Effective distribution of hydrogen in refinery hydrogen networks is a major concern for refiners tackling the stringent specifications on maximum sulphur levels in middle distillates and the increasing global demand of diesel fuel. A major challenge is the implementation of a shift from conventional to ultra-deep methods of desulphurisation. Meanwhile, the capacity of secondary conversion processes such as fluid catalytic cracking (FCC) and hydrocracking in refineries has steadily increased in converting the bottom of the barrel into high-value lighter products resulting in increased levels of hydroprocessing, which exerts a higher demand on refinery hydrogen systems. Previous methodologies on hydrogen network optimization have been developed mainly based on the assumption of fixed hydroprocessing performance with constant hydrogen consumption and light hydrocarbon yields, in order to reduce the complexity of the optimisation problem. Consequently, critical interactions among feed and catalyst properties, hydroprocessor operating conditions, product quality and yields, and hydrogen consumption are usually neglected. This research work involves three major aspects: 1. Development of semi-empirical nonlinear lumped hydrodesulphurisation (HDS) and hydrocracker models that are robust and sufficiently detailed to capture the behaviour of the process with changes in feed characteristics and operating conditions. The formation of light hydrocarbons during HDS reactions have been accounted for. Hydrocracker conversion models and five/six-lumped product yield models for vacuum gas oil (VGO) and vacuum residue (VR) feedstocks have been developed from a combination of first principles and empirical methods based on several process parameters. The proposed models are validated with different feedstocks and shows good agreement with industrial data. 2. Integration of HDS and hydrocracker performance models into refinery hydrogen network models to explore existing interactions between processes and the hydrogen network, and their combined effect on the overall network objective. 3. Optimization of the overall superstructure under different operating scenarios to facilitate the efficient distribution and utilization of hydrogen and the maximization of clean high-value products. The integrated superstructure network model is developed and optimized within the General Algebraic Modelling System (GAMS). The model is representative of the dynamic interactions between hydrodesulphurisation and hydrocracking processes in the refinery hydrogen network as demonstrated by the reproducibility of industrial refinery data. Thus, this work presents a holistic and realistic implementation of refinery hydrogen management technique.

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

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

<p><strong>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</strong></p><p>U ovom radu izvr&scaron;ena su ispitivanja deaktivacije katalizatora za hidrodesulfurizaciju (HDS), uz simulaciju starenja u laboratorijskim uslovima i paralelna ispitivanja katalizatora iz realnog industrijskog postrojenja. &Scaron;irok interval uslova u laboratorijskoj simulaciji (temperatura, vreme tretmana, oksidacione i inertne atmosfere) pružio je osnov za ocenu uticaja različitih parametara na brzinu starenja katalizatora i definisanje kritičnih uslova, posebno pri regeneraciji katalizatora. Ispitivanja dva tipa HDS katalizatora, NiO-MoO₃/y-Al₂O₃ i CoO- MoO₃/y-Al₂O₃ i binarnih modelnih sistema NiO/ Al₂O₃, uz primenu komplementamih metoda za ispitivanje stukture i teksture čvrstih poroznih materijala, omogućila su uvid u mehanizme starenja u ovim složenim katalitičkim sistemima. Utvrđeno je da je oksidaciona atmosfera, posebno vodena para, kritičan faktor u kinetici stukturnih i teksturalnih promena u katalitičkom sistemu. Segregacija aktivne faze, interakcija sa nosačem, sinterovanje i gubitak aktivne faze iz sistema simultani su procesi koji dovode do trajne deaktivacije katalizatora. Visina radne temperature i moguća lokalna pregrevanja u sloju katalizatora, podstaknuta promenama difuzionih karakteristika kataličkog zrna, ključni su za destrukciju aktivne faze katalizatora, uz segregaciju prekursora oksidne faze molibdena, čiji je uticaj izrazit u fazi regeneracije. Intermedijarno prisustvo tečne faze oksida molidena, koja obliva povr&scaron;inu nosača, uslovljavajući intenzivno sinterovanje i ubrzanu interakciju izmedju ostalih faza u sistemu, predstavlja osnovni mehanizam u starenju katalizatora za HDS.</p> / <p><strong>Abstract was processed by technology for Optical character recognition (OCR).</strong></p><p>Deactivation studies of hydrodesulphurization catalysts were performed, based on both aging simulation in laboratory conditions and investigation of catalysts from an industrial HDS plant. Broad interval of conditions applied in laboratory simulation (temperature, treatment duration, oxidation and inert atmospheres) was the basis for evaluating the effect of different parameters on catalyst aging kinetics and defining critical conditions, with emphasis on regeneration procedure. The investigations of two catalyst types, NiO-MoO3/y-Al2O3 and C0O-MoO3/y-Al2O3, and NiO/Al2O3 binary model systems, using complementary methods for structural and textural investigations of porous solid systems, enabled the insight in aging mechanisms of these complex catalytic systems. The oxidation atmosphere, especially water vapor, is critical for the rate of structural and textural changes in the catalysts. Segregation in active phase, interaction with the support, sintering and loss of active component from the catalyst are the simultaneous processes bringing about the irreversible deactivation of the catalyst. The temperature gradient in working conditions and possible formation of hot spots in catalyst reactor bed, affected also by changes of diffusion characteristics of catalyst grain, are crucial factors for segregation of molybdenum oxide precursor, which effect is pronounced during regeneration. The mechanism of HDS catalyst aging is based on intermediary presence of moIybdenum oxide liquid phase on the support surface, facilitating intensive sintering and interactions of other phases of catalytic system.</p>

