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

Multi-walled carbon nanotubes (MWCNTs) are a potential alternative to commonly used catalyst support structures in hydrotreating processes. Synthesis of MWCNTs with specific pore diameters can be achieved by chemical vapor deposition (CVD) of a carbon source onto an anodic aluminum oxide (AAO) template. AAO films consist of pore channels in a uniform hexagonal arrangement that run parallel to the surface of the film. These films are created by the passivation of an aluminum anode within an electrolysis cell consisting of certain weak acid electrolytes. Changing the concentration of the electrolyte (oxalic acid) and the electrical potential of the electrolysis cell altered the pore channel diameter of these AAO films. Controlling the pore diameter of these templates enabled the pore diameter of MWCNTs synthesized by CVD to be controlled as well. The produced MWCNTs were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Raman spectroscopy, and N2 adsorption analysis. Anodizing conditions of 0.40 M oxalic acid concentration and 40.0 V maximum anodizing potential were found to produce AAO films that resulted in MWCNTs with optimum surface characteristics for a catalyst support application. CVD parameter values of 650°C reaction temperature and 8.00 mL/(min·g) C2H2-to-AAO ratio were found to produce the highest yield of MWCNT product.<p> The MWCNTs were synthesized for the purpose of supporting hydroprocessing catalysts, with several grades of NiMo/MWCNT sulfide catalysts being prepared to determine the optimum pore size. These catalysts were characterized by techniques of TEM, CO chemisorption, N2 adsorption, and H2 temperature programmed reduction (TPR). A MWCNT grade with 67 nm inner diameters (found from TEM analysis) was found to offer the best hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities for the treatment of coker light gas oil (CLGO). After determining the most suitable pore diameter, the optimum catalyst metal loadings were found to be 2.5 wt.% for Ni and 19.5 wt.% for Mo. The optimum catalyst was found to offer HDS conversions of 90.5%, 84.4%, and 73.5% with HDN conversions of 75.9%, 65.8%, and 55.3% for temperatures of 370°C, 350°C, and 330°C, respectively. An equal mass loading of commercial NiMo/ã-Al2O3 catalyst offered HDS conversions of 91.2%, 77.9%, and 58.5% with HDN conversions of 71.4%, 53.2%, and 31.3% for temperatures of 370°C, 350°C, and 330°C, respectively.<p> A kinetic study was performed on the optimum NiMo/MWCNT catalyst to help predict its HDS and HDN activities while varying the parameters of temperature, liquid hourly space velocity (LHSV), pressure, and gas-to-oil flow rate ratio. Rate expressions were then developed to predict the behavior of both the HDS and HDN reactions. Power law models were best fit with reaction orders of 2.6 and 1.2, and activation energies of 161 kJ/mol and 82.3 kJ/mol, for the HDS and HDN reactions, respectively. Generalized Langmuir-Hinshelwood models were found to have reaction orders of 3.0 and 1.5, and activation energies of 155 kJ/mol and 42.3 kJ/mol, for the HDS and HDN reactions, respectively.

