Bibliografie tematiche / Hydrodesulfurization (HDS)

Letteratura scientifica selezionata sul tema "Hydrodesulfurization (HDS)"

Autore: Grafiati

Pubblicato: 7 luglio 2024

Ultima modifica: 7 luglio 2024

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Articoli di riviste sul tema "Hydrodesulfurization (HDS)":

Mohammed, Abdul Halim A. Karim, Hussein Qasim Hussein e Tariq M. Naife. "Comparative Study of New Re-Ni-Mo/Al2o3 and Conventional Hydrodesulphurization Catalyst". Iraqi Journal of Chemical and Petroleum Engineering 16, n. 4 (30 dicembre 2015): 1–9. http://dx.doi.org/10.31699/ijcpe.2015.4.1.

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New types of hydrodesulfurization (HDS) catalyst Re-Ni-Mo/ γ-Al2O3 was prepared and tested separately with two prepared conventional HDS catalysts (Ni-Mo/ γ-Al2O3 and Co-Mo//γ-Al2O3) by using a pilot plant hydrotreatment unit. Activities of three prepared hydrodesulfurization catalysts were examined in hydrodesulfurization (HDS) of atmospheric gas oil at different temperatures 275 to 350 °C and LHSV 1 to 4 h-1, the reactions conducted under constant pressure 40 bar and H2/HC ratio 500 ml/ml .Moreover, the hydrogenation of aromatic (HAD) in gas oil has been studied. HDS was much improved by adding promoter Re to the Ni-Mo/Al2O3 catalyst. The results showed that Re-Ni-Mo/ γ-Al2O3 have more activity in desulfurization than Ni-Mo//γ-Al2O3 and Co-Mo/ γ-Al2O3 catalysts. The efficiency of hydrodesulfurization was markedly reduced over the Co -Mo/ γ-Al2O3.Also the result showed that Ni-Mo//γ-Al2O3 have a minimum aromatic content 15.44 %.

Miño, Andres, Christine Lancelot, Pascal Blanchard, Carole Lamonier, Loïc Rouleau, Magalie Roy-Auberger, Sébastien Royer e Edmond Payen. "Potential of templated mesoporous aluminas as supports for HDS CoMo catalysts". New Journal of Chemistry 40, n. 5 (2016): 4258–68. http://dx.doi.org/10.1039/c5nj02865e.

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Timoshkina, V. V., S. V. Yudintsev, E. D. Frenkel’ e A. A. Pimerzin. "V-Containing Heteropoly Acids with Keggin Structure as Precursors of Sulfide Catalysts: Regularities of the Convertion of Dibenzothiophene and Naphthalene on Nonpromoted Mo–V Catalysts". Petroleum Chemistry 62, n. 7 (luglio 2022): 779–87. http://dx.doi.org/10.1134/s0965544122050085.

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Abstract Mixed PMoV heteropoly acids with Keggin structures H3+xPMo12–xVxO40 (x = 1–6) and modified sulfide catalysts on their basis were synthesized, their physicochemical characteristics were determined, and their performance in the reactions of hydrodesulfurization (HDS) of dibenzothiophene (DBT) and hydrogenation of naphthalene was evaluated. Modification of the Mo-containing catalysts with vanadium by impregnation with a solution of mixed heteropoly acids was found to enhance their catalytic activity in the studied reactions, as well as to increase the selectivity for the direct hydrodesulfurization route of the DBT HDS reaction.

Jayanti, A. D., e A. Indarto. "Evaluation of phase separator number in hydrodesulfurization (HDS) unit". IOP Conference Series: Materials Science and Engineering 162, n. 1 (novembre 2016): 012005. http://dx.doi.org/10.1088/1757-899x/162/1/012005.

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Gheni, Saba A., Saad A. Awad, Safaa M. R. Ahmed, Ghassan H. Abdullah e Muthanah Al Dahhan. "Nanoparticle catalyzed hydrodesulfurization of diesel fuel in a trickle bed reactor: experimental and optimization study". RSC Advances 10, n. 56 (2020): 33911–27. http://dx.doi.org/10.1039/d0ra05748g.

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AlKhafaji, Khlood S., Bashir Y. Al-Zaidi, Zaidoon M. Shakor e Sattar J. Hussein. "Comparison between Conventional and Metakaolin bi-functional Catalyst in the Hydrodesulfurization Operation". Journal of Petroleum Research and Studies 12, n. 2 (21 giugno 2022): 64–80. http://dx.doi.org/10.52716/jprs.v12i2.658.

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The present study investigates hydrodesulfurization (HDS) of gas oil with 9300 ppm (0.93 wt%) sulfur supplied from Al-Dura Refinery by using an economic catalyst prepared from raw mineral (kaolin clay) cemented by alumina as composite support alumina meta-kaolin (AMK). Characterization of the prepared catalyst was achieved by using Energy Dispersive X-Ray Analysis (EDAX), scanning electron microscopy (SEM), BET surface area, pore volume , Bulk density, X-ray diffraction analysis (XRD) and Fourier-transform infrared spectroscopy (FTIR). AMK was modified as a bifunctional catalyst with active metal (Co and Mo). The hydrodesulfurization (HDS) efficiency was evaluated and compared with the traditional catalyst (CoMo-Al2O3) in a hydrotreating reaction carried out in one stage reactor at temperature 375 oC, pressure 40 bar, LHSV 1hr-1, and H2/HC ratio 200 vol. ratio. 62.2% and 90% of hydrodesulfurization efficiency were achieved for prepared catalyst (CoMo-AMK) and commercial CoMo-Al2O3 respectively at the same operating conditions.

