseur doit être adapté selon la composition de la charge traitée.La dissolution par acide du support alumine a permis d'obtenir à partir d'échantillons sulfurés MonW12-n/Al2O3 des catalyseurs massiques MoWS avec une concentration en phase active supérieure à 90%. Des analyses par ToF-SIMS et EXAFS ont montré que la phase MoWS2 mixte est présente à la fois dans les catalyseurs synthétisés à partir des HPA mixtes et dans les échantillons obtenus à partir du mélange de deux HPA. Cependant, la concentration en sulfures mixtes dans le premier cas est beaucoup plus élevée, du fait que des cristallites mixtes étaient déjà présentes dans le solide supporté, alors que dans le cas du mélange des deux HPA, une phase mixte se forme à la suite du frittage des particules lors de la re-sulfuration. La concentration élevée en sulfures mixtes a permis d’obtenir une activité plus élevée des catalyseurs dans des réactions modèles.Enfin, le remplacement de l'alumine par une silice mésostructurée a permis d'augmenter l'activité des catalyseurs MoW non promus. Cependant, les valeurs similaires du degré de sulfuration, de la dispersion ainsi que des résultats des tests catalytiques entre les catalyseurs obtenus à partir des deux types de précurseurs semblent indiquer que la formation de phase mixte MoWS ne se produit pas sur ce type de support<br>Refiners have to face the strengthening of environmental requirements for the sulfur content in fuels together the use of heavier crude oil for producing market fuels using hydrotreatment catalytic processes. One of the approaches to improve catalytic activity is the development of bulk and supported ternary NiMoW sulfide catalysts following the recent introduction of industrial mixed bulk NiMoW catalysts NEBULA and Celestia. Previously, for supported alumina catalysts, the use of mixed precursors, H4SiMo1W11O40 and H4SiMo3W9O40 Keggin heteropyacids, has shown a better positive effect on the formation of a highly active mixed MoWS phase than the use of two corresponding monometallic H4SiMo12O40 and H4SiMo12O40 precursors. In this study, a new protocol for the synthesis of mixed Keggin-type H4SiMonW12-nO40 precursors with n = 6 and 9 has been developed. The new compounds were characterized by IR and Raman spectroscopy, as well as single-crystal XRD. Bulk and supported hydrotreating catalysts based on the whole series of H4SiMonW12-nO40 HPAs were synthesized. The influence of the atomic Mo/(Mo+W) ratio on the composition and structure of the active phase and its effect on the catalytic activity of unpromoted alumina supported catalysts in model hydrotreating reactions (hydrodesulfurization of dibenzothiophene and hydrogenation of naphthalene) were studied in detail. It was found that for an atomic Mo/(Mo+W) ratio equal to 0.25 and 0.5, the structure of the active phase under gas-phase sulfidation conditions is a core-shell structure, according to HAADF. A further increase in the molybdenum content up to 0.75 leads to disordering of the active phase structure, which has a negative effect on the catalytic activity. In contrast, for the catalysts obtained from a mixture of monometallic H4SiMo12O40 and H4SiMo12O40 HPAs, the active phase consisted mainly of monometallic MoS2 and WS2 crystallites, regardless of the atomic Mo/(Mo+W) ratio, as a result of which the catalysts showed lower activity compared to the samples prepared from mixed HPAs.The study of the influence of atomic Mo/(Mo+W) ratio for Ni-promoted systems, under the liquid-phase sulfidation in order to be as close as possible to industrial conditions, is also reported. It was shown that the introduction of Ni does not prevent the formation of a mixed MoWS active phase, which was confirmed by HAADF and EXAFS. Moreover, testing in the presence of a nitrogen-containing component made it possible to further study the inhibition on catalytic reactions. It was found that tungsten-rich NiMoW/Al2O3 catalysts are more resistant to the action of nitrogen-containing compounds indicating that the choice of the catalyst composition should be adapted to the composition of the processed feedstock.The use of acid (HF) etching of the alumina support made it possible to obtain from sulfided MonW12-n/Al2O3 samples bulk MoWS catalysts with an active phase concentration of more than 90%. ToF-SIMS and EXAFS showed that the mixed MoWS2 phase is present both in the catalysts synthesized from the mixed HPAs and in the samples obtained from the mixture of two HPAs. However, the concentration of mixed sulfides in the first case is much higher, due to the fact that mixed crystallites have already been formed, whereas in the case of a mixture of two HPAs, a mixed phase is formed as a result of the sintering of particles during re-sulfidation. The high concentration of mixed sulfides made it possible to provide a higher activity of catalysts in model reactions.Replacing alumina with mesostructured silica made it possible to increase the activity of unpromoted MoW catalysts. At the same time, similar values of the degree of sulfidation and dispersion, as well as the results of catalytic tests, seem to indicate that the formation of mixed MoWS2 phase does not occur on this type of supports, which requires additional research to be confirmed
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Garcia, de Castro Insua Ricardo Antonio. "Catalyseurs d’hydrotraitement modèles à base du Mo et supportés sur α-Al2O3 : étude sur l’incorporation du cobalt, phosphore et triéthylène glycol par une approche de science de surfaces". Electronic Thesis or Diss., Sorbonne université, 2020. http://www.theses.fr/2020SORUS145.