The pore diameter of a catalyst support controls the diffusion of reactant molecules to the catalytic active sites; thus, affecting the rates and conversions of the hydrotreating reactions. Desirable textural properties of SBA-15 makes it a potential alternative to the conventionally used γ-Al2O3 support due to the fact that its pore size can be manipulated via controlling the synthesis parameters, while maintaining relatively high surface area. Larger pore diameter SBA-15 supports may facilitate the diffusion of bulky molecules as that of the asphaltenes present in the heavy petroleum fractions, making it a potential catalyst support for hydrotreating operations. Considering the very sour nature of Canadas bitumen with high sulfur contents in the range of 2-6 wt %, the appreciably high sulfur contents particularly present in Athabasca derived heavy gas oils (about 4 wt % sulfur), the rising demand for cleaner fuels, and also the increasing stringency on environmental standards, the need for novel and improved hydrotreating catalysts cannot be overemphasized. By varying the molar ratio of hexane to ammonium fluoride, the pore channels of SBA-15 could be varied. Controlling the pore diameter of these supports via micelle swelling facilitated the production of larger pore diameter SBA-15-supported catalysts. In this project, four mesoporous silica SBA-15 catalyst supports with pore diameters in the range of 5-20 nm were synthesized in the preliminary phase using hexane as the micelle swelling agent and subsequently utilized for the loading of 2 wt.% Fe and 15 wt.% W catalyst metals, respectively. The hexagonal mesoscopic structure of these materials were characterized using powder small-angle X-ray scattering (SAXS), N2 adsorption-desorption isotherms, TEM and SEM images. Powder XRD analysis evidenced inhomogeneous metal dispersion on the largest pore diameter catalyst. An optimum pore diameter of 10 nm was found for Cat-B and subsequently used to obtain the optimum Fe and W loadings required to achieve the best hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities. The optimum catalyst was found to be Cat-H with metal loadings of 3 wt.% Fe and 30 wt.% W. At these loadings and temperatures of 375°C, 388°C, and 400°C, HDS activities of 53.4%, 64.1%, and 73.3% with corresponding HDN activities of 21.9%, 26.2%, and 38.3%, respectively, were recorded. Catalytic performance evaluations conducted on equal mass loading using a reference commercial γ-Al2O3-supported FeW catalyst offered HDS activities of 69.3%, 80.4%, and 89.1%, with corresponding HDN activities of 16.4%, 32.4%, and 49.3% at the same temperatures studied. However, no significant changes in HDS and HDN activities were observed for similar evaluations on volume percent metals loading basis. Kinetic studies performed with the optimum FeW/SBA-15 catalyst suggested activation energies of 147.2 and 150.6 kJ/mol for HDS and HDN, respectively, by the Langmuir-Hinshelwoods model. Similar results were predicted by the Power Law and Multi-parameter models for HDS (129.6 and 126.7 kJ/mol, respectively), which does not conclusively make the latter model clearly stand out as the best. Data fitting by the Power Law suggested reaction orders of 2 and 1.5 for HDS and HDN, which seem to be consistent for the hydrotreatment of heavy gas oil. Finally, a long-term deactivation study spanning a period of 60 days time-on-stream showed the optimum catalyst to be stable under hydrotreating experiments conducted in a downward flow micro-trickle bed reactor at temperature, pressure, liquid hourly space velocity (LHSV), and gas/oil ratio of 375400˚C, 8.8 MPa, 1h-1, and 600 mL/mL (at STP), respectively.

It is observed that the flowing bottom-hole temperature (FBHT) changes as a result of production, injection or shutting the well down. Variations in temperature mainly occur due to geothermal gradient, injected fluid temperature, frictional heating and the Joule-Thomson effect. The latter is the change of temperature because of expansion or compression of a fluid in a flow process involving no heat transfer or work. CMG STARS thermal simulation sector model developed in this study was used to analyze FBHT changes and understand the reasons. Twenty three main and five additional cases that were developed by using this model were simulated and relation of BHT with other parameters was investigated. Indeed the response of temperature to the change of some parameters such as bottom-hole pressure and gas-oil ratio was detected and correlation was tried to set between these elements. Observations showed that generally FBHT increases when GOR decreases and/or flowing bottom-hole pressure (FBHP) increases. This information allows estimating daily gas-oil ratios from continuously measured BHT. Results of simulation were compared with a real case and almost the same responses were seen. The increase in temperature after the start of water and gas injection or due to stopping of neighboring production wells indicated interwell communications. Additional cases were run to determine whether there are BHT changes when initial temperature was kept constant throughout the reservoir. Different iteration numbers and refined grids were used during these runs to analyze iteration errors / however no significant changes were observed due to iteration number differences and refined grids. These latter cases showed clearly that variations of temperature don&rsquo / t occur only due to geothermal gradient, but also pressure and saturation changes. On the whole, BHT can be used to get data ranging from daily gas-oil ratios to interwell connection if analyzed correctly.