Hillerová, Eva, e Miroslav Zdražil. "Activity and selectivity of carbon-supported transition metal sulfides in simultaneous hydrodearomatization and hydrodesulfurization". Collection of Czechoslovak Chemical Communications 54, n. 10 (1989): 2648–56. http://dx.doi.org/10.1135/cccc19892648.

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Hydrodesulfurization (HDS) and hydrodearomatization (HYD) activities of carbon-supported sulfides of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ru, Rh, Pd, W, Re, Ir, and Pt, and of the commercial Co-Mo/Al2O3 catalysts were evaluated. Simultaneous hydrodesulfurization of benzothiophene and hydrogenation of naphthalene to tetralin at pressure of 2 MPa were used as the model reaction. Platinum group metal sulfides and Re sulfide exhibited the highest HDS activity and Pd and Rh sulfides reached the activity of a good commercial Ni-Mo catalyst. Tha catalysts strongly differed in the selectivity of dihydrobenzothiophene formation during HDS; up to 55% of dihydrobenzothiophene was obtained over W sulfide, while Rh, Ni, Co-Mo and Ni-Mo catalysts produced less than 8% of it. The highest HYD activity exhibited platinum group metal sulfides; the best were Ir and Pt sulfides which were four times and three times more active than the commercial Ni-Mo catalyst, respectively. The selectivity HDA/HDS depend strongly on the type of transition metal. The sulfides of W, Ir and Pt were much more selective for HYD than the Ni-Mo catalyst, and the Co-Mo sample showed by far the lowest HDA/HDS selectivity.

Barba, Daniela. "Catalysts and Processes for H2S Conversion to Sulfur". Catalysts 11, n. 10 (15 ottobre 2021): 1242. http://dx.doi.org/10.3390/catal11101242.

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Hydrogen sulfide is one of the main waste products of the petrochemical industry; it is produced by the catalytic hydrodesulfurization processes (HDS) of the hydrocarbon feedstocks, and it is a byproduct from the sweetening of sour natural gas and from the upgrading of heavy oils, bitumen, and coals [...]

Tanimu, Abdulkadir, Saheed A. Ganiyu, Sagir Adamu e Khalid Alhooshani. "Synthesis, application and kinetic modeling of CeOx–Si–CoMo catalysts for the hydrodesulfurization of dibenzothiophene". Reaction Chemistry & Engineering 4, n. 4 (2019): 724–37. http://dx.doi.org/10.1039/c8re00330k.

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Bianchini, Claudio, M. Victoria Jimenez, Andrea Meli, Simonetta Moneti, Francesco Vizza, Veronica Herrera e Roberto A. Sanchez-Delgado. "Hydrodesulfurization (HDS) Model Systems. Opening, Hydrogenation, and Hydrodesulfurization of Dibenzothiophene (DBT) at Iridium. First Case of Catalytic HDS of DBT in Homogeneous Phase". Organometallics 14, n. 5 (maggio 1995): 2342–52. http://dx.doi.org/10.1021/om00005a035.

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Più fonti

Tesi sul tema "Hydrodesulfurization (HDS)":

Gott, Travis Matthew. "Spectroscopic and Kinetic Studies of Hydrodenitrogenation and Hydrodesulfurization over Supported Nickel Phosphide (Ni2P)". Diss., Virginia Tech, 2008. http://hdl.handle.net/10919/29536.

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This dissertation describes preparation and characterization of Ni2P catalysts and their application in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN). The work carried out includes synthesis of Ni2P on different siliceous supports, SiO2 and MCM-41. It also includes characterization of these catalytic materials using X-ray diffraction (XRD), temperature-programmed reduction (TPR), Fourier transform infrared (FTIR) spectroscopy and X-ray absorbance fine structure (XAFS) spectroscopy. In situ FTIR was employed to study the acidity of Ni2P/SiO2 and probe the catalytic sites involved in the HDN of pyridine. Transient and steady-state kinetics of a surface intermediate that is formed upon pyridine adsorption and reaction was studied to elucidate the mechanism of HDN over Ni2P/SiO2. Additionally, in situ FTIR and X-ray absorption near edge structure (XANES) spectroscopy was utilized to probe the bonding, mechanism and kinetics of thiophene HDS over a novel MCM-41-supported Ni2P catalyst. The use of these techniques allowed for better understanding of the surface intermediates, mechanisms and the nature of the active sites involved in HDN and HDS.
Ph. D.

Lee, Yong-Kul. "Reactivity and Structure of Supported Nickel Phosphides (Ni2P) in Deep Hydrodesulfurization Catalysis". Diss., Virginia Tech, 2004. http://hdl.handle.net/10919/30228.

