Nowadays, computers are extensively used in engineering modeling and simulation fields in many different ways, one of which is in chemical engineering. Simulation and modeling of a chemical process plant and the sizing of the equipment with the assistance of computers, is of special interests to process engineers and investors. This is due to the ability of high speed computers, which make millions of mathematical calculations in less than a second associated with the new powerful software that make the engineering calculations more reliable and precise by making very fast iterations in thermodynamics, heat and mass transfer calculations. This combination of new technological hardware and developed software enables process engineers to deal with simulation, design, optimization, control, analysis etc. of complex plants, e.g. refinery and petrochemical plants, reliably and satisfactorily. The main chemical process simulators used for static and dynamic simulations are ASPEN PLUS, ASPEN HYSYS, PRO II, and CHEMCAD. The basic design concepts of all simulators are the same and one can fairly use all simulators if one is expert in any of them. Hydrogenation process is an example of the complex plants, to which a special attention is made by process designers and manufacturers. This process is used for upgrading of hydrocarbon feeds containing sulfur, nitrogen and/or other unsaturated hydrocarbon compounds. In oil and gas refineries, the product of steam cracking cuts, which is valuable, may be contaminated by these unwanted components and thus there is a need to remove those pollutants in downstream of the process. Hydrogenation is also used to increase the octane number of gasoline and gas oil. Sulfur, nitrogen and oxygen compounds and other unsaturated hydrocarbons are undesired components causing environmental issues, production of by-products, poisoning the catalysts and corrosion of the equipment. The unsaturated C=C double bonds in dioleffinic and alkenyl aromatics compounds, on the other hand, cause unwanted polymerization reactions due to having the functionality equal to or greater than 2. Hydrogenation process of the undesired components will remove those impurities and/or increase the octane number of aforementioned hydrocarbons. This process is sometimes referred to as “hydrotreating”; however, “upgrader” is a general word and is, of course, of more interest. In this thesis, a hydrogenation process plant was designed on the basis of the chemistry of hydrocarbons, hydrogenation reaction mechanism, detailed study of thermodynamics and kinetics and then a steady-state simulation and design of the process is carried out by ASPEN HYSYS 2006 followed by design evaluation and some modifications and conclusions. Hydrogenation reaction has a complicated mechanism. It has been subjected to hot and controversial debates over decades. Many kinetic data are available, which contradict one another. Among them, some of the experimental researches utilize good assumptions in order to simplify the mechanism so that a “Kinetic Reaction” modeling can be employed. This thesis takes the benefit of such research works and applies some conditions to approve the validity of those assumptions. On the basis of this detailed study of reaction modeling and kinetic data, a hydrogenation plant was designed to produce and purify over 98 million kilograms of different products; e.g. Benzene, Toluene, Iso-octane etc. with fairly high purity.

