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Petroleum refining processes provide the daily requirements of energy for the global market. Each refining process produces wastes that have the capacity to harm the environment if not properly disposed of. The treatment of refinery waste is one of the most complex issues faced by refinery managers. Also, the hazardous nature of these wastes makes them rather costly to dispose of for the refineries. In this thesis, system analysis tools are used to design a program that allows for the selection of the optimal control, minimization and treating options for petroleum refinery waste streams. The performance of the developed model is demonstrated via a case study. Optimal mitigation alternatives to meet the emission reduction targets were studied by evaluating their relative impact on the profitable operation of the given facility. It was found that the optimal mitigation steps was to reduce emission precursors by conducting feed switches at the refinery. In all cases, the optimal solution did not include a capital expansion of the emission control facilities and equipment.

The fouling characteristics of a desalted crude oil were investigated in a systematic investigation. There are two main parts in this study, the dry bulk tests (dehydrated crude oil) and the wet bulk tests (to which desalter brine was added). Three barrels of desalted crude oil provided by Amoco Oil Company were studied. For the dry bulk tests, no brine was added to the crude oil. The effects of fluid velocity and surface temperature on fouling were investigated. The higher the surface temperature the greater the fouling was observed. Fouling decreased with an increase of fluid velocity. Fluid velocity had a stronger effect on fouling at low surface temperatures than at high surface temperatures. It was also observed that the fouling behavior of crude oil depended on small difference in composition. The threshold surface temperatures for the initiation of fouling were 400-450 °F (3.0 ft/sec), 525-550 °F (5.5 ft/sec), 550-600 °F (8.0 ft/sec) and about 600 °F (10.0 ft/sec) for Barrel No. 2 and Barrel No. 3. For Barrel No. 1 however, the threshold surface temperatures were about 550 °F (3.0 ft/sec) and 600 °F (5.5 ft/sec). For the wet bulk tests, a certain amount desalter brine (weight percentage = 0.8%) was added to the crude oil for each run. The effects of fluid velocity, surface temperature and the presence of brine on fouling were investigated. Higher surface temperature enhanced fouling considerably. Fouling was reduced as fluid velocity was increased. It was shown that brine had a strong effect on fouling. No fouling occurred for velocities of 5.5 and 8.0 ft/sec at a surface temperature of 350 °F which was a condition for which an aqueous phase was present and the salt remained in solution. Significant fouling occurred for velocities of 5.5 and 8.0 ft/sec at a surface temperature operated at a low 400 °F (Tb = 300 °F) which was a condition for which the aqueous phase at the heat transfer surface was dissolved or boiled to extinction and the salt was deposited on the heat transfer surface. / Graduation date: 1991

Petroleum refining processes provide the daily requirements of energy for the global market. Each refining process produces wastes that have the capacity to harm the environment if not properly disposed of. The treatment of refinery waste is one of the most complex issues faced by refinery managers. Also, the hazardous nature of these wastes makes them rather costly to dispose of for the refineries. In this thesis, system analysis tools are used to design a program that allows for the selection of the optimal control, minimization and treating options for petroleum refinery waste streams. The performance of the developed model is demonstrated via a case study. Optimal mitigation alternatives to meet the emission reduction targets were studied by evaluating their relative impact on the profitable operation of the given facility. It was found that the optimal mitigation steps was to reduce emission precursors by conducting feed switches at the refinery. In all cases, the optimal solution did not include a capital expansion of the emission control facilities and equipment.

Thesis. 1977. Ph.D.--Massachusetts Institute of Technology. Dept. of Chemical Engineering. / M̲i̲c̲ṟo̲f̲i̲c̲ẖe̲ c̲o̲p̲y̲ a̲v̲a̲i̲ḻa̲ḇḻe̲ i̲ṉ A̲ṟc̲ẖi̲v̲e̲s̲ a̲ṉḏ S̲c̲i̲e̲ṉc̲e̲.̲ / Vita. / Bibliography : leaves 378-385. / by John A. Wilkens. / Ph.D.

This dissertation examines three facets of U.S. energy use and policy. First, I examine the Gulf Coast petroleum refining industry to determine the structure of the industry. Using the duality between cost-minimization and production functions, I estimate the demand for labor to determine the underlying production function. The results indicate that refineries have become more capital intensive due to the relative price increase of labor. The industry has consolidated in response to higher labor costs and costs of environmental compliance. Next, I examine oil production in the United States. An empirical model based on the theoretical framework of Pindyck is used to estimate production. This model differs from previous research by using state level data rather than national level data. The results indicate that the production elasticity with respect to reserves and the price elasticity of supply are both inelastic in the long run. The implication of these findings is that policies designed to increase domestic production through subsidies, tax breaks, or royalty reductions will likely provide little additional oil. We simulate production under three scenarios. In the most extreme scenario, prices double between 2005 and 2030 while reserves increase by 50%. Under this scenario, oil production in 2030 is approximately the same as the 2005 level. The third essay estimates demand for fossil fuels in the U.S. and uses these estimates to forecast CO2 emissions. The results indicate that there is almost no substitution from one fossil fuel to another and that all three fossil fuels are inelastic in the long run. Additionally, all three fuels respond differently to changes in GDP. The result of the differing elasticities with respect to GDP is that the energy mix has changed over time. The implication for forecasting CO2 emissions is that models that cannot distinguish changes in the energy mix are not effective in forecasting CO2 emissions.

