Browsing by Author "Balangero, Gerardo Simón"

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    hidrogenación e hidrodesulfurización de compuestos poliaromáticos utilizando Pt-Pd/AI203.
    (Univesidsad Tecnológica Nacional., 2016) Balangero, Gerardo Simón; Falcón, Horacio; Beltramone, Andrea Raquel
    Se estudió la hidrogenación de compuestos poliaromáticos como tetralin y fenantreno en presencia de dibenzotiofeno y 4,6-dimetildibenzotiofeno utilizando un catalizador bimetálico Pt-Pd soportado sobre alúmina. El catalizador fue caracterizado por TEM, SEM y BET. Se obtuvo un catalizador con partículas metálicas bien dispersas y de muy pequeño tamaño. Los resultados fueron comparados con un catalizador comercial NiMo/Al2O3. Las reacciones se llevaron a cabo en un reactor de flujo continuo a 345°C y 500 psi (35 atm) variando los tiempos de contacto. Los resultados preliminares muestran que el catalizador desarrollado es más activo que el catalizador comercial. Se observó que los compuestos con mayor número de anillos aromáticos inhiben la velocidad de compuestos con menor número de anillos. Este efecto puede ser explicado en términos de una competitiva adsorción. Se realizó un test de desactivación y se observó que el catalizador no pierde su actividad luego de 20 horas de reacción.
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    Hydrodenitrogenation of over Ir supporteD Ti-SBA-15 modified with F AND AI.
    (Univesidsad Tecnológica Nacional., 2015) Ledesma , Brenda Cecilia; Vallés , Verónica Alejandra; Rivoira , Lorena Paola; Balangero, Gerardo Simón; Anunziata , Oscar Alfredo; Beltramone, Andrea Raquel; Anunziata , Oscar Alfredo; Rivoira , Lorena Paola; Vallés , Verónica Alejandra
    The hydrodenitrogenation of Indole has been studied over a series of Ti-modified SBA 15 supports and their respective Ir-catalysts. Ti-SBA-15 was synthesized using sol-gel method and Ti was added during the synthesis using TEOT as Ti source. Ti was incorporated into the framework replacing the Si atoms in the mesoporous structure. Ir/Ti-SBA-15 with and without F and/or Al were prepared to improve the catalytic activity. F and Al have been incorporated by wetness impregnation method. The effect of the incorporation of F and Al in the mesoporous structure was tested in the hydrodenitrogenation reaction of indole. The catalysts were extensively characterized by X-ray diffraction (XRD), N2 adsorption isotherms, TEM, FTIR and UV-vis-DRS and Raman spectroscopy. The low angle X-ray analysis showed for all the materials intensive reflection, characteristic of SBA-15 structure. The mesoporous structure was maintained after F and Al incorporation. The results showed that Ti incorporation reduces significantly the cluster size and improves considerably the Ir cluster dispersion. The catalytic activity of Ir/Ti-SBA-15 modified with F and Al, with higher acidity, avoided the irreversible adsorption of indole. The catalytic activity was studied in a 4563 Parr reactor, at 250°C, 15 atm of pressure of hydrogen and 360 rpm. The catalysts synthesized had good activity measured in hydrodenitrogenation of indole at mild conditions. The preliminary results show these materials as promising catalysts for HDN reactions.
