Estudo teórico aplicado ao petróleo: estabilidade dos alcenos e recuperação terciária

The present work aims to study the theoretical level of some processes employed in the refining of petroleum fractions and tertiary recovery of this fluid. In the third chapter, we investigate a method of hydrogenation of oil fractions by QTAIM (Quantum Theory of Atoms in Molecules) and thermodynamic parameters. The study of hydrogenation reactions, and the stability of the products formed, is directly related to product improvement in the petrochemical refining. In the fourth chapter, we study the theoretical level of intermolecular interactions that occur in the process of tertiary oil recovery, or competitive interactions involving molecules of non-ionic surfactants, oil and quartz rock where oil is accumulated. Calculations were developed using the semiempirical PM3 method (Parametric Model 3). We studied a set of ten non-ionic surfactants, natural and synthetic origin. The study of rock-surfactant interactions was performed on the surface of the quartz (001) completely hydroxylated. Results were obtained energetic and geometric orientations of various surfactants on quartz. QTAIM was obtained through the analysis of the electron density of interactions, and thus, providing details about the formation of hydrogen bonds and hydrogen-hydrogen systems studied. The results show that the adsorption of ethoxylated surfactants in the rock surface occurs through the hydrogen bonding of the type CH---O, and surfactants derivatives of polyols occurs by OH---O bonds. For structures adsorption studied, the large distance of the surfactant to the surface together with the low values of charge density, indicate that there is a very low interaction, characterizing physical adsorption in all surfactants studied. We demonstrated that surfactants with polar group comprising oxyethylene units, showed the lowest adsorption onto the surface of quartz, unlike the derivatives of polyols

Síntese e caracterização de zeólita beta hierarquizada e materiais híbridos micro-mesoporosos aplicados no craqueamento de PEAD

A catalyst of great interest to the scientific community tries to unite the structure of ordered pore diameter from mesoporous materials with the properties of stability and acid activity to microporous zeolites. Thus a large number of materials was developed in the past decades, which although being reported as zeolites intrinsically they fail to comply with some relevant characteristics to zeolites, and recently were named zeolitic materials of high accessibility. Among the various synthesis strategies employed, the present research approaches the synthesis methods of crystallization of silanized protozeolitic units and the method of protozeolitic units molded around surfactant micelles, in order for get materials defined as hierarchical zeolites and micro-mesoporous hybrid materials, respectively. As goal BEA/MCM-41 hybrid catalysts with bimodal pore structure formed by nuclei of zeolite Beta and cationic surfactant cetyltrimethylammonium were developed. As also was successfully synthesized the hierarchical Beta zeolite having a secondary porosity, in addition to the typical and uniform zeolite micropores. Both catalysts were applied in reactions of catalytic cracking of high density polyethylene (HDPE), to evaluate its properties in catalytic activity, aiming at the recycling of waste plastics to obtain high value-added raw materials and fuels. The BEA/MCM-41 hybrid materials with 0 days of pre-crystallization did not show enough properties for use in catalytic cracking reactions, but they showed superior catalytic properties compared to those ordered mesoporous materials of Al-MCM-41 type. The structure of Beta zeolite with hierarchical porosity leads the accessibility of HDPE bulky molecules to active centers, due to high external area. And provides higher conversion to hydrocarbons in the gasoline range, especially olefins which have great interest in the petrochemical industry

Aspectos metalúrgicos de revestimentos em dutos depositados com a superliga de níquel ERNiCrMo-4 pelos processos MIG convencional e MIG com adição de arame frio