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La genèse de la phase active dans les catalyseurs d’hydrotraitement est influencée par la nature du support. Néanmoins, une description à l’échelle moléculaire des interactions métal-support est encore balbutiante dû aux sites de sorption mal définis du support industriel γ-Al2O3. Une approche de science des surfaces en phase aqueuse a contourné cette limitation en utilisant des monocristaux de α-Al2O3 selon 4 orientations : C(0001), A(112 ̅0), M(101 ̅0), et R(11 ̅02) pour étudier la genèse de MoS2 en contrôlant la spéciation des sites de surface. Cette approche a montré que des propriétés de MoS2 sont contrôlées par les interactions Mo-support qui sont à la fois déterminées par le type de OH de surface. Ce travail vise à se rapprocher aux catalyseurs industriels en intégrant du cobalt, du phosphore, et du TEG. Des techniques de caractérisation de surface ont été utilisées pour étudier cette dépendance. Il est montré que le phosphore interagit de manières diverses selon le support, ce qui conduit à un effet sur la sulfuration. Au contraire, la promotion de MoS2 par le Co ne dépend que de la sulfuration du Mo. Enfin, il est montré que l’absence de l’étape de calcination et l’ajout de TEG diminue les interactions métal-support, menant à des taux de sulfuration plus élevés. L’activité catalytique des catalyseurs promus a été étudiée en hydrodésulfuration du thiophène. Elle est plus importante chez les catalyseurs supportés sur la face A(112 ̅0), ce qui suggère que les interactions métal-support intermédiaires mènent à des activités plus élevées. Ces résultats peuvent donner lieu à la synthèse de catalyseurs plus efficaces au travers du contrôle de la morphologie du support<br>The genesis of the active phase in hydrotreating catalysts is deeply influenced by the nature of the support. However, a fine description of active phase-support interactions at the molecular level is still missing since the traditional support γ-Al2O3 exhibits ill-defined sorption sites. A surface-science approach in aqueous phase circumvented this limitation by using α-Al2O3 single crystals with four different orientations: C(0001), A(112 ̅0), M(101 ̅0), and R(11 ̅02) as surrogates to study the genesis of MoS2 exerting control over surface sites. Such approach revealed that properties of MoS2 were dictated by Mo-support interactions which are, in turn, determined by the nature of surface -OH. The present work aims to take a step further in closing the gap between model and industrial catalysts by incorporating cobalt, phosphorus and TEG in model catalyst formulation. Surface-sensitive techniques are used to expose such dependencies. It is shown that phosphorus interacts differently depending on support orientation, leading to a surface-dependent sulfidation. Conversely, it is shown that cobalt promotion of MoS2 is exclusively dependent on Mo sulfidation. At last, it is shown how omitting calcination and TEG incorporation reduces metal-support interactions leading to higher sulfidation. The catalytic activity of promoted catalysts is studied through a thiophene hydrodesulfurization reaction revealing that A(112 ̅0)-based catalysts display the highest activity. In that sense, intermediate metal-support interactions are key to achieve higher catalytic performance. These results could lead to a new generation of hydrotreating catalysts through control of support morphology
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Chagas, Luciano Honorato. "Produção, caracterização e determinação de propriedades físico-químicas de catalisadores e suportes utilizados em processos de hidrotratamento." Universidade Federal de Juiz de Fora (UFJF), 2013. https://repositorio.ufjf.br/jspui/handle/ufjf/4318.
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Previous issue date: 2013-11-22<br>O grande interesse na hidrodessulfurização (HDS) de gasolina é realizar remoção profunda de enxofre e, ao mesmo tempo, reduzir a perda do numero de octanos que ocorre no processo de HDS minimizando a hidrogenação (HID) de olefinas, as quais são benéficas para a octanagem. Além do componente ativo e do promotor, o suporte deve ser considerado uma parte integral do catalisador. Nesse sentido, diversos suportes (incluindo aluminas e óxidos mistos) foram preparados a partir da calcinação de diferentes precursores. Uma amostra de Boehmita comercial foi usada como precursora de polimorfos de alumina. Para comparação, três outros precursores foram sintetizados a partir de diferentes métodos. Particularmente, o uso de excesso de ureia promoveu uma forma muito cristalina de carbonato básico de alumínio. Cada precursor foi calcinado em várias temperaturas gerando polimorfos de alumina, os quais foram analisados estruturalmente por DRX e RMN de 27Al. Devido ao interesse em suportes para catalisador, atenção especial foi dada à fase γ-Al2O3, a qual em adição a investigação estrutural foi submetida à análise textural. Essas quatro amostras de γ-Al2O3 foram utilizadas como suportes para catalisadores do tipo CoMo, que foram testados em reações de HDS de tiofeno e HID de cicloexeno. Os testes catalíticos mostraram que as atividades catalíticas crescem com o aumento do diâmetro médio de poros das fases CoMo/γ-Al2O3, e estão diretamente relacionados à dispersão do molibdênio sobre o suporte. Os resultados mostraram que a partir de diferentes rotas de síntese, e usando uma rota comum de calcinação, podem-se obter materiais com a mesma composição, mas com diferentes propriedades estruturais e texturais. Além disso, catalisadores do tipo CoMo