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    Hydrogenation of tetralin over Ir-containing mesoporous catalysts
    (2012) Vallés, Verónica; Balangero, Gerardo Simón; Martínez, María Laura; Gómez Costa, Marcos Bruno; Anunziata, Oscar Alfredo; Beltramone, Andrea Raquel
    The yield in fluid catalytic cracking (FCC) depends on the extent of aromatic hydrogenation in the gas oil hydrotreater. To optimize the gas oil hydrotreater, it is crucial to understand the aromatic hydrogenation reaction chemistry occurring in the gas oil hydrotreater. Gas oils, which consist of hydrocarbons in the boiling point range of 290−570 °C, contain several aromatic compounds (including three rings, two rings, and one ring). Light cycle oil (LCO), which contains large concentrations of aromatics, has a poor cetane value and, hence, by itself, is a very poor-quality diesel. Because the current regulations [on cetane and polynuclear aromatic (PNA) hydrocarbons] are not stringent, LCO is currently blended with diesel. However, it is anticipated (based on existing regulations in Europe and California) that diesel quality in the near future will be more stringently regulated in terms of cetane and aromatics. To find alternative processes, it is necessary to develop new and more active catalysts to replace the current ones. Optimal design and operation of such hydrogenation processes can be achieved through the use of reliable simulation tools; however, such tools require detailed knowledge of kinetic pathways and rates.1−3 Kinetic experiments on hydrogenation are typically performed in the gas phase under atmospheric pressure on group VIII metal catalysts. Previously, Beltramone et al.4,5 reported a detailed study and a quantitative network analysis of polynuclear aromatics aromatization at industrial conditions, and Korre and Klein6 reported an exhaustive study in a batch reactor at high pressure. Otherwise, the sulfur and nitrogen compounds found in synthetic feedstocks and heavy petroleum fractions can strongly inhibit hydroprocessing reactions through competitive adsorp- tion. The presence of these species even at low concentrations can limit the observed catalytic activity and necessitate the use Article Current processes for dearomatization use catalysts combin- ing the acidity of a support and the hydrogenation and hydrogenolysis/ring-opening activity of an incorporated metal. Hydrogenation/hydrocracking is most often practiced on cyclic molecules over primarily acidic zeolite, alumina, or silica- alumina-supported noble and other group VIII metal catalysts. Different processes have used catalysts such as NiMo, CoMo, NiW, Pt, and Pd on various supports.7−17 The dominance of the acid function can lead to cracking, and thus, a primary focus is the optimization of the acid function. In fact, it was shown recently that significant enhancements in hydrogenation can be made by focusing on the metal function. The metal function is usually provided by Pt and/or Pd, but it has been shown that Ir, Ru, and Rh also have exceptional activities and selectivities for the target reaction of hydrogenation and, depending on the reaction conditions, selective ring-opening.18−20 Some alumina- supported transition-metal catalysts have much higher hydro- denitrogenation (HDN) and hydrodesulfurization (HDS) activities than the conventional NiMo system.21−25 For example, Rh, Ir, Ru, and Pt supported on silica or alumina are known to effectively catalyze nitrogen removal from methylamine, quinoline, or pyridine also in the reduced state.26 Noble-metal sulfides, either unsupported as bulk compounds27 or supported on active carbon,28 have been studied extensively in hydrorefining. It has been shown that transition-metal sulfides of the second and third rows such as those containing Ru, Rh, Os, and Ir are especially active during HDS reactions.27 Similarly, sulfides of Ir, Os, and Re were found to be most active in the HDN of quinoline,28 and sulfides of Ir and Pt were found to be most active in the HDN of pyridine.29 However, catalytic properties of metal deposited on alumina or other supports have been studied less frequently, and moreover, the primary attention to date has been devoted only to Ru.30 It was shown by Cinibulk and Vit́31 that the HDN of higher pressures and temperatures to obtain desired conversions. Therefore, the need for more active catalysts is crucial in this process. The development of highly active and selective hydrotreating catalysts is one of the most pressing problems facing the petroleum indu
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    Inhibition of the hydrogenation of tetralin by nitrogen and sulfur compounds over Ir/SBA-16
    (2011) Balangero, Gerardo Simón; Martínez, María Laura; Gómez Costa, Marcos Bruno; Anunziata, Oscar Alfredo; Beltramone, Andrea Raquel
    In this work we study the catalytic properties of 5 wt.% Ir-containing SBA-16 catalysts (with and without aluminum as heteroatom), in the hydrogenation of tetralin to decalin, in the presence of 100 ppm of N as quinoline, indole and carbazole, and 100 ppm of S as dibenzothiophene and 4,6-dimethyl- dibenzothiophene at 250 ◦C and 15 atm of pressure of hydrogen, using a Parr reactor. Ir/SBA-16 and Ir/Al-SBA-16 were prepared by wetness impregnation using Iridium Acetylacetonate as source of Ir. The Ir/SBA-16 catalyst synthesized by us had high activity measured in tetralin hydrogenation at mild con- ditions. The experimental data was quantitatively represented by a modified Langmuir–Hinshelwood type rate equation, using the apparent adsorption constants calculated from the inhibition results for the individual compounds. The catalyst showed a good resistance to sulfur and nitrogen compounds. The inhibiting effect increased in the order: DBT < quinoline < 4,6-dimethyl-DBT < indole < carbazole. The inhibiting effect of the nitrogen/sulfur compounds was strong, but the activity was still higher than with commercial NiMo/alumina catalyst. We present in this contribution a successfully developed, high loaded and well dispersed Ir/SBA-16 catalysts, that have been shown to maintain a useful catalytic activity, even in the presence of relatively high amounts of sulfur compounds (up to 100 ppm, sulfur basis). Consequently, economically successful processes have evolved, based on this class of catalysts.