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This dissertation describes preparation and characterization of Ni2P catalysts and their application in deep hydrodesulfurization (HDS) of a model sulfur compound, 4,6-dimethyldibenzothiophene (4,6-DMDBT), one of the most refractory S-compounds. This topic is of great importance in addressing recently enacted environmental regulations limiting the sulfur content in fuels. The work carried out includes synthesis of Ni2P on different siliceous supports, SiO2, MCM-41, and ultra-stable Y zeolite (USY). It also includes determining the characteristics of the supported Ni2P catalysts with a wide range of techniques: X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and X-ray absorption fine structure (XAFS) spectroscopy. The use of these techniques allowed better understanding of the nature of the active sites as well as the effect of supports. Activity tests were conducted in the HDS of 4,6-DMDBT and the HDN of quinoline. The performance of the catalysts will be compared to that of a conventional sulfide hydrotreating catalyst, Ni-Mo-S/Al2O3. Investigation of the reaction mechanism in the hydrodenitrogenation (HDN) of 2-methylpiperidine together with in situ FT-IR measurements were conducted to understand how catalyst properties affect activity and selectivity.
Ph. D.

Zhao, Haiyan. "Catalytic Hydrogenation and Hydrodesulfurization of Model Compounds". Diss., Virginia Tech, 2009. http://hdl.handle.net/10919/26526.

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This dissertation describes two related studies on hydrogenation and hydrodesulfurization of heterocyclic S-containing compounds. Alkyl substituted thiophenes are promising candidates for hydrogen carriers as the dehydrogenation reactions are known to occur under mild conditions. Four types of catalysts including supported noble metals, bimetallic noble metals, transition metal phosphides and transition metal sulfides have been investigated for 2-methylthiophene (2MT) hydrogenation and ring opening. The major products were tetrahydro-2-methylthiophene (TH2MT), pentenes and pentane, with very little C5-thiols observed. The selectivity towards the desired product TH2MT follows the order: noble metals > bimetallics > phosphides > sulfides. The best hydrogenation catalyst was 2% Pt/Al2O3 which exhibited relatively high reactivity and selectivity towards TH2MT at moderate temperatures. Temperature-programmed desorption (TPD) of hydrogen indicated that the H2 desorption amount was inversely related to the rate of TH2MT formation. Temperature programmed reaction (TPR) experiments revealed that pentanethiol became the major product, especially with HDS catalysts like CoMoS/Al2O3 and WP/SiO2, which indicates that poisoned or modified conventional HDS catalysts would be good candidates for further 2MT hydrogenation studies. The role of tetrahedral Ni(1) sites and square pyramidal Ni(2) sites in Ni2P hydrotreating catalysts was studied by substitution of Ni with Fe. The Fe component was deemed as a good probe because Ni2P and Fe2P adopt the same hexagonal crystal structure, yet Fe2P is completely inactive for hydrodesulfurization (HDS). For this purpose a series of NiFeP/SiO2 catalysts were prepared with different Ni:Fe molar ratios (1:0, 3:1, 1:1, 1:3, and 0:1) and investigated in the HDS of 4,6-dimethyldibenzothiophene at 300 and 340 oC. The uniformity of the NiFe series was demonstrated by x-ray diffraction analysis and by Fourier transform infrared (FTIR) spectroscopy of adsorbed CO. The position of substitution of Fe was determined by extended X-ray absorption fine structure (EXAFS) analysis. It was found that at 300 oC the HDS activity of the catalysts decreased with increasing Fe content and that this could be explained by the substitution of Fe at the more active Ni(2) sites. As temperature was raised to 340 oC, the activity of the Fe-containing samples increased, although not to the level of Ni2P, and this could be understood from a reconstruction of the NiFe phase to expose more Ni(2) sites. This was likely driven by the formation of surface Ni-S bonds, which could be observed by EXAFS in spent samples.
Ph. D.

Steiner, Petr. "Kinetic and Deactivation Studies of Hydrodesulfurization Catalysts". Doctoral thesis, Norwegian University of Science and Technology, Department of Chemical Engineering, 2002. http://urn.kb.se/resolve?urn=urn:nbn:no:ntnu:diva-94.

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Hydrodesulfurization is an important part of the hydrotreating process. More stringent regulations on the quality of fuels bring new requirements to the catalytic processes. The removal of sulfur has become a key issue in the oil refining and this work aims to address several aspects of the process.

Kinetic studies of the hydrodesulfurization reaction over conventional (molybdenum-based) and new (Pt/Y-zeolite) catalysts are reported. The hydrodesulfurization of both the real oil (light gas oil from Statoil Mongstad refinery) and model compounds (thiophene and dibenzothiophene) over a NiMo/γ-Al₂O₃ catalyst were studied. In a high-pressure study of the light gas oil, substituted alkyl-DBTs were found to be the most difficult to desulfurize and the order of reactivity was found to be DBT > 4-MDBT > 4,6-DMDBT. Steric hindrance together with electronic effects were identified as possible reasons for this behavior. The difference in reactivities of the individual compounds was found to decrease with the increasing reaction temperature. A gas chromatograph equipped with the atomic emission detector (GC-AED) was used for the analysis of the individual components of the oil.