Este trabalho tem por objetivo apresentar a evolução da indústria do refino de petróleo no Brasil desde suas origens, sua evolução ao longo dos anos, explicitando as mudanças no perfil de produção, na matéria prima processada e na complexidade das nossas refinarias. Busca, também, apresentar os próximos passos para o refino de petróleo nacional, seus desafios face a produção de petróleos pesados e ácidos, bem como os impactos provocados pela necessidade de produção de derivados com especificações cada vez mais restritivas e com menor impacto ambiental. Optou-se pelo hidrorrefino como o primeiro grande passo para os próximos anos concluindo-se que unidades para o hidrotratamento de correntes intermediárias ou mesmo produto final assumirão um papel fundamental nos futuros esquemas de refino. Outra vertente importante analisada foi a necessidade de aumento de conversão, ressaltando-se que o caminho hoje escolhido de implantação de Unidades de Coqueamento Retardado se esgota no início da próxima década abrindo caminho para a tecnologia de hidroconversão de resíduo. Com relação à qualidade da gasolina e do óleo diesel foi apresentada uma proposta de esquema de refino para permitir o atendimento de especificações mais rígidas / This thesis aims to present the oil refining industry in Brazil since its origin, its evolution along the years, showing the changes in the production profile, in the crude oils processed and in the complexity of our refineries. Tries, additionally, to present the next steps for the national oil refining industry, its challenges facing the acid and heavy crude oil production, besides the impacts coming from the necessity of producing derivatives with stricter specifications and reduced environmental impact. Hydro-refining is showed to be the option for the next years, once intermediary and final products hydro-treating will assume a fundamental role on future refining scheme. Another important issue analyzed was the increased conversion necessity, highlighting that the current solution adopted which is the delayed coking units reaches its deadline in the beginning of the next decade, opening the door for residuum hydro-conversion technology. Related to gasoline and diesel oil quality, a refining configuration proposal was presented in order to achieve tighter specifications

Este trabalho tem por objetivo apresentar a evolução da indústria do refino de petróleo no Brasil desde suas origens, sua evolução ao longo dos anos, explicitando as mudanças no perfil de produção, na matéria prima processada e na complexidade das nossas refinarias. Busca, também, apresentar os próximos passos para o refino de petróleo nacional, seus desafios face a produção de petróleos pesados e ácidos, bem como os impactos provocados pela necessidade de produção de derivados com especificações cada vez mais restritivas e com menor impacto ambiental. Optou-se pelo hidrorrefino como o primeiro grande passo para os próximos anos concluindo-se que unidades para o hidrotratamento de correntes intermediárias ou mesmo produto final assumirão um papel fundamental nos futuros esquemas de refino. Outra vertente importante analisada foi a necessidade de aumento de conversão, ressaltando-se que o caminho hoje escolhido de implantação de Unidades de Coqueamento Retardado se esgota no início da próxima década abrindo caminho para a tecnologia de hidroconversão de resíduo. Com relação à qualidade da gasolina e do óleo diesel foi apresentada uma proposta de esquema de refino para permitir o atendimento de especificações mais rígidas / This thesis aims to present the oil refining industry in Brazil since its origin, its evolution along the years, showing the changes in the production profile, in the crude oils processed and in the complexity of our refineries. Tries, additionally, to present the next steps for the national oil refining industry, its challenges facing the acid and heavy crude oil production, besides the impacts coming from the necessity of producing derivatives with stricter specifications and reduced environmental impact. Hydro-refining is showed to be the option for the next years, once intermediary and final products hydro-treating will assume a fundamental role on future refining scheme. Another important issue analyzed was the increased conversion necessity, highlighting that the current solution adopted which is the delayed coking units reaches its deadline in the beginning of the next decade, opening the door for residuum hydro-conversion technology. Related to gasoline and diesel oil quality, a refining configuration proposal was presented in order to achieve tighter specifications