suportados, contendo 20 % de MoO3 e 3 % de CoO, foram preparados por impregnação ao ponto úmido com soluções aquosas de molibdênio e cobalto sobre óxidos mistos obtidos a partir de hidrotalcitas. Os precursores contendo variadas quantidades de Mg, Co e Al ou Ni, Co e Al foram sintetizados pelo método de hidrólise de ureia. A calcinação leva a óxidos mistos cujas características estruturais dependem da composição. A caracterização dos suportes foi feita pelas técnicas de BET, DRX, RMN, IV, UV-vis/DRS e TPR. As amostras sulfetadas foram usadas como catalisadores em reações simultâneas de HDS de tiofeno e HID de cicloexeno. Os resultados foram comparados com catalisadores convencionais CoMo/γ-Al2O3, indicando que as atividades catalíticas dependem dos métodos de preparação dos precursores e suportes. Na série Mg-Co-Al o catalisador com maior quantidade de magnésio mostrou as maiores atividades de HDS e HID, sugerindo que a basicidade está associada com a performance catalítica. Adicionalmente, a amostra sem magnésio e contendo alta quantidade de cobalto exibiu as menores atividades e a maior seletividade (HDS/HID = 3,86). Os resultados indicam que o excesso de cobalto diminui a atividade enquanto a presença de magnésio contribui para aumentá-la. Por outro lado, a série Ni-Co-Al exibiu as menores razões HDS/HID. Nesse caso, as altas atividades para hidrogenação são atribuídas às altas quantidades de níquel. Adicionalmente, uma comparação entre catalisadores contendo 10 % de MoO3 e 3 % de CoO, suportados em óxidos mistos derivados de HDL e um catalisador suportado em alumina, revela que o suporte mais ácido tem maior influência sobre a capacidade de hidrogenação do catalisador. Entretanto, apesar da composição e das características estruturais dos suportes, o método de preparação pode influenciar significativamente no desempenho de um catalisador suportado.<br>The great interest in hydrodesulfurization (HDS) of gasoline is to perform a deep sulfur removal and, at the same time, to reduce the loss of the octane number occurring in the HDS process, by minimizing the hydrogenation of olefins which are beneficial to this property. Besides the active component and the promoter, the support has to be considered an integral part of the catalyst. In this sense, several supports (enclosing aluminas and mixed oxides) were prepared from calcination of different precursors. A commercial sample of Boehmite was used as precursor of alumina polymorphs. For comparison, three other precursors were synthesized from different methods. Particularly, the use of excess of urea promoted a very crystalline form of basic aluminum carbonate. Each precursor of alumina was calcined at various temperatures generating alumina polymorphs, which were structurally analyzed by XRD and 27Al MAS NMR. Due to interest in catalysis supports, special attention was given to the γ-Al2O3 phase, which in addition to structural investigation was subjected to textural analysis. These four γ-Al2O3 samples were used as catalyst supports like CoMo, which were tested in reactions of HDS of thiophene and HID of cyclohexene. The catalytic tests show that catalytic activities increase with pore diameters of CoMo/γ-Al2O3 phases and are directly related to dispersion of molybdenum on the support. The results showed that, from different synthesis procedures and common route of calcination, one can obtain materials with the same composition but with different structural and textural properties. Furthermore, supported CoMo catalysts containing 20 % of MoO3 and 3 % of CoO were prepared by incipient wetness impregnation of molybdenum and cobalt aqueous solutions over mixed oxides obtained from hydrotalcite precursors. The precursors, containing varying amounts of Mg, Co and Al or Ni, Co and Al cátions, were synthesized by urea hydrolysis method. The calcination led to mixed oxides whose structural characteristics depend on the composition. Characterization of the supports by BET, XRD, NMR, FTIR, UV-vis/DRS and TPR techniques was carried out. The sulfided samples were used as catalysts in simultaneous hydrodesulfurization of thiophene and hydrogenation of cyclohexene. The results were compared with conventional CoMo/γ-Al2O3 catalysts, which indicate that the catalytic activities depend on the preparation method of the precursors and supports. In the Mg-Co-Al series, the high magnesium content catalyst show higher HDS and HYD activities, suggesting that the support basicity is associated with catalytic performance. Furthermore, the free magnesium and high cobalt content catalyst show lower activities and higher selectivity (HDS/HYD = 3.86). The results indicate that the excess of cobalt decreases the activities while the presence of magnesium contributes to improve them. Otherwise, the Ni-Co-Al series show the smaller HDS/HYD ratios. In this case, the higher hydrogenation activities are assigned to high nickel content. Additionally, a comparison between catalysts containing 10 % of MoO3 and 3 % of CoO, supported on mixed oxides derived of LDH and a catalyst supported on alumina reveals that the most acidic support (alumina) has great influence over hydrogenation capacity of the catalyst. However, besides the composition and structural characteristics of the supports, the preparation method can to influence significantly the performance of a supported catalyst.
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Arancon, Rick Arneil. "Exploration of Transition Metal Sulfide Catalysts Prepared by Controlled Surface Chemistry." Thesis, Lyon, 2018. http://www.theses.fr/2018LYSEN063.