The initial deactivation and the steady-state kinetics were studied during the HDS of thiophene at atmospheric pressure. Unpromoted Mo/γ-Al₂O₃, CoMo/γ-Al₂O₃, NiMo/γ-Al₂O₃, and phosphorus modified NiMo/γ-Al₂O₃ were used for the deactivation study, while NiMo/γ-Al₂O₃,CoMo/γ-Al₂O₃, and Pt/Y-zeolite (with three different pretreatments) were used for the steadystate study. Several experiments related to the deactivation of Mo/γ-Al₂O₃ and NiMo/γ-Al₂O₃catalysts prepared with the chelating agent (NTA) were also performed and NTA was found to have no significant effect on the activity of the catalysts.

In the deactivation study, a fast initial decrease in the activity was observed on all the catalysts. However, nickel promoted catalysts were found to be more resistant to deactivation than unpromoted ones. The presence of phosphorus slightly increased the activity of the catalyst towards the thiophene HDS, but had no effect on the deactivation behavior. Several methods to regenerate the catalyst were investigated. During the resulfiding experiments, a difference between Mo/γ-Al₂O₃ and NiMo/γ-Al₂O₃ was observed. Deactivation of the Mo catalyst was more severe with increasing temperature, while for the NiMo catalyst the opposite behavior was observed. Carbon deposition on catalysts followed the similar trend: More carbon was observed on the Mo catalyst at higher temperatures, while the opposite is true for NiMo. The restoration of the activity of NiMo was complete, while the reactivation of the Mo catalyst was only partial. The results from the reactivation experiments with pure H₂ and inert gas (helium) suggest that several mechanisms of the restoration of activity exist: Resulfiding of the desulfided active sites, hydrogenation and removal of the deposited carbonaceous species, and the desorption of the reactants and products from the active sites of the catalyst. Based on the observed results, the higher hydrogenation activity of nickel is assumed to be the reason for the behavior. Hydrogenation causes the faster removal of the deposited carbonaceous species and this leads to the conclusion that the desulfiding of the active sites and the adsorption of the reaction species is significantly less pronounced on the NiMo/γ-Al₂O₃catalyst.

Characterization studies show differences between standard and NTA-based catalysts. The higher amount of carbon on the NTA catalysts is attributed to the presence of the carboncontaining precursor - NTA. The changes in the surface area and the pore volume were observed only during the sulfiding process. In the case of standard catalysts the surface area and the pore volume decreased, while for the NTA-based catalysts the opposite is true. No change in the surface area and the pore volume with the increasing time on stream indicates that the deactivation is not due to structural changes of the catalyst. The amount of sulfur was found to be constant during the time on stream for all the catalysts.

In the steady-state study of the HDS of thiophene, CoMo and NiMo catalysts were found to be equally active. The activity of the Pt/Y-zeolite catalyst was found to be comparable to conventional catalysts when based on the amount of active material, but a fast deactivation was observed. The product selectivities during the HDS of thiophene were found to be the same for all standard catalysts, but slightly different for the Pt/Y-zeolite catalyst. This was attributed to a higher hydrogenation activity of the Pt/Y-zeolite catalyst.

The inhibition effect of other sulfur compounds and aromatics on the high-pressure hydrodesulfurization of dibenzothiophene (DBT), the so-called “matrix effect” was studied. Thiophene and DMDS have the same inhibiting effect on the total conversion of DBT, but differences exist in the effect on the selectivities of the products at low concentrations. The results indicate that the inhibiting effect of H₂S on the direct desulfurization route is stronger than the effect of thiophene on the hydrogenation pathway. In the study of aromatics, both toluene and naphthalene affect the total conversion of DBT. Naphthalene was found to be a much stronger inhibitor and inhibits mainly the direct desulfurization pathway, while the hydrogenation route is more affected by the presence of toluene.

Quilfen, Cyril. "Supercritical fluids synthesis, characterization and test of HDS catalysts : Assessment of criticality of metals contained in HDS catalysts". Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0405/document.

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

Pereira, Barata Beatriz. "XAS hyperspectral imaging : in situ monitoring of the impregnation and drying of CoMoP hydrodesulfurization catalysts". Electronic Thesis or Diss., université Paris-Saclay, 2023. http://www.theses.fr/2023UPASF091.