Este trabalho estuda o perfil metalúrgico de revestimentos em dutos depositados pelos processos MIG C e MIG AF. A indústria petroquímica, e outras que utilizam dutos como meio de transporte de seus insumos, depara-se com um grande desafio: como aumentar a vida útil desses dutos em um ambiente severo de trabalho. No caso específico da petroquímica, os dutos servem como meio de transporte para petróleo e gás, que são produtos extremamente agressivos às paredes internas desses tubos que sofrem degradação por corrosão causada, principalmente, pela composição química, pressão e temperatura desses produtos. Nesse contexto a soldagem de revestimentos realizada com ligas à base de Níquel, torna-se uma excelente opção para a construção, reparo e manutenção de equipamentos cuja aplicação seja voltada a ambientes severos de trabalho, tornando possível aperfeiçoar as características requeridas, como por exemplo, a resistência à corrosão. É nesse cenário que surge o mote para a realização desta pesquisa, baseada em trabalhos que indicam que o processo de soldagem MIG/MAG com o da adição de arame frio possui a finalidade de avaliar as características metalúrgicas do revestimento em dutos depositados pelo processo derivativo MIG convencional – MIG-C e MIG com adição de arame frio – MIG AF – utilizando a liga de Níquel ERNiCrMo-4 em dutos de aço carbono. As soldas foram depositadas em dutos de diâmetro de 228,6 mm, formando uma camada de revestimento interno de quatro passes, divididos em três segmentos da circunferência do duto, em três diferentes energias de soldagem: 1,1; 0,9 e 0,7 kJ/mm. Desses segmentos retiraram-se corpos de prova dos dutos para a produção das amostras. Após a metalografia, realizada nas amostras, seguiu-se com a análise e caracterização ao microscópio óptico, microscópio eletrônico de varredura e ensaio de microdureza. Os revestimentos apresentaram excelente qualidade superficial para todos os pacotes operacionais aplicados na obtenção das soldas. As análises das regiões estudadas: metal de base; zona parcialmente misturada e zona termicamente afetada, mostraram-se compatíveis com os da literatura estudada, tanto para o MIG com adição de arame frio, quanto para o convencional. Na ZTA, foram observados valores de Tungstênio em torno de 1,0%, o aumento dos níveis de dureza foi creditado a esse fato. Os resultados de microdureza indicaram que para ambos os casos, MIG C e MIG AF, nas 4 regiões analisadas ocorreram de maneira semelhante, sendo a região da ZTA a que apresentou maiores valores na faixa de 400 a 500 HV, enquanto que nas demais regiões a faixa ficou entre 250 a 350 HV. Os resultados indicam que o processo com arame frio, MIG AF, mostrou-se tão eficiente quanto o convencional, MIG C. A energia de soldagem aumentou a diluição de Fe no metal de solda. Precipitados ricos em Mo e Cr foram encontrados no metal de solda.

Avaliação do potencial genotóxico e mutagênico do efluente de uma refinaria de petróleo e dos rios sob sua influência, por meio de bioensaios com Oreochromis niloticus (Perciformes, Cichlidae)

The petrochemical industry represents a sector of intense activity, in constant expansion and great economic importance for Brazil. In order to be used in various human activities petroleum needs to suffer a refinement process that, besides requiring large amounts of water, produces large amounts of wastes, which are discharged in hydric resources. Petroleum is a complex mixture mainly comprised by hydrocarbons, many of them are recognized as toxic chemicals, which are able to induce a considerable environmental pollution. Since water is an important resource for the maintenance of ecosystems and is also the final receiver of effluent discharges of the petroleum industry, there is an imminent need to monitor, constantly, the hydric resources that are influenced by this industrial activity, so that it can be ensured the environmental health. This study aimed, mainly, to analyze the quality of water samples derived from refinement process performed of the largest petroleum refinery in Brazil (REPLAN), in distinct steps of the industry treatment, and waters of rivers associated to its activity. Micronuclei and Nuclear Abnormalities tests were performed in erythrocytes of the fish species Oreochromis niloticus exposed to water samples derived from refinery use and to rivers under the influence of their effluents, in order to evaluate its possible toxic, genotoxic and mutagenic effects. The results obtained show that the treatment carried out by the refinery, during the evaluated periods, was effective, since the substances present in the water samples did not induce significant genotoxic and/or mutagenic alterations in the genetic material of the test organisms. On the other hand, when the substances present in the refinery effluent mix with the ones derived from other industrial activities developed upstream of this industry, the resultant compound, in some periods, presented genotoxic potencial, characterized by a rise of erythrocytic...

Avaliação mecânica da colagem estrutural entre compósitos poliméricos e materiais metálicos utilizados em dutos petroquímicos

The development of technology for structural composites has as one of its ends form a set of materials that combine high values of mechanical strength and stiffness and low density. Today, companies like Embraer and PETROBRAS and research institutions like NASA, working with these materials with recognized advantages in terms of weight gain, increased performance and low corrosion. We have developed a systematic study to determine the bond strength between composite carbon fiber / epoxy and fiberglass / epoxy laminate both bonded to a carbon steel which are widely used in the petrochemical industry and repair. For morphological evaluation and bonding between materials of different natures, ultrasound analysis, optical microscopy and stereoscopy were performed. To simulate actual conditions, the composites were subjected to conditioning by using heat shock temperatures from -50 to 80 ° C for 1000 cycles for composite carbon fiber / epoxy composites and 2000 cycles for fiberglass / epoxy . The use of composites studied here proved to be efficient to perform repairs in metallic pipes with application petrochemical, as when exposed to sudden changes of temperature (-50 ° to 80 ° C) cycling at 1000 to 2000 times, its mechanical properties (shear and tensile) practically do not change