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L'hydrotraitement est un procédé catalytique important dans le raffinage du pétrole qui utilise des catalyseurs bimétalliques sulfurés NiWS ou NiMoS (ou CoMoS) supportés sur alumine. Leur mode conventionnel de préparation implique l’imprégnation d'une solution aqueuse de sels de Mo/W et de Ni/Co, puis l’activation par un agent sulfo-réducteur (H2S/H2). Pour répondre aux exigences environnementales et améliorer l'efficacité de l'hydrotraitement, des améliorations permanentes de la performance de ces systèmes catalytiques sont attendues. Ce travail se concentre sur la préparation de catalyseurs d'hydrotraitement hautement actifs par une approche de chimie de surface contrôlée (CSC) qui implique l'imprégnation successive de précurseurs moléculaires de MoV et NiII en solvant organique sur un support silice-alumine traité thermiquement. Dans la première partie de cette thèse, la genèse de la phase active du catalyseur CSC et conventionnel Mo et NiMo est étudiée par quick-XAS combinée à d’autres techniques (chimiométrie, XPS, RPE, STEM-HAADF, modélisation moléculaire). Nous proposons ainsi des structures moléculaires depuis les précurseurs oxydes de Mo et Ni supportés jusqu’aux nombreuses espèces intermédiaires (oxysulfure et sulfures) en fonction de la température. Cette analyse multi-technique permet d'abord de révéler les spécificités de la genèse des catalyseurs CSC et conventionnels qui peuvent expliquer leurs différentes activités catalytiques. Ensuite, elle révèle également de nouvelles connaissances sur les mécanismes d’insertion du Ni dans la phase NiMoS en fonction de la préparation. Dans la seconde partie, la possibilité de remplacer Co et Ni comme promoteurs est explorée. Ceci est entrepris en synthétisant des catalyseurs alternatifs de type XYMoS, où X et Y sont des métaux de transition 3d. Comme suggéré par des études de modélisation quantiques antérieures, certaines formulations XYMoS peuvent présenter un effet de synergie analogue à ceux des phases actives CoMoS et NiMoS. L’étude des formulations les plus prometteuses méritent d'être approfondies afin de mieux comprendre leur fonctionnement<br>Hydrotreating is an important catalytic process in petroleum refining which uses sulfided bimetallic catalysts NiWS or NiMoS (or CoMoS) supported on alumina. Their conventional preparation involves an incipient wetness impregnation of an aqueous solution of Mo/W and Ni/Co salts, and then activation by a sulfo-reductive agent (such as H2S/H2). To meet environmental regulations and improve the energy efficiency of hydrotreatment, permanent improvements on the performance of these catalytic systems are expected. This work is thus focused on the preparation of highly active hydrotreating catalysts through a controlled surface chemistry (CSC) approach; which involves the successive impregnation of Mo5+ and Ni2+ molecular precursors in an organic solvent on a thermally treated silica-alumina support. In the first part of this thesis, the active phase genesis of CSC and conventional Mo and NiMo catalysts is studied by in situ quick-XAS combined with various other techniques (chemometrics, XPS, EPR, STEM-HAADF, molecular modeling). We thus propose molecular structures from the oxide of supported Mo and Ni precursors up to the numerous intermediate sulfided species as a function of temperature. This multi-technique analysis enables first to reveal the specific features of the genesis of CSC and conventional catalysts which may explain their different catalytic activities. Then, it also reveals new insights into the mechanisms of Ni promoter incorporation into the NiMoS phase as a function of the preparation. In the second part, the feasibility of replacing Co and Ni as promoters is explored. Using the CSC method, we attempted to synthesize alternative catalysts of the form XYMoS ternary sulfides, where X and Y are 3d transition metals. As suggested by previous quantum simulations, certain XY formulations possibly reveal a synergy effect as observed in CoMoS and NiMoS active phases. The most promising formulations merit further investigations
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Baubet, Bertrand. "Influence de la morphologie 2D de la phase active sur la sélectivité des catalyseurs sulfures en HDS des essences." Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10067.
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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<br>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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ARAÚJO, Alexsandro Fausto de. "Modelagem matemática e simulação computacional do reator de conversão de diolefinas e do reator de hidrotratamento de nafta." Universidade Federal de Pernambuco, 2016. https://repositorio.ufpe.br/handle/123456789/17982.
