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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Sonochemical and impregnated Co-W/γ-Al2O3 catalysts : performances and kinetic studies on hydrotreatment of light gas oil

Vishwakarma, Santosh Kumar 30 January 2007
γ-Al2O3 supported Co-W based catalysts with varying Co (1 - 3 wt %) and W (7 - 13 wt %) loadings were prepared using impregnation and sonochemical methods. All prepared catalysts were characterized with elemental analysis, BET analysis, X-ray diffraction (XRD), NH3 temperature programmed desorption (TPD), temperature programmed reduction (TPR) and thermogravimetry analysis (TGA). <p>The performances of all the synthesized catalysts were tested at a pressure of 8.9 MPa, LHSV of 2 h-1 and temperatures of 340, 350 and 360 °C in a laboratory trickle bed microreactor for hydrodesulphurization (HDS) and hydrodenitrogenation (HDN) of light gas oil (LGO) derived from Athabasca bitumen. The performance tests with impregnated catalysts indicated a maximum in activity for HDS and HDN reactions (sulfur and nitrogen conversions at 93.0 and 57.1 % at 360 °C) for Co(3 wt %)-W(10 wt %)/γ-Al2O3 whereas the performance tests with sonochemically prepared catalysts showed a maximum in activity (sulfur and nitrogen conversions at 87.9 and 42.5 % at 360 °C) for Co(3 wt %)-W(11.5 wt %)/ γ-Al2O3. These two catalysts were selected for detail performance, optimization and kinetic studies. The effects of reaction temperature (340 - 380 °C), pressure (7.6 - 10.3 MPa), liquid hourly space velocity (1.5 - 2.0 h-1) and hydrogen gas/gas oil ratio (400 - 800 mL/mL) were examined on HDS and HDN of LGO with these catalysts. The reaction kinetics for HDS was best fitted with a Power Law model whereas same for HDN was found to be best represented by a Langmuir-Hinshelwood model with a reasonable accuracy (0.90 <R2 <0.95). The activation energy for HDS of LGO were 14 and 12 kJ/mol for selected impregnated and sonochemically prepared catalysts whereas the same for HDN were 9 and 14 kJ/mol for these catalysts, respectively. Calculation showed that the fitted HDS rate expressions were apparent and HDN rate expressions were intrinsic under existing reaction conditions. It also showed that the pore diffusion resistances for both HDS and HDN increased with an increase in reaction temperature from 340 to 380 °C.
2

Sonochemical and impregnated Co-W/γ-Al2O3 catalysts : performances and kinetic studies on hydrotreatment of light gas oil

Vishwakarma, Santosh Kumar 30 January 2007 (has links)
γ-Al2O3 supported Co-W based catalysts with varying Co (1 - 3 wt %) and W (7 - 13 wt %) loadings were prepared using impregnation and sonochemical methods. All prepared catalysts were characterized with elemental analysis, BET analysis, X-ray diffraction (XRD), NH3 temperature programmed desorption (TPD), temperature programmed reduction (TPR) and thermogravimetry analysis (TGA). <p>The performances of all the synthesized catalysts were tested at a pressure of 8.9 MPa, LHSV of 2 h-1 and temperatures of 340, 350 and 360 °C in a laboratory trickle bed microreactor for hydrodesulphurization (HDS) and hydrodenitrogenation (HDN) of light gas oil (LGO) derived from Athabasca bitumen. The performance tests with impregnated catalysts indicated a maximum in activity for HDS and HDN reactions (sulfur and nitrogen conversions at 93.0 and 57.1 % at 360 °C) for Co(3 wt %)-W(10 wt %)/γ-Al2O3 whereas the performance tests with sonochemically prepared catalysts showed a maximum in activity (sulfur and nitrogen conversions at 87.9 and 42.5 % at 360 °C) for Co(3 wt %)-W(11.5 wt %)/ γ-Al2O3. These two catalysts were selected for detail performance, optimization and kinetic studies. The effects of reaction temperature (340 - 380 °C), pressure (7.6 - 10.3 MPa), liquid hourly space velocity (1.5 - 2.0 h-1) and hydrogen gas/gas oil ratio (400 - 800 mL/mL) were examined on HDS and HDN of LGO with these catalysts. The reaction kinetics for HDS was best fitted with a Power Law model whereas same for HDN was found to be best represented by a Langmuir-Hinshelwood model with a reasonable accuracy (0.90 <R2 <0.95). The activation energy for HDS of LGO were 14 and 12 kJ/mol for selected impregnated and sonochemically prepared catalysts whereas the same for HDN were 9 and 14 kJ/mol for these catalysts, respectively. Calculation showed that the fitted HDS rate expressions were apparent and HDN rate expressions were intrinsic under existing reaction conditions. It also showed that the pore diffusion resistances for both HDS and HDN increased with an increase in reaction temperature from 340 to 380 °C.
3