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Dans le contexte énergétique actuel qui limite les émissions à 10 ppm de soufre, des catalyseurs d'hydrodésulfuration (HDS) plus efficaces sont exigés. Leur préparation commence par l'imprégnation d'une solution de précurseurs (Mo, Co) et généralement de phosphore (P) sur des extrudés d’alumine, suivie d'une maturation et d'un séchage qui aboutissent à la phase oxyde. Il existe diverses espèces Mo, telles que les P-heteropolyanions (P-HPA), qui ont permis d'augmenter les performances catalytiques ces dernières années. Lors de l'imprégnation/maturation, il y a un changement dans l'équilibre entre les espèces Mo dans la solution d'imprégnation acide, en raison du contact avec le support d'alumine basique, conduisant à une distribution hétérogène des espèces, ce qui peut avoir un impact sur l'activité catalytique. Donc, l'amélioration de l'activité catalytique dépend d'une meilleure compréhension de l'impact des étapes de préparation sur la localisation, la nature et la concentration des espèces Mo sur le support. Une caractérisation chimique in situ, quantitative et résolue dans l'espace est donc nécessaire. Dans ce travail, une imagerie hyperspectrale de spectroscopie d'absorption des rayons X (XAS) au seuil K du Mo a été développée sur la ligne ROCK-SOLEIL. Des cubes de données 3D résolus en énergie dans l'espace ont été enregistrés à l'aide d'une caméra CMOS pixellisée (pixels de 1,625 µm après grossissement x4, 1 cube/11s). Deux cellules ont été conçues pour la préparation de catalyseurs in situ. Un extrudé de support (1,5x1,6 mm) peut être inséré dans la cavité de la cellule d'imprégnation, où ~2 μL de solution est injectée. Après 3h de maturation, l’extrudé est placé dans la cellule de séchage, chauffé de la température ambiante à 120°C, suivi d'un palier isotherme de 1h. La quantification des espèces en Mo est obtenue par combinaison linéaire d'une bibliothèque de spectres EXAFS de références. Dans une première partie, nous nous sommes concentrés sur l'étude de l'imprégnation et du séchage sur un support cylindrique en alumine avec du phosphore d'un CoMoP P/Mo 0,56 Co/Mo 0,4 0,75 M [Mo] (pH=1,3) contenant l'HPA de Strandberg. Lors de l’imprégnation, les P-HPAs sont partiellement préservés sur les bords de l'extrudé, tandis qu'un cœur riche en monomolybdate se forme. L'HPA d'Anderson est distribué de manière presque homogène. Une courbe d'absorption en forme de S a été associée à un front de monomolybdate. À la fin de la maturation, le catalyseur est homogène en P-HPAs. L'évolution de la spéciation Mo a été expliquée par (i) la forte affinité des ions phosphate avec l'alumine, qui a entraîné la diminution des phosphates libres en solution (ii) le PZC du support, conduisant à différentes interactions avec les espèces Mo (iii) le pH de la solution d'imprégnation et celui dans les pores du support. Au cours du séchage, l'élimination de l'eau entraîne les transformations des espèces Mo, associées à la rampe de température. Cela se produit en raison (i) du départ de l'eau d'abord sur le cœur, décomposant l'HPA d'Anderson, conduisant à des interactions plus fortes du support (ii) du transfert d'eau sur les bords de l'extrudé, conduisant à un excès d'eau et à une transformation liée au pH. À la fin du séchage, la plupart des P-HPA sont perdus. Dans une deuxième partie, nous avons étudié l'impact du promoteur (Co). Nous avons montré que le Co a un impact sur le pH et la spéciation Mo de la solution d'imprégnation et sur sa diffusion. Un profil de Mo de type « egg white » est obtenu à la fin pour le MoP. À la fin du séchage, le MoP et le CoMoP ont des profils de Mo différents mais des spéciations de Mo similaires. Grâce à ce travail, nous avons pu pour la première fois suivre la dynamique de la spéciation du Mo au cours de la préparation d'un catalyseur. Cette méthodologie puissante permet d'acquérir de grandes quantités de données expérimentales nécessaires à la modélisation mathématique de l'imprégnation et du séchage
In today's energy context, where emission policies allow up to 10 ppm sulfur, there is a demand for more efficient hydrodesulfurization (HDS) catalysts. Their preparation begins with impregnation of a solution containing metal precursors (Mo, Co) and usually phosphorus (P) onto alumina support extrudates, followed by maturation and drying, resulting in the oxide dry phase. In that phase, many Mo-species are be found. In particular, P-heteropolyanions (P-HPAs) have allowed to increase catalytic performance in recent years. Upon impregnation/maturation, there is a change in the equilibrium between the Mo-species in the acidic impregnation solution, due to the contact with the basic alumina support, leading to a heterogeneous distribution of the species, which can impact the catalytic activity. Therefore, improving catalytic activity depends on a better understanding the impact of the preparation stages on the location, nature, and concentration of the Mo-species on the support. To improve this, in situ chemical, quantitative and spatially resolved characterization is required. In this work, a hyperspectral full field time-resolved Mo K-edge X-ray Absorption Spectroscopy (XAS) imaging has been developed at the ROCK-SOLEIL beamline. Space-energy resolved 3D data cubes were recorded using a pixelated CMOS camera (1.625 µm pixel size after magnification by a x4 objective, 1 cube/11s). Two cells were designed for in situ catalyst preparation. A support extrudate (1.5x1.6mm) can be loaded inside the cavity of the impregnation cell, where ~2 μL solution is injected. After 3h-maturation, the same extrudate is placed in the drying cell, heated from room temperature to 120°C, followed by 1h isothermal plateau. The quantification of Mo-species is obtained by linear combination fitting of a library of EXAFS spectra of bulk references. In a first part of this work, we focused on the study of the impregnation and drying on a cylindrical alumina support with phosphorus of a CoMoP P/Mo 0.56 Co/Mo 0.4 0.75 M [Mo] solution (pH=1.3) containing mainly Strandberg’s HPA. We observed that P-HPAs are partially preserved upon impregnation at the edges of the extrudate, while a monomolybdate-rich core is formed. Anderson’s HPA is distributed nearly homogeneously. A S-shape uptake curve was observed, associated with a monomolybdate front. At the end of the maturation, the catalyst had a homogeneous profile, rich in P-HPAs. The evolution of the Mo-speciation was explained by (i) the high affinity of phosphate ions with alumina, that resulted in the decrease of free phosphates in solution; (ii) the PZC of the support, leading to different interactions with the Mo-species; (iii) the pH of the impregnation solution and the local pH on the pores of the support. During drying, the removal of water is driving the Mo-transformations, associated to the temperature ramp. This occurs due to (i) the departure of water first on the core, decomposing the Anderson’s HPA, leading to stronger interactions of the support and to the partial to full decomposition of the P-HPAs (ii) the transfer of water at the extrudate edges, leading to an excess of water and driving pH related transformation. At the end of drying, most of the P-HPAs are lost. In a second part of this work, we studied the impact of the promoter (Co). We have shown that the Co precursor impacts the pH and the Mo-speciation of the impregnation solution and its diffusion. An egg white Mo-profile is obtained at the end for the MoP catalyst. At the end of drying, MoP and CoMoP had different Mo-profiles but similar Mo-speciations. Thanks to this work, we were able for the first time to follow the dynamics of the Mo-speciation during the key preparation steps of a catalyst. This powerful approach/methodology allows one to acquire large amounts of experimental data required for the mathematical modelling of impregnation and drying