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Previous issue date: 1998-11-13<br>Com a crescente exigência dos mercados e da sociedade por produtos derivados do petróleo cada vez mais livres de contaminantes que prejudicam o meio ambiente e a qualidade dos mesmos, os parques de refino de petróleo vêm investindo cada vez mais em tecnologias que permitam uma produção mais limpa, rentável e econômica. Desse modo, O hidrotratamento tem assumido um papel cada vez mais importante dentro das refinarias, sendo aplicado em diversos cortes do petróleo, desde os mais leves até os mais pesados. O hidrotratamento consiste na adição de hidrogênio na carga a ser hidrotratada com o propósito de, através de reações de hidrogenação, reduzir ou eliminar os componentes contaminantes presentes na carga, como o enxofre, nitrogênio, oxigênio, olefinas, diolefinas e metais. A adição de hidrogênio é feita em cocorrente descendente, onde a carga e o hidrogênio entram misturados e pré aquecidos no topo do reator a uma razão pré-definida (Razão H2/Carga), sendo esta forma a mais utilizada em escala industrial devido aos seus inúmeros benefícios. O foco da unidade de HDT é o reator, pois é nele que os contaminantes são removidos da carga. O tipo de reator mais utilizado é o de leito fixo (Trickle Bed Reactor - TBR). A nafta é a principal matéria prima do setor petroquímico nacional, de modo que todas as unidades instaladas são baseadas nela. A partir dela são produzidos os componentes da primeira geração do setor petroquímico. O HDT de nafta ainda é um tema pouco explorado mas que vem recebendo maior importância nos últimos anos. Por isso, este trabalho foi desenvolvido sobre esse tema, construindo e simulando modelos dinâmicos de reatores de leito fixo, com alimentação em cocorrente de uma unidade reacional de HDT de nafta, composta por um reator trifásico de conversão de diolefinas, utilizado para o pré-tratamento da nafta de coqueamento retardado e dois reatores bifásicos (G-S) de HDT de nafta, dispostos em série com resfriamento por quenchs independentes entre os leitos dos reatores e entre os reatores, para a redução de teores de enxofre, nitrogênio e olefinas presentes na nafta através das reações de hidrodessulfurização, hidrodesnitrogenação e saturação de olefinas. Foram construídos dois programas em ambiente MATLAB®, um para simular o reator trifásico de conversão diolefinas e outro para os reatores bifásicos de HDT de nafta, ambos simularam correntes de alimentação de nafta com diferentes níveis de contaminação, para que fossem avaliados os efeitos. Os programas simularam os perfis dinâmicos das temperaturas das fases envolvidas e das concentrações dos contaminantes e hidrogênio. Os resultados obtidos para o reator de conversão de diolefinas e os reatores de HDT de nafta se mostraram bem coerentes com relação aos fenômenos envolvidos. O reator de conversão de diolefinas atingiu o estado estacionário aos 80 minutos e os reatores de HDT de nafta aos 2 minutos, com os teores de contaminantes próximos de zero na saída do reator. Os resultados das simulações realizadas para os dois tipos de nafta apresentaram perfis dinâmicos semelhantes diferindo apenas quanto à temperatura mais elevada atingida no início do primeiro reator de HDT de nafta no caso da nafta com maior teor de contaminação.<br>With the growing demand of markets and society by oil products increasingly free of contaminants that harm the environment and their quality, oil refining plants have been increasingly investing in technologies to cleaner production, profitable and economical. Thus, the hydrotreating has assumed an increasingly important role in the refinery and is used in many petroleum cuts, from the lightest to the heaviest. The hydrotreating is the addition of hydrogen in the load to be hydrotreated in order to, via hydrogenation reactions, reduce or eliminate the contaminating components present in the load, such as sulfur, nitrogen, oxygen, olefins, diolefins and metals. The addition of hydrogen is done in descending current, where load and hydrogen enter mixed and pre heated at the top of the reactor to a pre-defined (ratio H2/Oil), and this way the most used at industrial scale due to its numerous benefits. The focus of the HDT unit is the reactor, because that is where the contaminants are removed from the load. The most used type of reactor is the fixed bed (Trickle Bed Reactor - TBR). Naphtha is the main raw material of the national petrochemical industry, so that all installed units are based on it. From there, the components of the first generation of the petrochemical industry are produced. The naphtha HDT is still a subject little explored but it's getting more important in recent years. Therefore, this study was conducted on this issue, building and simulating dynamic models of fixed bed reactors with feed in cocurrente of a reactional unit of HDT naphtha, consisting of a three-phase reactor diolefins conversion, used for pretreatment naphtha delayed coking and two dual-phase reactors (G-S) naphtha HDT arranged in series with cooling by independent quenchs between beds of the reactor and between the reactors to reduce contents of sulfur, nitrogen and olefins present in the naphtha through reactions of hydrodesulfurization, hidrodesnitrogenação and saturation of olefins. Were built two programs in MATLAB®, one to simulate the three-phase reactor diolefins conversion and one for the dual-phase reactors naphtha HDT, both simulated currents naphtha feed with different levels of contamination, so that the effects are assessed. The simulated programs dynamic profiles of the temperatures of the phases involved and the concentrations of contaminants and hydrogen. The results obtained for diolefins conversion reactor and the reactors of naphtha HDT were well consistent with relation to the phenomena involved. The diolefins conversion reactor reached steady state at 80 minutes and the HDT reactors naphtha after 2 minutes, with near zero contaminant levels in the reactor output. The results of simulation performed for the two types of naphtha showed similar dynamic profiles differing only as to the highest temperature reached at the beginning of the first naphtha HDT reactor in the case of naphtha higher contamination level.
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Ouafi, Driss. "Caracterisation par spectroscopie infrarouge des catalyseurs d'hydrotraitement ni-w supportes, a l'etat oxyde ou sulfure." Caen, 1986. http://www.theses.fr/1986CAEN2021.
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El, Gemayel Gemayel. "Integration and Simulation of a Bitumen Upgrading Facility and an IGCC Process with Carbon Capture." Thèse, Université d'Ottawa / University of Ottawa, 2012. http://hdl.handle.net/10393/23274.