Partial structure factors and fast sound in binary gas mixtures

Bot, Arjen. January 1990 (has links)
Thesis (doctoral)--Uiversiteit van Amsterdam, 1990. / Summary also in Dutch. Includes bibliographical references.
4

Hydrodesulphurization of Light Gas Oil using Hydrogen from the Water Gas Shift Reaction

Alghamdi, Abdulaziz January 2009 (has links)
The production of clean fuel faces the challenges of high production cost and complying with stricter environmental regulations. In this research, the ability of using a novel technology of upgrading heavy oil to treat Light Gas Oil (LGO) will be investigated. The target of this project is to produce cleaner transportation fuel with much lower cost of production. Recently, a novel process for upgrading of heavy oil has been developed at University of Waterloo. It is combining the two essential processes in bitumen upgrading; emulsion breaking and hydroprocessing into one process. The water in the emulsion is used to generate in situ hydrogen from the Water Gas Shift Reaction (WGSR). This hydrogen can be used for the hydrogenation and hydrotreating reaction which includes sulfur removal instead of the expensive molecular hydrogen. This process can be carried out for the upgrading of the bitumen emulsion which would improve its quality. In this study, the hydrodesulphurization (HDS) of LGO was conducted using in situ hydrogen produced via the Water Gas Shift Reaction (WGSR). The main objective of this experimental study is to evaluate the possibility of producing clean LGO over dispersed molybdenum sulphide catalyst and to evaluate the effect of different promoters and syn-gas on the activity of the dispersed Mo catalyst. Experiments were carried out in a 300 ml Autoclave batch reactor under 600 psi (initially) at 391oC for 1 to 3 hours and different amounts of water. After the hydrotreating reaction, the gas samples were collected and the conversion of carbon monoxide to hydrogen via WGSR was determined using a refinery gas analyzer. The sulphur content in liquid sample was analyzed via X-Ray Fluorescence. Experimental results showed that using more water will enhance WGSR but at the same time inhibits the HDS reaction. It was also shown that the amount of sulfur removed depends on the reaction time. The plan is to investigate the effect of synthesis gas (syngas) molar ratio by varying CO to H2 ratio. It is also planned to use different catalysts promoters and compare them with the un-promoted Mo based catalysts to achieve the optimum reaction conditions for treating LGO. The results of this study showed that Ni and Co have a promoting effect over un-promoted Mo catalysts for both HDS and WGSR. Ni was found to be the best promoter for both reactions. Fe showed no significant effect for both WGSR and HDS. V and K have a good promoting effect in WGSR but they inhibited the HDS reaction. Potassium was found to be the strongest inhibitor for the HDS reaction since no sulfur was removed during the reaction
5

Hydrodesulphurization of Light Gas Oil using Hydrogen from the Water Gas Shift Reaction