SONIA REGINA PRADO

A dissertação teve como objetivo principal estudar como uma Instituição de Ensino Superior Privada (IES) atuante no Brasil tem crescido pós Lei de Diretrizes e Bases (LDB) de 1996 até 2015, por meio da análise do curso de bacharelado em Administração de Empresas, nas modalidades: presencial, EAD e Flex (semipresencial). Para este fim, foi realizada uma pesquisa exploratória, de caráter qualitativo baseada no método do estudo de caso. Para coleta de evidências foram analisados relatórios corporativos (Annual Report, Relatórios Internos e outros documentos), entrevistas baseadas em roteiro semiestruturado com gestores da IES privada e observações. Dentre os principais achados, verificou-se que as principais estratégicas de crescimento da IES privada estudada se basearam em fusões e aquisições de outras IES, abertura de novos polos de EAD, na abertura de novas unidades próprias, bem como em inovações em várias dimensões da organização. Os programas governamentais de financiamento aos alunos também são fortes contribuintes para este crescimento, como o Fundo de Financiamento ao Estudante do Ensino Superior (FIES) e o Programa Universidade para Todos (Prouni). Com essa nova realidade, o ensino superior privado recebeu incentivo e facilitação para o seu crescimento, a um ritmo acelerado. Consequentemente pode-se concluir que a IES privada estudada adotou as seguintes estratégias de crescimento: Expansão orgânica com fusões/ aquisições de Instituições menores, com desenvolvimento de planos para todos os campi Brasil; Greenfield (por meio de solicitação de autorização de novas unidades e/ou cursos) em cidades sem possibilidades de aquisições/fusões, e aumentando o número de vagas/ matriculas nas unidades já existentes, aderiu aos programas do governo e também cuidou da evasão por meio de: Seguro educacional; gestão preparada para atender necessidades do discente; Sistema de Ensino com currículos integrados nacionalmente; Intercâmbio de alunos e professores entre as diversas unidades em todas as regiões do país e padronização dos processos.

Avaliação da biodegradação do dibenzotiofeno utilizando lodos ativados

During the oil refining process a huge discard volume of water occurs, which carries the contaminants from the process. A class of contaminant compounds resulting from the petrochemical industry are the Polyaromatic Hydrocarbons (PAH's). To evaluate the biodegradation of Dibenzothiophene in refinery water a synthetic wastewater was prepared to be treated using activated sludge. For this, a 2 3 Composite Design (plus 3 central points and six axial points) was carried out. The planning had as independent variables (factors) the initial concentration of DBT, pH and time of biodegradation. Biodegradation of DBT was assayed following the parameters COD, pH, temperature, SS, VSS, FVS, SVI. Concerned to the chromatographic conditions, a methodology was validated in order to verify the presence of DBT and its metabolite, 2-HBF, in the final wastewater treated by activated sludge system using a liquid - liquid extraction coupled to HPLC / UV analysis. The parameters used for validation were DL, QL, linearity, recovery and repeatability. As for optimization, the results indicated that the studied methodology can be used in monitoring the DBT degradation and 2- HBF by activated sludge, as they showed excellent linearity values, coefficients of variation, so as satisfactory recovery percentage. COD reduction efficiency tests showed an average percentage of 64.4%. The increasing trend for the results for the TSS and VSS tests showed that the activated sludge was well tailored. The best operating conditions for the reduction of COD were observed when operated with median concentrations of DBT, a higher time to biodegradation, and pH in both the acidic range as the basic one. The biodegradability of the DBT was confirmed by determining the presence of HBF-2. The highest concentrations of HBF-2 were obtained in extreme concentrations of DBT and pH, and higher biodegradation times.

Aplicação de tratamentos eletroquímicos integrados para remediação de solos e águas contaminadas com petróleo e pesticidas