Submitted by Lucienne Costa (lucienneferreira@ufcg.edu.br) on 2018-04-04T20:52:13Z No. of bitstreams: 1 JÉSSICA BARBOSA DA SILVA DO NASCIMENTO - DISSERTAÇÃO (PPGEM) 2017.pdf: 5634263 bytes, checksum: 929da71867fefc79201bbfa0a102a100 (MD5) / Made available in DSpace on 2018-04-04T20:52:13Z (GMT). No. of bitstreams: 1 JÉSSICA BARBOSA DA SILVA DO NASCIMENTO - DISSERTAÇÃO (PPGEM) 2017.pdf: 5634263 bytes, checksum: 929da71867fefc79201bbfa0a102a100 (MD5) Previous issue date: 2017-08-17 / Capes / Os separadores são equipamentos utilizados no processamento primário da indústria do petróleo com o objetivo de separar a mistura multifásica proveniente dos poços produtores. O trabalho avaliou o efeito dos dispositivos internos do vaso separador sobre a dinâmica do escoamento no processo de separação gás/óleo. Foi definido uma modelagem matemática com base na dinâmica de fluidos computacional (CFD) do separador horizontal bifásico. Adotou-se a abordagem Euleriana-Euleriana, considerando o modelo de mistura, disponibilizado no software Ansys CFX 15.0. O domínio consiste em um separador horizontal cilíndrico constituído de uma placa porosa que o divide em duas regiões: a região de separação primária, contendo três dispositivos internos (um defletor e duas chicanas) e a região de decantação. Foi gerada uma malha numérica empregando elementos tetraédricos, para a discretização das equações de conservação de massa, momento linear e de turbulência k padrão usando o método dos volumes finitos. Assumiu-se o escoamento em regimes permanente e transiente, isotérmico, com propriedades dos fluidos constantes e das forças interfaciais foram consideradas apenas as forças de arraste. Os resultados dos campos vetoriais de velocidade, assim como a fração volumétrica das fases indicam que a dinâmica do escoamento é fortemente dependente dos dispositivos internos. Na região de separação primária observou-se um alto nível de mistura causada pela turbulência gerada pelo impacto dos fluidos sobre a placa defletora posicionada imediatamente após a seção de entrada. A placa porosa possibilitou uma redução da turbulência dos fluidos, causada pela resistência do meio poroso ao escoamento. / The separators are equipments used in the primary processing of the petroleum industry to separate the multiphase mixture from the producing wells. The work evaluated the effect of the internal devices of the separator vessel on the flow dynamics in the gas/oil separation process. A mathematical model was defined based on computational fluid dynamics (CFD) of the horizontal two-phase separator. The Eulerian-Eulerian approach was adopted, considering the mixture model, available in Ansys CFX 15.0 software. The domain consists of a horizontal cylindrical separator consisting of a porous plate that divides it in to two regions: the primary separation, containing three internal devices (one deflector plate and two baffles) and the settling region. A numerical grid was generated employing tetrahedral elements, for the discretization of the mass conservation, linear momentum and k standard turbulence equations using the finite volume method. Isothermal flow with constant fluid properties in both steady state and transient regimes were assumed, and, from the interfacial forces, only the drag forces were considered. The velocity vector field results as well as the volumetric fraction of the phases indicate that the flow dynamics are strongly dependent on the internal devices. In the primary separation region, a high-level of mixing was observed due to the turbulence generated by the impact of the fluids on a deflector plate positioned immediately after the inlet section. The porous plate allowed a reduction of the turbulence of the fluids, caused by the resistance of the porous medium to the flow.

Ship exhausts contain high levels of sulphur oxides, nitrogen oxides, carbon dioxide and particles dueto the heavy fuel oil, HFO, used for combustion and the combustion characteristics of the engine.As a result of upcoming stricter regulations for shipping pollution, as well as growing attentionto greenhouse gas emissions, air pollution and uncertainty of future petroleum oil supply, a shifttowards a cleaner burning fuel is needed.This work explores potential alternative fuels, both conventional and unconventional, and abatementtechnologies, to be used by tankers in the worldwide spot market to comply with upcomingenvironmental regulations in the near and coming future. As a reference the product tanker M/TGotland Marieann is used and recommendations for which fuel that shall be used by the referenceship in 2015 and 2020 are presented.The environmental assessment and evaluation of the fuels are done from a life cycle perspective usingresults from Life Cycle Assessment, LCA, studies.This study illustrates that, of the various alternatives, methanol appears to be the best candidatefor long-term, widespread replacement of petroleum-based fuels within tanker shipping. It does notemit any sulphur oxides nor particles and the nitrogen oxides are shown to be lower than those ofmarine gas oil, MGO. The global warming potential of the natural gas produced methanol is notlower than that of MGO, but when gradually switching to bio-methanol the greenhouse gas emissionsare decreasing and with methanol the vision of a carbon free society can be reached.For 2015 a switch towards methanol is not seen as realistic. Further research and establishment ofregulations and distribution systems are needed, however there are indications that a shift will bepossible sometime between 2015 and 2020. For 2015 a shift towards MGO is suggested as it involveslow investment costs and there is no need for infrastructure changes. As MGO is more expensivethan methanol, a shift is preferable as soon as the market, technology and infrastructure are ready.