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)

Michaux, Olivier. "Etude de la reactivite des sulfures metalliques pour la reaction d'hydrodesulfuration (hds) : une application de la rmn du metal solide a la catalyse". Université Louis Pasteur (Strasbourg) (1971-2008), 1986. http://www.theses.fr/1986STR13073.

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Proposition d'un nouveau modele de surface active grace a l'utilisation de la rmn du cobalt 59 et a l'activite des sulfures de tous les metaux de transitions. Proposition d'un nouveau modele pour l'empoisonnement des catalyseurs hds par le vanadium

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.
Tikrit University, Iraq

Capitoli di libri sul tema "Hydrodesulfurization (HDS)":

Rashidi, Alimorad, Fatemeh Mohammadzadeh e Sedigheh Sadegh Hassani. "Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports". In Nanotechnology in Oil and Gas Industries, 193–210. Cham: Springer International Publishing, 2017. http://dx.doi.org/10.1007/978-3-319-60630-9_7.

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Huirache-Acuña, Rafael, Gabriel Alonso-Nuñez, Eric M. Rivera-Muñoz, Omar Gutierrez e Barbara Pawelec. "Trimetallic Sulfide Catalysts for Hydrodesulfurization". In Applying Nanotechnology to the Desulfurization Process in Petroleum Engineering, 240–62. IGI Global, 2016. http://dx.doi.org/10.4018/978-1-4666-9545-0.ch008.

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The more stringent environmental regulations enacted throughout the world have increased the need of more active hydrotreating (HDT) catalysts, in the petroleum refining industry. Usually, the catalysts used for diesel oil hydrotreatment are ?-Al2O3 supported molybdenum or tungsten sulfides promoted with cobalt or nickel. Current strategies for the design of novel HDS catalysts often include variations in the support formulation, catalyst preparation method and active phase formulation. In this sense, the new generations of catalysts, such as NEBULA®, are based on a totally different concept of bulk-like. In this chapter, we present recent research related to the synthesis, characterization and performance of trimetallic sulfide nanocatalysts for hydrodesulfurization. The present chapter analyses the state of art of the ternary sulfide hydrotreating catalysts.

Paixão, Susana M., Tiago P. Silva, Bruno F. Arez e Luís Alves. "Advances in the Reduction of the Costs Inherent to Fossil Fuels' Biodesulfurization Towards Its Potential Industrial Application". In Biotechnology, 1985–2020. IGI Global, 2019. http://dx.doi.org/10.4018/978-1-5225-8903-7.ch081.

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Biodesulfurization (BDS) process consists on the use of microorganisms for the removal of sulfur from fossil fuels. Through BDS it is possible to treat most of the organosulfur compounds recalcitrant to the conventional hydrodesulfurization (HDS), the petroleum industry's solution, at mild operating conditions, without the need for molecular hydrogen or metal catalysts. This technique results in lower emissions, smaller residue production and less energy consumption, which makes BDS an eco-friendly process that can complement HDS making it more efficient. BDS has been extensively studied and much is already known about the process. Clearly, BDS presents advantages as a complementary technique to HDS; however its commercial use has been delayed by several limitations both upstream and downstream the process. This study will comprehensively review and discuss key issues, like reduction of the BDS costs, advances and/or challenges for a competitive BDS towards its potential industrial application aiming ultra low sulfur fuels.

Paixão, Susana M., Tiago P. Silva, Bruno F. Arez e Luís Alves. "Advances in the Reduction of the Costs Inherent to Fossil Fuel Biodesulfurization Towards Its Potential Industrial Applications". In Nanocomposites for the Desulfurization of Fuels, 235–83. IGI Global, 2020. http://dx.doi.org/10.4018/978-1-7998-2146-5.ch007.