Nowadays, computers are extensively used in engineering modeling and simulation fields in many different ways, one of which is in chemical engineering. Simulation and modeling of a chemical process plant and the sizing of the equipment with the assistance of computers, is of special interests to process engineers and investors. This is due to the ability of high speed computers, which make millions of mathematical calculations in less than a second associated with the new powerful software that make the engineering calculations more reliable and precise by making very fast iterations in thermodynamics, heat and mass transfer calculations. This combination of new technological hardware and developed software enables process engineers to deal with simulation, design, optimization, control, analysis etc. of complex plants, e.g. refinery and petrochemical plants, reliably and satisfactorily. The main chemical process simulators used for static and dynamic simulations are ASPEN PLUS, ASPEN HYSYS, PRO II, and CHEMCAD. The basic design concepts of all simulators are the same and one can fairly use all simulators if one is expert in any of them. Hydrogenation process is an example of the complex plants, to which a special attention is made by process designers and manufacturers. This process is used for upgrading of hydrocarbon feeds containing sulfur, nitrogen and/or other unsaturated hydrocarbon compounds. In oil and gas refineries, the product of steam cracking cuts, which is valuable, may be contaminated by these unwanted components and thus there is a need to remove those pollutants in downstream of the process. Hydrogenation is also used to increase the octane number of gasoline and gas oil. Sulfur, nitrogen and oxygen compounds and other unsaturated hydrocarbons are undesired components causing environmental issues, production of by-products, poisoning the catalysts and corrosion of the equipment. The unsaturated C=C double bonds in dioleffinic and alkenyl aromatics compounds, on the other hand, cause unwanted polymerization reactions due to having the functionality equal to or greater than 2. Hydrogenation process of the undesired components will remove those impurities and/or increase the octane number of aforementioned hydrocarbons. This process is sometimes referred to as “hydrotreating”; however, “upgrader” is a general word and is, of course, of more interest. In this thesis, a hydrogenation process plant was designed on the basis of the chemistry of hydrocarbons, hydrogenation reaction mechanism, detailed study of thermodynamics and kinetics and then a steady-state simulation and design of the process is carried out by ASPEN HYSYS 2006 followed by design evaluation and some modifications and conclusions. Hydrogenation reaction has a complicated mechanism. It has been subjected to hot and controversial debates over decades. Many kinetic data are available, which contradict one another. Among them, some of the experimental researches utilize good assumptions in order to simplify the mechanism so that a “Kinetic Reaction” modeling can be employed. This thesis takes the benefit of such research works and applies some conditions to approve the validity of those assumptions. On the basis of this detailed study of reaction modeling and kinetic data, a hydrogenation plant was designed to produce and purify over 98 million kilograms of different products; e.g. Benzene, Toluene, Iso-octane etc. with fairly high purity.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-03-02T22:55:04Z No. of bitstreams: 1 HerbertSenzanoLopes_DISSERT.pdf: 1964831 bytes, checksum: a1f3b710808bf3ed42490612f2700bca (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-03-04T00:31:31Z (GMT) No. of bitstreams: 1 HerbertSenzanoLopes_DISSERT.pdf: 1964831 bytes, checksum: a1f3b710808bf3ed42490612f2700bca (MD5) / Made available in DSpace on 2016-03-04T00:31:31Z (GMT). No. of bitstreams: 1 HerbertSenzanoLopes_DISSERT.pdf: 1964831 bytes, checksum: a1f3b710808bf3ed42490612f2700bca (MD5) Previous issue date: 2014-12-23 / A parte pesada do petr?leo pode ser utilizada para in?meras finalidades, uma delas ? a obten??o de ?leos lubrificantes. Com base nesse contexto, muitos pesquisadores v?m estudando alternativas de separa??o desses constituintes de petr?leo bruto, entre elas pode ser citada a destila??o molecular, uma t?cnica de evapora??o for?ada diferente dos outros processos convencionais presentes na literatura. Este processo pode ser classificado como um caso especial de destila??o a alto v?cuo com press?es que chegam a atingir faixas extremamente baixas da ordem de 0,1 Pascal. As superf?cies de evapora??o e de condensa??o devem apresentar uma dist?ncia entre si da ordem de grandeza do percurso livre m?dio das mol?culas evaporadas, isto ?, as mol?culas evaporadas facilmente atingir?o o condensador, pois as mesmas encontrar?o um percurso sem obst?culos, o que ? desej?vel. Logo, a principal contribui??o deste trabalho consiste na simula??o do processo de destila??o molecular de filme descendente do