Alghamdi, Abdulaziz January 2009 (has links)
The production of clean fuel faces the challenges of high production cost and complying with stricter environmental regulations. In this research, the ability of using a novel technology of upgrading heavy oil to treat Light Gas Oil (LGO) will be investigated. The target of this project is to produce cleaner transportation fuel with much lower cost of production. Recently, a novel process for upgrading of heavy oil has been developed at University of Waterloo. It is combining the two essential processes in bitumen upgrading; emulsion breaking and hydroprocessing into one process. The water in the emulsion is used to generate in situ hydrogen from the Water Gas Shift Reaction (WGSR). This hydrogen can be used for the hydrogenation and hydrotreating reaction which includes sulfur removal instead of the expensive molecular hydrogen. This process can be carried out for the upgrading of the bitumen emulsion which would improve its quality. In this study, the hydrodesulphurization (HDS) of LGO was conducted using in situ hydrogen produced via the Water Gas Shift Reaction (WGSR). The main objective of this experimental study is to evaluate the possibility of producing clean LGO over dispersed molybdenum sulphide catalyst and to evaluate the effect of different promoters and syn-gas on the activity of the dispersed Mo catalyst. Experiments were carried out in a 300 ml Autoclave batch reactor under 600 psi (initially) at 391oC for 1 to 3 hours and different amounts of water. After the hydrotreating reaction, the gas samples were collected and the conversion of carbon monoxide to hydrogen via WGSR was determined using a refinery gas analyzer. The sulphur content in liquid sample was analyzed via X-Ray Fluorescence. Experimental results showed that using more water will enhance WGSR but at the same time inhibits the HDS reaction. It was also shown that the amount of sulfur removed depends on the reaction time. The plan is to investigate the effect of synthesis gas (syngas) molar ratio by varying CO to H2 ratio. It is also planned to use different catalysts promoters and compare them with the un-promoted Mo based catalysts to achieve the optimum reaction conditions for treating LGO. The results of this study showed that Ni and Co have a promoting effect over un-promoted Mo catalysts for both HDS and WGSR. Ni was found to be the best promoter for both reactions. Fe showed no significant effect for both WGSR and HDS. V and K have a good promoting effect in WGSR but they inhibited the HDS reaction. Potassium was found to be the strongest inhibitor for the HDS reaction since no sulfur was removed during the reaction
6

Lättgaskanonens innerballistik : Teori, simulering och parameterstudie / Internal Ballistics of a Light Gas Gun : Theory, Simulation and Parametric Study