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The biodesulfurization (BDS) process consists of the use of microorganisms for the removal of sulfur from fossil fuels. Through BDS it is possible to treat most of the organosulfur compounds recalcitrant to the conventional hydrodesulfurization (HDS), the petroleum industry's solution, at mild operating conditions, without the need for molecular hydrogen or metal catalysts. This technique results in lower emissions, smaller residue production, and less energy consumption, which makes BDS an eco-friendly process that can complement HDS making it more efficient. BDS has been extensively studied and much is already known about the process. Clearly, BDS presents advantages as a complementary technique to HDS; however, its commercial use has been delayed by several limitations both upstream and downstream the process. This study will comprehensively review and discuss key issues, like reduction of the BDS costs, advances, and/or challenges for a competitive BDS towards its potential industrial application aiming ultra-low sulfur fuels.

Paixão, Susana M., Tiago P. Silva, Bruno F. Arez e Luís Alves. "Advances in the Reduction of the Costs Inherent to Fossil Fuels' Biodesulfurization towards Its Potential Industrial Application". In Applying Nanotechnology to the Desulfurization Process in Petroleum Engineering, 390–425. IGI Global, 2016. http://dx.doi.org/10.4018/978-1-4666-9545-0.ch013.

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Farag, Hamdy, e Masahiro Kishida. "Kinetic Models for Complex Parallel–Consecutive Reactions Assessment of Reaction Network and Product Selectivity". In Petrochemical Catalyst Materials, Processes, and Emerging Technologies, 330–51. IGI Global, 2016. http://dx.doi.org/10.4018/978-1-4666-9975-5.ch012.

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Kinetic models were developed to account for the partial contributions of intermediates in complex parallel–consecutive reactions. The models allow precise estimation of the apparent rate constants of all steps in such a reaction network. The hydrodesulfurization (HDS) of dibenzothiophene (DBT) over CoMo-based alumina and carbon catalysts, and over an unsupported molybdenum sulfide catalyst, were investigated in a batch reactor and used to represent this type of reaction. The HDS reactions proceeded through two parallel–consecutive reaction pathways, i.e., direct desulfurization (DDS) and hydrogenation (HYD), in which two main intermediates, namely biphenyl and partially hydrogenated DBT, were involved. Different selectivities in terms of yield fraction (percentage ratio of HYD/DDS) were observed for these catalysts. The results are discussed in the context of proposed HDS reaction networks. Use of these models enables more accurate assessment of differences among the performances of different catalysts.

Wang, Zhoujun, Pingyi Wu, Ling Lan e Shengfu Ji. "Preparation, Characterization and Desulfurization of the Supported Nickel Phosphide Catalysts". In Petrochemical Catalyst Materials, Processes, and Emerging Technologies, 431–58. IGI Global, 2016. http://dx.doi.org/10.4018/978-1-4666-9975-5.ch015.

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Hydrodesulfurization (HDS) is an important technology to produce clean fuels, in which the nickel phosphide catalysts exhibit excellent catalytic performances. In this work, a series of NixP/SBA-15 catalysts with various P/Ni molar ratios were prepared using the mesoporous molecular sieve SBA-15 as the support. The structure and surface properties of the catalysts were characterized by X-ray diffraction (XRD), N2 sorption analysis, transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FTIR), and in situ diffuse reflectance infrared Fourier transfer spectroscopy (DRIFTS). The catalytic performances for the HDS of dibenzothiophene (DBT) were evaluated. The results demonstrated that the NixP/SBA-15 catalysts possessed high specific surface area and the mesoporous structures, which benefited the elimination of the internal diffusion limitation in the HDS reactions. Both Ni2P and Ni12P5 phases showed catalytic activity in HDS reactions while Ni2P was more active. The optimal P/Ni molar ratio was about 0.75. The DBT conversion can reach 95.8% under the reaction condition of pressure at 3.0 MPa, H2:oil=600, WHSV at 26.7 h-1, and temperature at 340oC. In situ DRIFTS spectra indicated that the coordinative unsaturated Nid+ (0<d<1) species on the catalysts surface were the active sites for the HDS of DBT.

Roe, Charles L., e Kirk H. Schulz. "Modeling molybdenum carbide-based hydrodesulfurization (HDS) catalysts using carbon-modified Mo(110) surfaces". In Studies in Surface Science and Catalysis, 121–28. Elsevier, 1999. http://dx.doi.org/10.1016/s0167-2991(99)80400-5.

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Saladino, Raffaele, Giorgia Botta e Marcello Crucianelli. "Advances in Nanotechnology Transition Metal Catalysts in Oxidative Desulfurization (ODS) Processes". In Applying Nanotechnology to the Desulfurization Process in Petroleum Engineering, 180–215. IGI Global, 2016. http://dx.doi.org/10.4018/978-1-4666-9545-0.ch006.