New catalyst development for the hydrotreating process, employing functionalized mesoporous carbon (mC) support is studied. mC support was prepared by the volume templating of alkali modified SBA-15 using sucrose as the carbon source and then functionalized using nitric acid of various concentrations (upto 8M HNO3). A series of NiMo catalysts (12% Mo and 2.4% Ni) were prepared using these functionalized mC supports. The supports and catalysts were characterized by N2 physisorption, SAXS, XRD, FTIR, TGA, SEM, TEM, H2-TPR and HRTEM. SAXS results indicated mild reduction in ordered structure of mesoporous carbons after functionalization. N2 physisorption analysis indicated progressive reduction in surface area and pore volume with the increase in nitric acid concentration. Enhancement of surface functional groups and acidity after functionalization were observed through FTIR spectroscopy and Boehm titration. SEM images showed the retention of needle like morphology in all functionalized carbon supports. TEM images showed that the increase in nitric acid concentration causes excessive etching, resulting in the reduction of ordered structure of functionalized mesoporous carbons. Hydrotreating study of these NiMo/mC catalysts were carried out under industrial operating conditions in a laboratory scale trickle bed reactor using coker light gas oil derived from Athabasca bitumen as feedstock. NiMo catalyst supported on 6M acid treated mC (i.e. NiMo/mC-6M) showed the highest activity due to higher surface functional groups, higher acidity and better textural properties. The HDS and HDN activities of NiMo/mC-6M catalyst were higher than that of NiMo/ã-Al2O3 catalyst owing to lower support metal interaction (SMI), higher surface area and effective functionalization. Using the mC-6M support, NiMo catalysts with different metal loading (12 27% Mo, 2.4 to 5.4% Ni) were prepared and characterized. Hydrotreating activity study of these catalysts indicated that the catalyst with 22% Mo and 2.9% Ni loading was the optimum catalyst on 6M functionalized mC support. Higher metal loading (>22%Mo) led to excessive pore blockage and improper metal dispersion resulting in decreased activity. Kinetic study of the optimum catalyst was carried out by varying temperature (330°C to 370°C), gas-to-oil ratio (400 1000 Nm3/m3), LHSV (1.0 to 2.5 hr-1) and pressure (7.8 to 9.8 MPa) and the data was fitted by non-linear regression method using power law model. The calculated reaction orders and activation energies were 2.8, 1.5 and 189 KJ/mol, 98.9 KJ/mol for HDS and HDN, respectively. The results of HRTEM and H2-TPR indicated lower SMI in mC supported catalyst resulting in the generation of qualitatively Type-II like NiMoS phase on functionalized mC supports, which is considered to be very active for hydrotreating. The hydrotreating activity of the optimum catalyst was higher than that of commercial catalyst (supported on ã-Al2O3). Long term deactivation experiment carried out over a total period of 10 weeks confirmed the durability of NiMo/mC catalyst for the duration of operation. This study reveals the immense capability of functionalized mC supports to become the potential alternative catalyst support to conventional ã-Al2O3 for the hydrotreating of gas oil feedstocks.