Landemoo, Viktor January 2021 (has links)
En lättgaskanon är en typ av kanon som används vid experiment där mycket snabba förlopp är av intresse, till exempel hypersonisk strömning och höghastighetskollisioner. Kanontypen når betydligt högre hastigheter än en konventionell kanon då projektilen accelereras genom eldröret av en gas med låg molekylmassa som vätgas eller helium istället för krutgaser. Denna lättgas komprimeras först till högt tryck och temperatur i pumptuben av en kolv som accelererats av en krutladdning. Pumptuben är ett rör anslutet till eldröret som initialt är frånskild av ett membran. För kanonen kan en mängd olika parametrar varieras och hur dessa ska väljas för att en viss mynningshastighet ska nås är inte självklart. Vid FOI har val av parametrar historiskt gjorts baserat på erfarenhet och genom experiment vilket kan vara tidsödslande. Syftet med examensarbetet var därför att simulera kanonen och undersöka hur olika parametrar påverkar dess prestanda. Forskningsfrågor som skulle besvaras var hur olika parametrar påverkar projektilens mynningshastighet och vilket utav två eldrörsalternativ som är bäst lämpat för en viss projektilvikt. Det innerballistiska förloppet i kanonen har simulerats för olika parameterkombinationer med ett program utvecklat specifikt för lättgaskanoner vid NASA:s Ames Research Center och modellen har i viss mån kunnat jämföras mot experimentell data. Resultatet av simuleringarna är att mängden lättgas och krut båda har stor inverkan på mynningshastigheten och att högre kolvvikt jämnar ut trycktoppar som uppstår till följd av stötar i gasen. Att ändra membranets öppningstryck ger ingen förbättring av kanonprestandan för den undersökta projektilvikten och utav de två eldrören som undersökts är det med större kaliber mer lämpligt för de aktuella experimenten. / A light gas gun is a type of gun which is used for experiments when high velocity phenomena are of interest, such as hypersonic flow and high-velocity impacts. The gun type can reach much higher velocities than a conventional gun as the projectile is accelerated down the barrel by a gas with low molecular mass such as hydrogen or helium instead of combustion gasses. This light gas is first compressed to high pressure and temperature in the pump tube with a piston which is accelerated with a propellant charge. The pump tube is connected to the barrel but initially separated from it with a membrane. A vast array of parameters can be varied on the gun in order to achieve a target muzzle velocity and their selection is not trivial. Historically parameters have been selected at FOI through experience and experiments which can be tedious. The purpose of this thesis was to simulate the gun and investigate how various parameters influence its performance. The research questions to be answered was how the parameters influence the muzzle velocity of the projectile and which of two barrels is the most suitable for a given projectile weight. The internal ballistics of the gun was simulated for various combinations of parameters using a program specifically developed for light gas guns at NASA's Ames Research Center and the model has to some extent been compared to experimental data. The result of the simulations shows that the amount of light gas and the propellant charge have a significant effect of the achieved velocity and that the weight of the piston has a reducing effect on the pressure peaks caused by shockwaves in the gas. Changing the opening pressure of the membrane does not improve gun performance for the investigated projectile weight and of the two barrels investigated the one with larger calibre is better suited for the experiments of interest.
7

Improvement of fuel quality by oxidative desulfurization: Design of synthetic catalyst for the process

Nawaf, A.T., Gheni, S.A., Jarullah, Aysar Talib, Mujtaba, Iqbal 04 May 2015 (has links)
Yes / The present study explored a novel oxidative desulfurization (ODS) method of light gas oil fuel, which combines a catalytic oxidation step of the dibenzothiophene compound directly in the presence of molecular air as oxidant to obtain high quality fuel for light gas oil. In chemical industries and industrial research, catalysis play a significant role. Heightened concerns for cleaner air together with stricter environmental legislations on sulphur content in addition to fulfill economic have created a driving force for the improvement of more efficient technologies and motivating an intensive research on new oxidative catalysts. As the lower quality fuel becomes more abundant, additional challenges arise such as more severe operation conditions leading to higher corrosion of the refinery installations, catalyst deactivation and poisoning. Therefore, among the technologies to face these challenges is to develop catalysts that can be applied economically under moderate conditions. The objective of this work is to design a suitable synthetic catalyst for oxidative desulfurization (ODS) of light gas oil (LGO) containing model sulphur compound (dibenzothiophene (DBT)) using air as oxidant and operating under different but moderate operating conditions. The impregnation method is used to characterize two homemade catalysts, cobalt oxide (Co3O4/γ-Al2O3) and manganese oxide (MnO2/γ-Al2O3). The prepared catalysts showed that the manganese oxide has a good impregnation (MnO2=13%), good pore size distribution and larger surface area. A set of experiments related to ODS of dibenzothiophene has been carried out in a continuous flow isothermal trickle bed reactor using light gas oil as a feedstock utilizing both catalysts prepared in-house. At constant pressure of 2 bar and with different initial concentration of sulphur within dibenzothiophene, the temperature of the process was varied from 403K to 473K and the liquid hourly space velocity from(LHSV) was varied from 1 to 3 hr-1. The results showed that an increase in reaction temperature and decreasing in LHSV, higher conversion was obtained. Although both catalysts showed excellent catalytic performance on the removal of molecule sulphur compound from light gas oil, the catalyst MnO2 catalyst exhibited higher conversion than Co3O4 catalyst at the same process operating conditions.
8