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Hydrocracking and hydrotreating are bitumen upgrading technologies designed to enhance fuel quality by decreasing its density, viscosity, boiling point and heteroatom content via hydrogen addition. The aim of this thesis is to model and simulate an upgrading and integrated gasification combined cycle then to evaluate the feasibility of integrating slurry hydrocracking, trickle-bed hydrotreating and residue gasification using the Aspen HYSYS® simulation software. The close-coupling of the bitumen upgrading facilities with gasification should lead to a hydrogen, steam and power self-sufficient upgrading facility with CO2 capture. Hydrocracker residue is first withdrawn from a 100,000 BPD Athabasca bitumen upgrading facility, characterized via ultimate analysis and then fed to a gasification unit where it produces hydrogen that is partially recycled to the hydrocracker and hydrotreaters and partially burned for power production in a high hydrogen combined cycle unit. The integrated design is simulated for a base case of 90% carbon capture utilizing a monoethanolamine (MEA) solvent, and compared to 65% and no carbon capture scenarios. The hydrogen production of the gasification process is evaluated in terms of hydrocracker residue and auxiliary petroleum coke feeds. The power production is determined for various carbon capture cases and for an optimal hydrocracking operation. Hence, the feasibility of the integration of the upgrading process and the IGCC resides in meeting the hydrogen demand of the upgrading facility while producing enough steam and electricity for a power and energy self-sufficient operation, regardless of the extent of carbon capture.
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Mennour, Ammar. "Caracterisation par spectroscopie infrarouge d'alumines modifiees et de catalyseurs w(mo) - ni(co) sulfures supportes sur alumine." Caen, 1987. http://www.theses.fr/1987CAEN2019.
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Kurdi, Mohamad. "Sur l'utilisation des sulfures en catalyse d'hydrotraitement le trisulfure du niobium /." Grenoble 2 : ANRT, 1988. http://catalogue.bnf.fr/ark:/12148/cb376148133.
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Hantzer, Sylvain. "Nouveaux materiaux pour la reaction d'hydrodesulfuration (hds)." Université Louis Pasteur (Strasbourg) (1971-2008), 1988. http://www.theses.fr/1988STR13120.
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Nouveau modele de phase active obtenu par interpretation des resultats de rmn du **(59)co et de microscopie electronique haute resolution pour des catalyseurs d'hydrotraitement a base de sulfure de molybdene et de cobalt. Application a d'autres systemes : nire, core, rhre et rhmo. Etude de l'empoisonnement par la porphyrine de catalyseur nimo/al::(2)o::(3)
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Scholte, Paola. "Arsenic effects on a NiMo/Al2O3 hydrotreating catalyst." Master's thesis, 2011. http://hdl.handle.net/10048/1718.
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Hydrotreating is the response to the necessity of a cleaner feed for downstream processes and reduced pollution. Hydrotreating catalysts are vital in this process; hence catalyst deactivation is a key issue. The principal objective of this research was the experimental study of hydrotreating catalyst deactivation due to arsenic compounds. The hydrotreating of light gas oil, in the presence and absence of an arsenic compound over a commercial NiMoS catalyst, was investigated in a trickle bed reactor (temperature 315-360˚C, space velocity = 1-3 h-1, pressure = 3MPa). Kinetics of first order for nitrogen and sulphur were found and activation energies values of 32 kj/mol and 76 kj/mol respectively. Studies of activity changes, suggested that arsenic mainly affects the conversion of sulfur compounds; which might indicate that arsenic prefers mainly the S edge of the catalysts. Activation energy values decreased after arsenic introduction, which may suggest pore plugging of the catalyst.<br>Chemical Engineering
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Attanatho, Lalita. "Performances and kinetic studies of hydrotreating of bio-oils in microreactor." Thesis, 2012. http://hdl.handle.net/1957/33050.
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Hydrotreating reaction of vegetable oil is an alternative method for the production of
renewable biodiesel fuel. This reaction involves conversion of triglycerides into
normal alkanes, leads to a deoxygenated and stable product, which is fully compatible
with petroleum derived diesel fuel. The hydrotreating process uses hydrogen to
remove oxygen from triglyceride molecules at elevated temperature in the presence of
a solid catalyst.
This work focused on the development of microtechnology-based chemical reaction
process for liquid biofuel production from oil-based biofuel feedstock. A hydrotreating
reaction of oleic acid and triolein as model compounds and jatropha oil as real
feedstock was studied in a continuous flow microchannel reactor of inner diameter
500 ��m and of varied length; 1.5 - 5 m. The microchannel reactor was fabricated from
SS-316. The walls of the microreactor were coated with a thin Al���O��� film, which was
then impregnated with Ni-Mo catalyst containing phosphorus as promoter. The
reactions were carried out in the temperature range of 275-325 ��C, residence time in
the range of 11-40 s and at constant system pressure of 500 psig.
The results showed that the microchannel reactor was suitable for the hydrotreating
process. Complete conversion of the fatty acid hydrotreating reaction was achieved at
a reaction temperature of 325 ��C. Hydrotreating of fatty acids occurred primarily via
hydrodeoxygenation and the main liquid products were octadecane and
heptadecane. Fatty alcohol, fatty acid and long chain esters were formed as reaction
intermediates. Hydrotreating of triglycerides proceeded via the hydrocracking of
triglycerides into diglycerides, monoglycerides and fatty acids. Then fatty acids were
subsequently deoxygenated to hydrocarbons. The conversion of fatty acids and
triglycerides increased with increasing temperatures.