petr?leo. O petr?leo bruto foi caracterizado utilizando o UniSim? Design R430 e o Aspen HYSYS? V8.5. Com os resultados desta caracteriza??o foram efetuados, em planilhas de c?lculo no Microsoft? Excel?, os c?lculos das propriedades f?sico-qu?micas dos res?duos de uma amostra de petr?leo, i.e., termodin?micas e de transporte. De posse dessas propriedades estimadas e das condi??es de contorno sugeridas pela literatura, foram resolvidas as equa??es dos perfis de temperatura e concentra??o atrav?s do m?todo de diferen?as finitas impl?cito utilizando a linguagem de programa??o Visual Basic? (VBA) for Excel?. O resultado do perfil de temperatura apresentou-se coerente com os reproduzidos pela literatura, havendo em seus valores iniciais uma leve distor??o em consequ?ncia da natureza do ?leo estudado ser mais leve que o da literatura. Os resultados dos perfis de concentra??o mostraram-se eficientes permitindo perceber que as concentra??es dos mais vol?teis diminuem e as dos menos vol?teis aumentam em fun??o do comprimento do evaporador. De acordo com os fen?menos de transporte presentes no processo, o perfil de velocidade tende a aumentar at? um ponto m?ximo e em seguida diminui e a espessura do filme diminui, ambos em fun??o do comprimento do evaporador. Conclui-se que o c?digo de simula??o em linguagem Visual Basic? (VBA) ? um produto final do trabalho que permite aplica??o para a destila??o molecular do petr?leo e de outras misturas similares. / The heavy part of the oil can be used for numerous purposes, e.g. to obtain lubricating oils. In this context, many researchers have been studying alternatives such separation of crude oil components, among which may be mentioned molecular distillation. Molecular distillation is a forced evaporation technique different from other conventional processes in the literature. This process can be classified as a special distillation case under high vacuum with pressures that reach extremely low ranges of the order of 0.1 Pascal. The evaporation and condensation surfaces must have a distance from each other of the magnitude order of mean free path of the evaporated molecules, that is, molecules evaporated easily reach the condenser, because they find a route without obstacles, what is desirable. Thus, the main contribution of this work is the simulation of the falling-film molecular distillation for crude oil mixtures. The crude oil was characterized using UniSim? Design and R430 Aspen HYSYS? V8.5. The results of this characterization were performed in spreadsheets of Microsoft? Excel?, calculations of the physicochemical properties of the waste of an oil sample, i.e., thermodynamic and transport. Based on this estimated properties and boundary conditions suggested by the literature, equations of temperature and concentration profiles were resolved through the implicit finite difference method using the programming language Visual Basic? (VBA) for Excel?. The result of the temperature profile showed consistent with the reproduced by literature, having in their initial values a slight distortion as a result of the nature of the studied oil is lighter than the literature, since the results of the concentration profiles were effective allowing realize that the concentration of the more volatile decreases and of the less volatile increases due to the length of the evaporator. According to the transport phenomena present in the process, the velocity profile tends to increase to a peak and then decreases, and the film thickness decreases, both as a function of the evaporator length. It is concluded that the simulation code in Visual Basic? language (VBA) is a final product of the work that allows application to molecular distillation of petroleum and other similar mixtures.

Yes / Evaluation of economic aspects is one of the main milestones that affect taking rapid actions in dealing with GHGs mitigation; in particular, avoiding CO2 emissions from large source points, such as power plants. In the present study, three kinds of capturing solutions for coal power plants as the most common source of electricity generation have been studied from technical and economic standpoints. Aspen HYSYS (ver.11) has been used to simulate the overall processes, calculate the battery limit, and assess required equipment. The Taylor scoring method has been utilized to calculate the costliness indexes, assessing the capital and investment costs of a 230 MW power plant using anthracite coal with and without post-combustion, pre-combustion, and oxy-fuel combustion CO2 capture technologies. Comparing the costs and the levelized cost of electricity, it was found that pre-combustion is more costly, to the extent that the total investment for it is approximately 1.6 times higher than the oxy-fuel process. Finally, post-combustion, in terms of maturity and cost-effectiveness, seems to be more attractive, since the capital cost and indirect costs are less. Most importantly, this can be applied to the existing plants without major disruption to the current operation of the plants.