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Organosulfur compounds show a negative environmental impact because of SOx emissions by combustion of fuel oils. As a consequence, removal of sulfur is becoming a worldwide challenge. The hydrodesulfurization (HDS) process achieves limited performances in the case of refractory S-containing aromatic compounds, such as thiophene and substituted benzothiophenes (BTs), which require highly energy-demanding conditions (high temperature and pressure conditions). Oxidative desulfurization (ODS) is considered the most promising alternative to HDS. During ODS treatment, the organosulfur compounds are oxidized to corresponding sulfoxides and sulfones, which can be successively removed by extraction with polar solvents. Different stoichiometric oxidants have been used in the ODS processes with a different degree of efficacy and environmental impact. The design and development of catalytic procedures can increase the ODS energy efficiency as well as make it more economical and environmentally acceptable. Here we describe the advances in nanostructured organometallic catalysis and biotechology applied to ODS treatment.

Ogunlaja, Adeniyi S., e Zenixole R. Tshentu. "Molecularly Imprinted Polymer Nanofibers for Adsorptive Desulfurization". In Applying Nanotechnology to the Desulfurization Process in Petroleum Engineering, 281–336. IGI Global, 2016. http://dx.doi.org/10.4018/978-1-4666-9545-0.ch010.

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Desulfurization of fuel oils is an essential process employed in petroleum refineries to reduce the sulfur concentration in fossil fuels in order to meet the mandated environmental protection limit of 10 ppm sulfur. The hydrodesulfurization (HDS) process, which is currently being employed for desulfurization, is limited in treating refractory organosulfur compounds as it only reduces sulfur content in fuels to a range of 200-500 ppm sulfur. Oxidative desulfurization (ODS) is considered a new technology for desulfurization of fuel oils as the process is capable of desulfurizing fuels to reach the ultra-low sulfur levels and can serve as a complementary step to HDS. The chapter discusses, briefly, the oxidation of refractory sulfur compounds found in fuels using vanadium as a catalyst to form organosulfones, a first step in ODS process. The chapter also discusses, in detail, the chemistry involved in molecular imprinting of organosulfones on functional polymers, and the electrospinning of the polymeric matrix to produce molecularly imprinted nanofibers employed for selective adsorption of organosulfones from the oxidized mildly hydrotreated fuels, a second step in the ODS process. Chemical interactions, apart from the imprinting effect, that can be exploited in molecularly imprinted polymers for selective extraction of organosulfones, such as hydrogen bonding, p-p interactions, van der Waals forces and electrostatic interactions, were discussed by employing density functional theory calculations. The possibilities of electrospinning on a large scale as well as prospects for future industrial applications of functional molecularly imprinted nanofibers in desulfurization are also discussed.

Atti di convegni sul tema "Hydrodesulfurization (HDS)":

Fassihi, M. R., R. G. Moore, P. Pereira Almao, S. A. Mehta, M. G. Ursenbach e D. G. Mallory. "New Insights on Catalysts-Supported in situ Upgrading of Heavy Oil During in situ Combustion Oil Recovery". In SPE Annual Technical Conference and Exhibition. SPE, 2023. http://dx.doi.org/10.2118/215092-ms.

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Abstract As part of GHG reduction initiatives, there have been many publications on CO2 capture, utilization, and storage (CCUS), reducing the carbon footprints in the oil and gas production, switching to renewable energies, and generating carbonless fuel (e.g., H2) via in situ processes. In situ upgrading of bitumen and heavy oils and converting them into low sulfur, low N2, and low asphaltene can help with both producing cleaner fuel as well as utilizing vast resources of energy that could otherwise be wasted due to extreme measures of no fossil fuel policies. Additionally, such processes could produce valuable products, enhanced shipping/pipelining, and less demanding downstream processing. Generating hydrogen could be another focus area for in situ upgrading. This paper provides new insights into the results of several combustion tube tests that were performed for Alberta Ingenuity Centre for In Situ Energy (AICISE) using different heavy oils with fresh supported catalyst. The catalysts were placed in the production end of the combustion tube so oil would pass over the catalyst bed before being produced. In practice, solid catalyst particles could be placed into the oil-bearing formation adjacent to the producing wellbore, ensuring that crude oil will flow over the catalysts during oil production. This paper utilizes many of the lab results that have never been published before. The objective is to understand whether using catalysts has merits in our future oil production activities under the current environmental restrictions. A commercial Ni/Mo catalyst was used in these tests. The results of these tests indicated at least temporary significant occurrence of reactions such as: hydroprocessing (HP), hydrotreating reactions, such as hydrocracking (HC), hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodeoxygenation (HDO). We will discuss the impact of pressure, temperature, water injection and dispersed versus supported catalysts on the degree of oil upgrading. Also, the key parameters that could impact in situ hydrogen generation will be presented. Specifically, the role of reactions such as Aquathermolysis (AQ), thermal cracking (TC), water-gas shift reaction (WGS) and coke gasification (CG) will be discussed. Notice that the products of these reactions could undergo additional methanation reactions (ME) which could reduce the H2 concentration in the produced gas. Finally, methods of upscaling these results to the field conditions will be presented.

Rapporti di organizzazioni sul tema "Hydrodesulfurization (HDS)":

Reynolds, Michael A. Organometallic Modeling of the Hydrodesulfurization (HDS) Process: Rhenium Carbonyl-promoted C-S Bond Cleavage and Hydrogenation of Thiophenes and Benozothiophenes. Office of Scientific and Technical Information (OSTI), settembre 2000. http://dx.doi.org/10.2172/764628.

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