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    Pt-Pd-F/AI203catalyst applied in the HDT process.
    (Univesidsad Tecnológica Nacional., 2015) Balangero, Gerardo Simón; Falcón , Horacio; Beltramone , Andrea Raquel
    The inhibiting effect of basic and non-basic nitrogen compounds on the hydrogenation of polyaromatic compounds and on the hydrodesulphurization (HDS) of dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6DMDBT), has been investigated on Pt-Pd-F/Al2O3 and compared with a commercial NiMo hydrotreating catalyst. Langmuir-Hinshelwood type rate equations were used to describe the reaction kinetics accurately with physically meaningful and well identified parameter values. Model parameters were tuned by fitting experimental data obtained in a continuous flow reactor at 345°C, 1000 psi pressure and different contact times. Pt-Pd-F/Al2O3 was more active than NiMo catalyst and conversion remained constant during 24 h of TOS. The model was able to correctly interpret all the experimental data. Parameter estimation results showed that phenanthrene and naphthalene inhibited the tetralin hydrogenation rate, whereas naphthalene and tetralin had no appreciable effect on the rate of phenanthrene conversion. This inhibition could be explained by the competitive adsorption and was described in the kinetic model by adsorption terms obtained from the multicomponent experiments. The inhibiting effect of different nitrogen compounds on the polyaromatic hydrogenation was determined. The following nitrogen compounds were investigated in this study: quinoline, 1,2,3,4-tetrahydroquinoline, indole, and indoline. The degree of inhibition was expressed in terms of an apparent adsorption constant derived from the kinetics.The inhibiting effect on the HDS of DBT and 4,6 DBT followed the same trend
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    Study of Ir/Ti-SBA-15 acidity influence on the HDN of indole.
    (Univesidsad Tecnológica Nacional., 2015) Ledesma , Brenda Cecilia; Vallés , Verónica Alejandra; Rivoira , Lorena Paola; Balangero, Gerardo Simón; Anunziata , Oscar Alfredo; Beltramone, Andrea Raquel; Anunziata , Oscar Alfredo; Rivoira , Lorena Paola; Vallés , Verónica Alejandra
    The hydrodenitrogenation of Indole has been studied over a series of Ti-modified SBA-15 supports and their respective Ir-catalysts. Ti-SBA-15 was synthesized using sol-gel method and Ti was added during the synthesis using TEOT as Ti source. Ti was incorporated into the framework replacing the Si atoms in the mesoporous structure. Ir/Ti-SBA-15 with and without F and/or Al were prepared to improve the catalytic activity. F and Al have been incorporated by wetness impregnation method. The effect of the incorporation of F and Al in the mesoporous structure was tested in the hydrodenitrogenation reaction of indole. The catalysts were extensively characterized by X-ray diffraction (XRD), N2 adsorption isotherms, TEM, FTIR and UV-vis-DRS and Raman spectroscopy. The low angle X-ray analysis showed for all the materials intensive reflection, characteristic of SBA-15 structure. The mesoporous structure was maintained after F and Al incorporation. The results showed that Ti incorporation reduces significantly the cluster size and improves considerably the Ir cluster dispersion. The catalytic activity of Ir/Ti-SBA-15 modified with F and Al, with higher acidity, avoided the irreversible adsorption of indole. The catalytic activity was studied in a 4563 Parr reactor, at 250°C, 15 atm of pressure of hydrogen and 360 rpm. The catalysts synthesized had good activity measured in hydrodenitrogenation of indole at mild conditions. The preliminary results show these materials as promising catalysts for HDN reactions