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.

Yes / Fluidized catalytic cracking (FCC) is regarded one of the most significant operations in the oil refining industries to convert feedstock (mainly vacuum gasoil) to valuable products (namely gasoline and diesel). The behavior of the fluidized catalytic cracking process is playing a main part on the overall benefits of refinery units and improving in process or control of fluidized catalytic cracking plants will result in exciting benefits economically. According to these highlights, this study is aimed to develop a new mathematical model for the FCC process taking into account the complex hydrodynamics of the reactor regenerator system with a new six lumps kinetic model for the riser. The mathematical model, simulation and optimization have done utilizing vacuum gas oil (VGO) as a feedstock and zeolite as a catalyst under the following operating conditions: temperature (733K, 783K, and 813K), weight hourly space velocity (5, 20 and 30hr−1) and catalyst to oil ratio (4, 7 and 10). The best kinetic parameters of the relevant reactions are estimated using the optimization technique based on the experimental results taken from literature. The effect of operating condition (mainly, reaction temp (T), catalyst to oil ratio (CTO) and weight hourly space velocity (WHSV) on the product composition has also been discussed. The optimal kinetic parameters obtained from the pilot plant scale have been employed to develop an industrial FCC process, where optimal operating condition based on maximum conversion of VGO with minimum cost in addition to maximizing the octane number of gasoline (GLN), have been studied. Minimum coke content deposition the catalyst within the regenerator is also investigated here. New results (the highest conversion and octane number, and the lowest coke content) have obtained in comparison with those reported in the literature.

Heightened concerns for cleaner air and increasingly more stringent regulations on sulphur content in transportation fuels will make desulphurization more and more important. The sulphur problem is becoming more serious in general, particularly for diesel fuels as the regulated sulphur content is getting an order of magnitude lower, while the sulphur contents of crude oils are becoming higher. This thesis aimed to develop a desulphurisation process (based on oxidation followed by extraction) with high efficiency, selectivity and minimum energy consumption leading to minimum environmental impact via laboratory batch experiments, mathematical modelling and optimisation. Deep desulphurization of model sulphur compounds (di-n-butyl sulphide, dimethyl sulfoxide and dibenzothiophene) and heavy gas oils (HGO) derived from Libyan crude oil were conducted. A series of batch experiments were carried out using a small reactor operating at various temperatures (40-100 °C) with hydrogen peroxide (H2O2) as oxidant and formic acid (HCOOH) as catalyst. Kinetic models for the oxidation process are then developed based on 'total sulphur approach'. Extraction of unoxidised and oxidised gas oils was also investigated using methanol, dimethylformamide (DMF) and N-methyl pyrolidone (NMP) as solvents. For each solvent, the 'measures' such as: the partition coefficient (KP), effectiveness factor (Kf) and extractor factor (Ef) are used to select the best/effective solvent and to find the effective heavy gas oil/solvent ratios. A CSTR model is then developed for the process for evaluating viability of the large scale operation. It is noted that while the energy consumption and recovery issues could be ignored for batch experiments these could not be ignored for large scale operation. Large amount of heating is necessary even to carry out the reaction at 30-40 °C, the recovery of which is very important for maximising the profitability of operation and also to minimise environmental impact by reducing net CO2 release. Here the heat integration of the oxidation process is considered to recover most of the external energy input. However, this leads to putting a number of heat exchangers in the oxidation process requiring capital investment. Optimisation problem is formulated using gPROMS modelling tool to optimise some of the design and operating parameters (such as reaction temperature, residence time and splitter ratio) of integrated process while minimising an objective function which is a coupled function of capital and operating costs involving design and operating parameters. Two cases are studied: where (i) HGO and catalyst are fed as one feed stream and (ii) HGO and catalyst are treated as two feed streams. A liquid-liquid extraction model is then developed for the extraction of sulphur compounds from the oxidised heavy gas oil. With the experimentally determined KP multi stage liquid-liquid extraction process is modelled using gPROMS software and the process is simulated for three different solvents at different oil/solvent ratios to select the best solvent, and to obtain the best heavy gas oil to solvent ratio and number of extraction stages to reduce the sulphur content to less than 10 ppm. Finally, an integrated oxidation and extraction steps of ODS process is developed based on the batch experiments and modelling. The recovery of oxidant, catalyst and solvent are considered and preliminary economic analysis for the integrated ODS process is presented.