A detailed mathematical model was developed to represent this two-phase chemical
reaction process. The mathematical model was entirely based on first principles, i.e.
no adjustable or correlation parameters were used. Kinetic parameter estimation was
performed and the predicted results were in good agreement with experimental
results.<br>Graduation date: 2013<br>Access restricted to the OSU Community, at author's request, from Sept. 17, 2012 - Sept. 17, 2013
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Jarullah, Aysar Talib, Iqbal M. Mujtaba, and Alastair S. Wood. "Improving fuel quality by whole crude oil hydrotreating: A kinetic model for hydrodeasphaltenization in a trickle bed reactor." 2012. http://hdl.handle.net/10454/6034.
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Fossil fuel is still a predominant source of the global energy requirement. Hydrotreating of whole crude oil has the ability to increase the productivity of middle distillate fractions and improve the fuel quality by simultaneously reducing contaminants such as sulfur, nitrogen, vanadium, nickel and asphaltene to the levels required by the regulatory bodies. Hydrotreating is usually carried out in a trickle bed reactor (TBR) where hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM) and hydrodeasphaltenization (HDAs) reactions take place simultaneously. To develop a detailed and a validated TBR process model which can be used for design and optimization of the hydrotreating process, it is essential to develop kinetic models for each of these reactions. Most recently, the authors have developed kinetic models for all of these chemical reactions except that of HDAs. In this work, a kinetic model (in terms of kinetic parameters) for the HDAs reaction in the TBR is developed.
A three phase TBR process model incorporating the HDAs reactions with unknown kinetic parameters is developed. Also, a series of experiments has been conducted in an isothermal TBR under different operating conditions affecting the removal of asphaltene. The unknown kinetic parameters are then obtained by applying a parameter estimation technique based on minimization of the sum of square errors (SSEs) between the experimental and predicted concentrations of asphaltene compound in the crude oil.
The full model with the estimated kinetic parameters is then applied to evaluate the removal of asphaltene (thus affecting fuel quality) under different operating conditions (than those used in experiments).
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"Badoga, Sandeep_PhD_thesis_April_2015." Thesis, 2015. http://hdl.handle.net/10388/ETD-2015-04-2019.
Full textAbstract:
Bitumen-derived heavy gas oil contains large amounts of sulfur (~4.0 wt.%) and nitrogen (~0.4 wt.%), which need to be lowered before it becomes suitable as a feedstock for refineries. The most widely used upgrading process is hydrotreating, and the conventional catalyst used for hydrotreating is Ni or Co and Mo or W supported on γ-Al2O3. Additionally, environmentally driven regulations impose strict limits on sulfur and nitrogen levels in transportation fuels. Therefore, the main focus of this work was to enhance the activity of a NiMo supported catalyst through its modification and to improve its selectivity to removal of bulky sulfur- and nitrogen-containing compounds from heavy gas oil under industrial hydrotreating conditions. This work was divided into four phases, and this thesis summarizes the research outcomes of each phase.
The first phase examined the effects of chelating ligands, specifically, ethylenediaminetetraacetic acid (EDTA), on hydrotreating activity and the sulfidation mechanism. EDTA was seen to have a beneficial effect on hydrotreating activity. Detailed mechanistic aspects of interactions between support and EDTA, EDTA and metallic species, support and metal, support and active phase, and metallic species and metallic species at different reaction conditions, were also studied. Characterization by XANES revealed that the presence of a chelating agent delayed nickel sulfidation, which was the main cause of improvement in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities. It also showed that EDTA plays a role in redistribution of active phases during sulfidation and favors the formation of octahedral molybdenum oxides.
The second phase studied the effects of support modification and combinations of different supports and EDTA. In this phase, several mesoporous materials, including M-SBA-15 (M= Al, Ti and Zr), mesoporous mixed metal oxides (TiO2-Al2O3, ZrO2-Al2O3 andSnO2-Al2O3) and mesoporous metal oxides (ZrO2, Al2O3), were synthesized and used as support materials for a NiMo catalyst. NiMo/M-SBA-15 catalysts showed higher HDS and HDN activities and, the increase in activity is attributed to incorporation of heteroatoms in an SBA-15 matrix, which resulted in increase in metal support interaction, acidic strength and dispersion of active metals. The addition of EDTA to these catalysts helps in the formation of octahedral molybdenum oxide, which are easily reducible during sulfidation. This is evident from the XANES Mo LIII-edge study of the oxide catalysts. The increase in hydrodenitrogenation (HDN), hydrodesulfurization (HDS) and hydrodearomatization (HDA) activities as compared to that shown by the NiMo/γ-Al2O3 catalyst were also observed on addition of EDTA in large-pore, high-surface-area mesoporous zirconia supported NiMo catalysts. The incorporation of different metal oxides in alumina, as in the case of mixed metal oxides, resulted in a change in acidic strength and metal support interactions. It was observed with acridine-FTIR analysis that the catalysts with higher acidic strength tightly held acridine at high temperatures. This implies that catalysts with higher acidity are prone to inhibition by nitrogen-containing compounds present in feed, which will affect catalytic activity. The HDS and HDN activities for hydrotreating of heavy gas oil suggest that mesoporous alumina and titania-alumina supported catalysts perform better as compared to the conventional NiMo/γ-Al2O3 catalyst. Therefore, the effects of EDTA to Ni molar ratio (EDTA/Ni = 0 to 2) on the activities of the NiMo/MesoAl2O3 and NiMo/MesoTiO2-Al2O3 catalysts were studied, and EDTA was observed to have a negative impact on catalytic activity for these catalysts. This is attributed to a decrease in the active metal dispersion in these catalysts caused by the addition of EDTA. The catalysts NiMo/MesoAl2O3 and NiMo/MesoTiO2-Al2O3 without EDTA showed high active metal dispersion due to their high surface area and ordered structure.