Researchers use metal-thiophene complexes to mimic reactions which occur inside hydrodesulfurization (HDS) reactors. Information obtained from these model studies may often be applied to understanding the mechanisms involved with commercially used catalysts. Certain mechanisms¹ for HDS propose thiophene ring cleavage,forming a metallacycle, prior to hydrogenation of one double bond. There are, however, limited examples of complexes derived from C-S cleavage.^2,3,4 Thermal reactions of the iridium complex, [Ir(COD)(PMe₃₎₃]Cl (COD=1,5- cyclooctadiene), with thiophene, thiazole, 4-methyl thiazole and 5-methyl thiazole yields the C-S addition metallacycles (Me₃P)₃Ir-(CH=CHCH=S)CI (I), \ (Me3P)3Ir-(CH=NCH=CHS)CI (II), (Me3P)3Ir-CCH=NC(CH3)=CHS)CI (III) and (Me3P)3Ir (CH=NCH=C(CH3)S)CI (IV), respectively. These compounds were characterized using the following methods: ¹H NMR, ¹³C NMR, ³¹P NMR, elemental analysis and single crystal x-ray diffraction. Following C-S addition to [Ir(COD)(PMe3)3]CI, nitrogen present in the thiazoles exhibit enhanced nucleophilicity. For exmnple, compounds II-IV react with methylene chloride to form dimers: CH2[NCR=CR'SIr(Cl)(PMe3)3CH]2. The above compounds are soluble in water and react with PF6 salts liberating the chloride atom from the Ir center. pKb measurements were recorded as well. This thesis describes the synthesis and examination of con1pounds I-IV as they may model the HDS process. Compounds II-IV represent the first examples of ring opened thiazole metallacycles with iridium. / Master of Science

Considerable work has been done on the economic production of shale oil from oil shale. Of the possible materials which could replace crude petroleum as used today, oil shale possesses the greatest possibilities since, when retorted, it produces a shale oil very similar to crude petroleum, and on refining the products produced are similar. Of the fuel resources available in the United States, 98.8 percent is attributed to coal, 0.8 percent to oil shale, 0.2 percent to crude petroleum, and 0.2 percent to natural gas. The purpose of this investigation was to study the effect of oil shale particle size on the shale oil obtained from oil shale retorted in a fluidized bed. Oil shale of minus 16 plus 28, minus 28 plus 70, minus 70 plus 100, and minus 100 plus 200 mesh (Tyler screen scale) was retorted at 715°F in a 4-inch diameter retort 36 inches long using carbon dioxide as the fluidizing medium. A retorting unit consisting of a fluidizing retort, fluidizing gas-heating section, disengaging section, cyclone separator, condensers, a surge tank, gas circulation system, and temperature measurement and control equipment was designed and constructed. The fluidizing gas-heating section was constructed from a flanged 5-foot section of 8-inch diameter black iron pipe with eight 1250-watt heaters placed in the heating section at 6-inch intervals along the vertical axis. Additional heaters were provided on the gas transfer line to reduce the heating time. The condensers were simple tube-in-shell heat exchangers constructed from 1-1/2-inch and 3/4-inch deoxidized copper pipe with headers for the oil receivers. The condensers were designed and constructed to operate counter-currently using return gas from the brine cooled condenser as the cooling medium in the first two condensers, water in the third condenser, and brine in the fourth condenser. A gas circulation section consisting of a gas pump and appropriate valves was constructed to circulate the gas through the system. Temperature control and measuring equipment were provided for control of the gas temperature to the retort, and for measuring the temperature of the entering and exit material in each section. On retorting 16-1/4 pounds of oil shale for one hour at a gas pressure of 10 pounds per square inch gage, yields of 50.5, 47.3, 40.9, and 39.4 percent of the available shale oil were obtained from oil shale of minus 16 plus 28, minus 28 plus 70, minus 70 plus 100, and minus 100 plus 200 mesh (Tyler screen scale), respectively. The A.P.I. gravity was found to increase from 15.2, 17.9, 18.6, and 22.4 degrees, and the kinematic viscosity decrease from 12.18, 4.64, 2.94, and 1.66 centipoises for a decrease in particle size from minus 16 plus 28, minus 28 plus 70, minus 70 plus 100, and minus 100 plus 200 mesh (Tyler screen scale), respectively. The mid-boiling point of the shale oil decreased 510, 500, 482, and 380°F for the above particle sizes as did the average boiling point which decreased from 824, 724, 690, and 590 for oil shale of the same particle size. The yield of non-condensable gases increased 0.67, 0.72, 1.01, and 1.2 cubic feet for oil shale of minus 16 plus 28, minus 28 plus 70, minus 70 plus 100, and minus 100 plus 200 mesh (Tyler screen scale). A decrease in particle size of oil shale retorted at 715°F in a 4-inch fluidized retort using carbon dioxide as the fluidizing medium, was found to definitely reduce the mid-boiling point, average boiling point, and the kinematic viscosity of the shale oil, and to increase the A.P.I. gravity of the shale oil obtained as well as the volume of retort gas. / Master of Science