Electrochemical technologies have been proposed as a promising alternative for the treatment of effluents and contaminated soils. Therefore, the objective of this work was to study the treatment of contaminated soils and wastewaters using electrochemical technologies. Thus, the study regarding the scale-up of the electrochemical system with continuous flow treatment of wastewater of the petrochemical industry was investigated using platinum electrodes supported on titanium (Ti / Pt), and boron-doped diamond (BDD). The results clearly showed that under the operating conditions studied and electrocatalytic materials employed, the better removal efficiency was achieved with BDD electrode reducing the chemical oxygen demand (COD) from 2746 mg L-1 to 200 mg L-1 in 5 h consuming 56.2 kWh m-3 . The decontamination of soils and effluents by petrochemical products was evaluated by studying the effects of electrokinetic remediation for removal of total petroleum hydrocarbons (HTP) from contaminated soil with diesel. The efficiency of this process was dependent on the electrolyte used Na2SO4 (96.46%), citric acid (81.36%) and NaOH (68.03%) for 15 days. Furthermore, the effluent after treatment of the soil was treated by electrochemical oxidation, achieving a good elimination of the organic polluting load dissolved. Depending on the physical behavior of wastewater contaminated with oil (emulsified state); atrazine emulsified effluents were investigated. The main characteristics of the effluent produced during the washing of contaminated soil were studied, being dependent on the surfactant dosage used; which determined its electrolytic treatment with BDD. The electrochemical oxidation of emulsified effluent of atrazine was efficient, but the key to the treatment is reducing the size of micelles.

Estimação e compensação de não linearidades inerentes aos atuadores dos processos industriais

The oscillations presents in control loops can cause damages in petrochemical industry. Canceling, or even preventing such oscillations, would save up to large amount of dollars. Studies have identified that one of the causes of these oscillations are the nonlinearities present on industrial process actuators. This study has the objective to develop a methodology for removal of the harmful effects of nonlinearities. Will be proposed an parameter estimation method to Hammerstein model, whose nonlinearity is represented by dead-zone or backlash. The estimated parameters will be used to construct inverse models of compensation. A simulated level system was used as a test platform. The valve that controls inflow has a nonlinearity. Results and describing function analysis show an improvement on system response

Controle preditivo neural aplicado à processos petroquímicos

A pesquisa tem como objetivo desenvolver uma estrutura de controle preditivo neural, com o intuito de controlar um processo de pH, caracterizado por ser um sistema SISO (Single Input - Single Output). O controle de pH é um processo de grande importância na indústria petroquímica, onde se deseja manter constante o nível de acidez de um produto ou neutralizar o afluente de uma planta de tratamento de fluidos. O processo de controle de pH exige robustez do sistema de controle, pois este processo pode ter ganho estático e dinâmica nãolineares. O controlador preditivo neural envolve duas outras teorias para o seu desenvolvimento, a primeira referente ao controle preditivo e a outra a redes neurais artificiais (RNA s). Este controlador pode ser dividido em dois blocos, um responsável pela identificação e outro pelo o cálculo do sinal de controle. Para realizar a identificação neural é utilizada uma RNA com arquitetura feedforward multicamadas com aprendizagem baseada na metodologia da Propagação Retroativa do Erro (Error Back Propagation). A partir de dados de entrada e saída da planta é iniciado o treinamento offline da rede. Dessa forma, os pesos sinápticos são ajustados e a rede está apta para representar o sistema com a máxima precisão possível. O modelo neural gerado é usado para predizer as saídas futuras do sistema, com isso o otimizador calcula uma série de ações de controle, através da minimização de uma função objetivo quadrática, fazendo com que a saída do processo siga um sinal de referência desejado. Foram desenvolvidos dois aplicativos, ambos na plataforma Builder C++, o primeiro realiza a identificação, via redes neurais e o segundo é responsável pelo controle do processo. As ferramentas aqui implementadas e aplicadas são genéricas, ambas permitem a aplicação da estrutura de controle a qualquer novo processo

Pirólise térmica e catalítica de resíduos de vácuo gerados no refino de petróleo

In this study, was used a very promising technique called of pyrolysis, which can be used for obtaining products with higher added value. From oils and residues, since the contribution of heavier oils and residues has intensified to the world refining industry, due to the growing demand for fuel, for example, liquid hydrocarbons in the range of gasoline and diesel. The catalytic pyrolysis of vacuum residues was performed with the use of a mesoporous material belonging the M41S family, which was discovered in the early 90s by researchers Mobil Oil Corporation, allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal arrangement of mesopores with pore diameters between 2 and 10 nm and a high specific surface area, making it very promising for use as a catalyst in petroleum refining for catalytic cracking, and their mesopores facilitate the access of large hydrocarbon molecules. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more positive for application in the petrochemical industry. The mesoporous material of the type Al-MCM41 (ratio Si / Al = 50) was synthesized by hydrothermal method starting from the silica gel, NaOH and distilled water added to the gel pseudobohemita synthesis. Driver was used as structural CTMABr. Removal of organic driver (CTMABr) was observed by TG / DTG and FTIR, but this material was characterized by XRD, which was observed the formation of the main peaks characteristic of mesoporous materials. The analysis of adsorption / desorption of nitrogen this material textural parameters were determined. The vacuum residues (VR's) that are products of the bottom of the vacuum distillation tower used in this study are different from oil fields (regions of Ceará and Rio de Janeiro). Previously characterized by various techniques such as FTIR, viscosity, density, SARA, elemental analysis and thermogravimetry, which was performed by thermal and catalytic degradation of vacuum residues. The effect of AlMCM-41 was satisfactory, since promoted a decrease in certain ranges of temperature required in the process of conversion of hydrocarbons, but also promoted a decrease in energy required in the process. Thus enabling lower costs related to energy expenditure from degradation during processing of the waste