Failure of polymeric materials at ultra-high strain rates

Callahan, Kyle Richard 10 May 2024 (has links) (PDF)
Understanding the failure behavior of polymers subjected to an ultrahigh strain rate (UHSR) impact is crucial for their applications in any protective shielding. But little is known about how polymers respond to UHSR events at the macroscale, or what effect their chemical makeups and morphology contribute. This dissertation aims to answer these questions by characterizing the responses of polymers subjected to UHSRs, investigating how the polymer molecular architecture and morphologies alter the macroscopic response during UHSRs via hypervelocity impact (HVI), linking the behaviors of UHSR events between the macro- and nano-length scales, and determining the consequences of UHSR impacts on polymer chains. Macroscale UHSR impacts are conducted using a two-stage light gas gun (2SLGG) to induce an HVI. Different molecular weights and thicknesses of polycarbonate were considered. The HVI behavior of polycarbonate is characterized using both real-time and postmortem techniques. The response depends on target thickness and impact velocity (vi). However, negligible difference is observed between the HVI results for the two differing entanglement densities. These contrasts previous conclusions drawn on the nanoscale during UHSR impacts which capture an increase in the energy arrested from the projectile with increasing entanglement density. To link the UHSR phenomena from nano to macroscale, laser-induced projectile impact testing (LIPIT) is conducted on polymethyl methacrylate (PMMA) thin films on the nanoscale in addition to ballistic and 2SLGG impacts at macroscale. Applying Buckingham-Π theorem, scaling relationships for the minimum perforation velocity and the residual velocity across these length scales were developed. It is shown that the ratios between target thickness to projectile radius, between projectile and target density, and the velocity of the compressive stress wave traveling through the target are the governing parameters for the UHSR responses of polymers across theses length scales. The effect UHSRs have on the polymer is investigated via ex-situ analysis by capturing polymer debris using a custom-built debris catcher. Different material-vi combinations are examined. X-ray diffraction and differential scanning calorimetry are used to characterize the HVI debris. Evidence of char was found within the debris. This dissertation advances the knowledge regarding the failure behavior of polymer materials subjected to UHSRs.
9

Kinetic and Deactivation Studies of Hydrodesulfurization Catalysts

Steiner, Petr January 2002 (has links)
<p>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.</p><p>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-Al<sub>2</sub>O<sub>3</sub> 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.</p><p>The initial deactivation and the steady-state kinetics were studied during the HDS of thiophene at atmospheric pressure. Unpromoted Mo/γ-Al<sub>2</sub>O<sub>3</sub>, CoMo/γ-Al<sub>2</sub>O<sub>3</sub>, NiMo/γ-Al<sub>2</sub>O<sub>3</sub>, and phosphorus modified NiMo/γ-Al<sub>2</sub>O<sub>3</sub> were used for the deactivation study, while NiMo/γ-Al<sub>2</sub>O<sub>3</sub>,CoMo/γ-Al<sub>2</sub>O<sub>3</sub>, and Pt/Y-zeolite (with three different pretreatments) were used for the steadystate study. Several experiments related to the deactivation of Mo/γ-Al<sub>2</sub>O<sub>3</sub> and NiMo/γ-Al<sub>2</sub>O<sub>3 </sub>catalysts prepared with the chelating agent (NTA) were also performed and NTA was found to have no significant effect on the activity of the catalysts.</p><p>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-Al<sub>2</sub>O<sub>3</sub> and NiMo/γ-Al<sub>2</sub>O<sub>3</sub> 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 H<sub>2</sub> 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-Al<sub>2</sub>O<sub>3 </sub>catalyst.</p><p>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.</p><p>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. </p><p>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 H<sub>2</sub>S 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.</p>
10

Kinetic and Deactivation Studies of Hydrodesulfurization Catalysts

Steiner, Petr January 2002 (has links)
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 &gt; 4-MDBT &gt; 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-Al2O3 catalysts 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-Al2O3 catalyst. 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.

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