Hydrocracking and hydrotreating are bitumen upgrading technologies designed to enhance fuel quality by decreasing its density, viscosity, boiling point and heteroatom content via hydrogen addition. The aim of this thesis is to model and simulate an upgrading and integrated gasification combined cycle then to evaluate the feasibility of integrating slurry hydrocracking, trickle-bed hydrotreating and residue gasification using the Aspen HYSYS® simulation software. The close-coupling of the bitumen upgrading facilities with gasification should lead to a hydrogen, steam and power self-sufficient upgrading facility with CO2 capture. Hydrocracker residue is first withdrawn from a 100,000 BPD Athabasca bitumen upgrading facility, characterized via ultimate analysis and then fed to a gasification unit where it produces hydrogen that is partially recycled to the hydrocracker and hydrotreaters and partially burned for power production in a high hydrogen combined cycle unit. The integrated design is simulated for a base case of 90% carbon capture utilizing a monoethanolamine (MEA) solvent, and compared to 65% and no carbon capture scenarios. The hydrogen production of the gasification process is evaluated in terms of hydrocracker residue and auxiliary petroleum coke feeds. The power production is determined for various carbon capture cases and for an optimal hydrocracking operation. Hence, the feasibility of the integration of the upgrading process and the IGCC resides in meeting the hydrogen demand of the upgrading facility while producing enough steam and electricity for a power and energy self-sufficient operation, regardless of the extent of carbon capture.

Hydrocracking and hydrotreating are bitumen upgrading technologies designed to enhance fuel quality by decreasing its density, viscosity, boiling point and heteroatom content via hydrogen addition. The aim of this thesis is to model and simulate an upgrading and integrated gasification combined cycle then to evaluate the feasibility of integrating slurry hydrocracking, trickle-bed hydrotreating and residue gasification using the Aspen HYSYS® simulation software. The close-coupling of the bitumen upgrading facilities with gasification should lead to a hydrogen, steam and power self-sufficient upgrading facility with CO2 capture. Hydrocracker residue is first withdrawn from a 100,000 BPD Athabasca bitumen upgrading facility, characterized via ultimate analysis and then fed to a gasification unit where it produces hydrogen that is partially recycled to the hydrocracker and hydrotreaters and partially burned for power production in a high hydrogen combined cycle unit. The integrated design is simulated for a base case of 90% carbon capture utilizing a monoethanolamine (MEA) solvent, and compared to 65% and no carbon capture scenarios. The hydrogen production of the gasification process is evaluated in terms of hydrocracker residue and auxiliary petroleum coke feeds. The power production is determined for various carbon capture cases and for an optimal hydrocracking operation. Hence, the feasibility of the integration of the upgrading process and the IGCC resides in meeting the hydrogen demand of the upgrading facility while producing enough steam and electricity for a power and energy self-sufficient operation, regardless of the extent of carbon capture.

Hydrocracking and hydrotreating are bitumen upgrading technologies designed to enhance fuel quality by decreasing its density, viscosity, boiling point and heteroatom content via hydrogen addition. The aim of this thesis is to model and simulate an upgrading and integrated gasification combined cycle then to evaluate the feasibility of integrating slurry hydrocracking, trickle-bed hydrotreating and residue gasification using the Aspen HYSYS® simulation software. The close-coupling of the bitumen upgrading facilities with gasification should lead to a hydrogen, steam and power self-sufficient upgrading facility with CO2 capture. Hydrocracker residue is first withdrawn from a 100,000 BPD Athabasca bitumen upgrading facility, characterized via ultimate analysis and then fed to a gasification unit where it produces hydrogen that is partially recycled to the hydrocracker and hydrotreaters and partially burned for power production in a high hydrogen combined cycle unit. The integrated design is simulated for a base case of 90% carbon capture utilizing a monoethanolamine (MEA) solvent, and compared to 65% and no carbon capture scenarios. The hydrogen production of the gasification process is evaluated in terms of hydrocracker residue and auxiliary petroleum coke feeds. The power production is determined for various carbon capture cases and for an optimal hydrocracking operation. Hence, the feasibility of the integration of the upgrading process and the IGCC resides in meeting the hydrogen demand of the upgrading facility while producing enough steam and electricity for a power and energy self-sufficient operation, regardless of the extent of carbon capture.