The third phase studied the combined effects of phosphorus and EDTA on the hydrotreating activity of NiMo supported catalysts. The effects of method of phosphorus addition (sequential and co-impregnation method) were also studied. When phosphorus was added using a co-impregnation method, as in the catalyst NiMoP/MesoAl2O3(CI), an increase in HDN, HDA and HDS activities was observed. However, the catalysts containing both EDTA and phosphorus showed a decrease in HDS and HDN activities.
The fourth phase included a kinetic study using the Power Law and L-H models. The catalyst, NiMoP/mesoAl2O3(CI), was found to have higher HDN and HDS activities as compared to a conventional γ-Al2O3 supported catalyst containing phosphorus.
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Jarullah, Aysar Talib, Iqbal M. Mujtaba, and Alastair S. Wood. "Kinetic parameter estimation and simulation of trickle-bed reactor for hydrodesulfurization of crude oil." 2011. http://hdl.handle.net/10454/6031.
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M, Rajesh. "Studies on the hydrotreating of Jatropha oil, gas oil and their blends to obtain hydrogenated oil (green diesel) using organic waste derived corbon based catalysts." Thesis, 2017. http://localhost:8080/xmlui/handle/12345678/7327.
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Ordouei, Mohammad Hossein. "Computer Aided Simulation and Process Design of a Hydrogenation Plant Using Aspen HYSYS 2006." Thesis, 2009. http://hdl.handle.net/10012/4431.
Full textAbstract:
Nowadays, computers are extensively used in engineering modeling and simulation fields in many different ways, one of which is in chemical engineering. Simulation and modeling of a chemical process plant and the sizing of the equipment with the assistance of computers, is of special interests to process engineers and investors. This is due to the ability of high speed computers, which make millions of mathematical calculations in less than a second associated with the new powerful software that make the engineering calculations more reliable and precise by making very fast iterations in thermodynamics, heat and mass transfer calculations. This combination of new technological hardware and developed software enables process engineers to deal with simulation, design, optimization, control, analysis etc. of complex plants, e.g. refinery and petrochemical plants, reliably and satisfactorily.
The main chemical process simulators used for static and dynamic simulations are ASPEN PLUS, ASPEN HYSYS, PRO II, and CHEMCAD. The basic design concepts of all simulators are the same and one can fairly use all simulators if one is expert in any of them.
Hydrogenation process is an example of the complex plants, to which a special attention is made by process designers and manufacturers. This process is used for upgrading of hydrocarbon feeds containing sulfur, nitrogen and/or other unsaturated hydrocarbon compounds. In oil and gas refineries, the product of steam cracking cuts, which is valuable, may be contaminated by these unwanted components and thus there is a need to remove those pollutants in downstream of the process. Hydrogenation is also used to increase the octane number of gasoline and gas oil.
Sulfur, nitrogen and oxygen compounds and other unsaturated hydrocarbons are undesired components causing environmental issues, production of by-products, poisoning the catalysts and corrosion of the equipment. The unsaturated C=C double bonds in dioleffinic and alkenyl aromatics compounds, on the other hand, cause unwanted polymerization reactions due to having the functionality equal to or greater than 2.
Hydrogenation process of the undesired components will remove those impurities and/or increase the octane number of aforementioned hydrocarbons. This process is sometimes referred to as “hydrotreating”; however, “upgrader” is a general word and is, of course, of more interest.
In this thesis, a hydrogenation process plant was designed on the basis of the chemistry of hydrocarbons, hydrogenation reaction mechanism, detailed study of thermodynamics and kinetics and then a steady-state simulation and design of the process is carried out by ASPEN HYSYS 2006 followed by design evaluation and some modifications and conclusions.
Hydrogenation reaction has a complicated mechanism. It has been subjected to hot and controversial debates over decades. Many kinetic data are available, which contradict one another. Among them, some of the experimental researches utilize good assumptions in order to simplify the mechanism so that a “Kinetic Reaction” modeling can be employed. This thesis takes the benefit of such research works and applies some conditions to approve the validity of those assumptions.
On the basis of this detailed study of reaction modeling and kinetic data, a hydrogenation plant was designed to produce and purify over 98 million kilograms of different products; e.g. Benzene, Toluene, Iso-octane etc. with fairly high purity.
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Nguyen, Ngoc Luan [Verfasser]. "Analysis of the influence of the hydrodynamics in hydrotreating of diesel oil in trickle bed reactors via MRI-measurements = Analyse des Einflusses der Hydrodynamik auf die hydrierende Entschwefelung von Dieselöl in Rieselbettreaktoren mittels MRI-Messungen / von Ngoc Luan Nguyen." 2011. http://d-nb.info/1012604624/34.
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