New catalyst development for the hydrotreating process, employing functionalized mesoporous carbon (mC) support is studied. mC support was prepared by the volume templating of alkali modified SBA-15 using sucrose as the carbon source and then functionalized using nitric acid of various concentrations (upto 8M HNO3). A series of NiMo catalysts (12% Mo and 2.4% Ni) were prepared using these functionalized mC supports. The supports and catalysts were characterized by N2 physisorption, SAXS, XRD, FTIR, TGA, SEM, TEM, H2-TPR and HRTEM. SAXS results indicated mild reduction in ordered structure of mesoporous carbons after functionalization. N2 physisorption analysis indicated progressive reduction in surface area and pore volume with the increase in nitric acid concentration. Enhancement of surface functional groups and acidity after functionalization were observed through FTIR spectroscopy and Boehm titration. SEM images showed the retention of needle like morphology in all functionalized carbon supports. TEM images showed that the increase in nitric acid concentration causes excessive etching, resulting in the reduction of ordered structure of functionalized mesoporous carbons. Hydrotreating study of these NiMo/mC catalysts were carried out under industrial operating conditions in a laboratory scale trickle bed reactor using coker light gas oil derived from Athabasca bitumen as feedstock. NiMo catalyst supported on 6M acid treated mC (i.e. NiMo/mC-6M) showed the highest activity due to higher surface functional groups, higher acidity and better textural properties. The HDS and HDN activities of NiMo/mC-6M catalyst were higher than that of NiMo/ã-Al2O3 catalyst owing to lower support metal interaction (SMI), higher surface area and effective functionalization. Using the mC-6M support, NiMo catalysts with different metal loading (12 27% Mo, 2.4 to 5.4% Ni) were prepared and characterized. Hydrotreating activity study of these catalysts indicated that the catalyst with 22% Mo and 2.9% Ni loading was the optimum catalyst on 6M functionalized mC support. Higher metal loading (>22%Mo) led to excessive pore blockage and improper metal dispersion resulting in decreased activity. Kinetic study of the optimum catalyst was carried out by varying temperature (330°C to 370°C), gas-to-oil ratio (400 1000 Nm3/m3), LHSV (1.0 to 2.5 hr-1) and pressure (7.8 to 9.8 MPa) and the data was fitted by non-linear regression method using power law model. The calculated reaction orders and activation energies were 2.8, 1.5 and 189 KJ/mol, 98.9 KJ/mol for HDS and HDN, respectively. The results of HRTEM and H2-TPR indicated lower SMI in mC supported catalyst resulting in the generation of qualitatively Type-II like NiMoS phase on functionalized mC supports, which is considered to be very active for hydrotreating. The hydrotreating activity of the optimum catalyst was higher than that of commercial catalyst (supported on ã-Al2O3). Long term deactivation experiment carried out over a total period of 10 weeks confirmed the durability of NiMo/mC catalyst for the duration of operation. This study reveals the immense capability of functionalized mC supports to become the potential alternative catalyst support to conventional ã-Al2O3 for the hydrotreating of gas oil feedstocks.