Reforma a seco de metano com catalisadores Ni/MCM-41 sintetizados a partir de fontes alternativas de sílica

The production of synthesis gas has received renewed attention due to demand for renewable energies to reduce the emissions of gases responsible for enhanced greenhouse effect. This work was carried out in order to synthesize, characterize and evaluate the implementation of nickel catalysts on MCM-41 in dry reforming reactions of methane. The mesoporous molecular sieves were synthesized using as silica sources the tetraethyl orthosilicate (TEOS) and residual glass powder (PV). The sieves were impregnated with 10% nickel to obtain the metallic catalysts (Ni/MCM-41). These materials were calcined and characterized by Thermogravimetric Analysis (TG), Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Temperature-Programmed Reduction (TPR) and N2 Adsorption/Desorption isotherms (BET/BJH). The catalytic properties of the samples were evaluated in methane dry reforming with CO2 in order to produce synthesis gas to be used in the petrochemical industry. The materials characterized showed hexagonal structure characteristic of mesoporous material MCM-41 type, being maintained after impregnation with nickel. The samples presented variations in the specific surface area, average volume and diameter of pores based on the type of interaction between the nickel and the mesoporous support. The result of the the catalytic tests showed conversions about 91% CO2, 86% CH4, yelds about 85% CO and 81% H2 to Ni/MCM-41_TEOS_C, and conversions about 87% CO2, 82% CH4, yelds about 70% CO and 59% H2 to Ni/MCM-41_PV_C. The similar performance confirms that the TEOS can be replaced by a less noble materials

Tecnologia eletroquímica como tratamento alternativo de efluentes derivados da indústria têxtil e petroquímica

In this work, the treatment of wastewater from the textile industry, containing dyes as Yellow Novacron (YN), Red Remazol BR (RRB) and Blue Novacron CD (NB), and also, the treatment of wastewater from petrochemical industry (produced water) were investigated by anodic oxidation (OA) with platinum anodes supported on titanium (Ti/Pt) and boron-doped diamond (DDB). Definitely, one of the main parameters of this kind of treatment is the type of electrocatalytic material used, since the mechanisms and products of some anodic reactions depend on it. The OA of synthetic effluents containing with RRB, NB and YN were investigated in order to find the best conditions for the removal of color and organic content of the dye. According to the experimental results, the process of OA is suitable for decolorization of wastewaters containing these textile dyes due to electrocatalytic properties of DDB and Pt anodes. Removal of the organic load was more efficient at DDB, in all cases; where the dyes were degraded to aliphatic carboxylic acids at the end of the electrolysis. Energy requirements for the removal of color during OA of solutions of RRB, NB and YN depends mainly on the operating conditions, for example, RRB passes of 3.30 kWh m-3 at 20 mA cm-2 for 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (estimated data for volume of treated effluent). On the other hand, in the study of OA of produced water effluent generated by petrochemical industry, galvanostatic electrolysis using DDB led to the complete removal of COD (98%), due to large amounts of hydroxyl radicals and peroxodisulphates generated from the oxidation of water and sulfates in solution, respectively. Thus, the rate of COD removal increases with increasing applied current density (15-60 mAcm-2 ). Moreover, at Pt electrode, approximately 50% removal of the organic load was achieved by applying from 15 to 30 mAcm-2 while 80% of COD removal was achieved for 60 mAcm-2 . Thus, the results obtained in the application of this technology were satisfactory depending on the electrocatalytic materials and operating conditions used for removal of organic load (petrochemical and textile effluents) as well as for the removal of color (in the case of textile effluents). Therefore, the applicability of electrochemical treatment can be considered as a new alternative like pretreatment or treatment of effluents derived from textiles and petrochemical industries.

Reestruturação produtiva e emprego industrial na região de Campinas-SP: um estudo para as indústrias petroquímica e metal-mecânica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)