Use of Hg-Electroplated-Pt Ultramicroelectrode for Determining Elemental Sulphur in Naphtha Samples

This paper describes the applicability of a Hg-electroplated-Pt ultramicroelectrode in the quantification of elemental sulphur in naphtha samples by square-wave voltammetry. A reproducible deposition methodology was studied and is reported in this paper. This methodology is innovative and relies on the quality of the mercury stock solution to obtain reproducible surfaces required for the analytical methodology. All analyses were performed using a Hg-electroplated-Pt ultramicroelectrode (Hg-Pt UME) due to the low sensibility of such devices to ohmic drops in resistive solutions. The responses of the peak areas in voltammetric experiments were linear in all of the range studied. The method developed here is accurate and reproducible, with a detection limit of 0.010 mg L-1 and a good recovery range for both standard solutions of elemental sulphur (85 to 99%) and real naphtha sample (79%). These results attest to the potential for the application of this electroanalytical methodology in determining elemental sulphur in naphtha samples containing mercaptans and disulphides.

Alternativas Processuais e Valorização de Correntes da Refinaria de Matosinhos.

Evolução, ato ou efeito de evoluir, sequência de transformações, desenvolvimento progressivo. Se tudo à nossa volta se transforma, a indústria tem de acompanhar esse sistema evolutivo, tornando assim imprescindível alterar ou melhorar processos de produção quando estes não se enquadram com a realidade, ou porque o mercado se altera, ou porque as necessidades mudam, ou por simplesmente ser mais rentável. Sendo a Galp Energia uma empresa que se encontra sempre na vanguarda da evolução tecnológica, encontra no Departamento de Engenharia Química do Instituto Superior de Engenharia do Porto um aliado na procura do melhor modo de valorizar os seus produtos. A Refinaria de Matosinhos tem atualmente duas correntes de gasolina leve e uma de refinado que apresentam grande potencialidade de valorização. Parte destas correntes incorporam atualmente a pool de nafta química da refinaria que é vendida à Repsol Polímeros. O desafio que é proposto baseia-se em valorizar essas correntes através da sua isomerização aumentando o seu RON podendo então ter como fim a pool de gasolinas. Tirando partido da tecnologia disponível para este efeito são apresentados quatro cenários de possíveis soluções. Sendo os dois primeiros excluídos por violarem restrições impostas, o terceiro e quarto cenários foram analisados de um ponto de vista económico. O terceiro cenário conduz a gasolina leve da Fábrica de Aromáticos para a pool de gasolinas sem qualquer tratamento e a gasolina leve da Fábrica de Combustíveis continua a integrar a pool de nafta química. O refinado da Fábrica de Aromáticos será enviado para um splitter, sendo a corrente de topo destinada à pool de nafta química e a corrente de fundo enviada a um reator de isomerização, Isomalk-4SM, passando previamente por uma torre de argila de forma a assegurar que a restrição em teor de olefinas no reator não é violada. O efluente, com RON maior, integrará igualmente a pool de gasolinas. No quarto cenário a corrente de refinado da Fábrica de Aromáticos não sofre qualquer tratamento, continuando a alimentar a unidade de solventes, a gasolina leve da Fábrica de Aromáticos irá diretamente para a pool de gasolinas e a gasolina leve da Fábrica de Combustíveis passará pelo Isomalk-2SM para aumentar o índice de octanos garantido assim ter condições de integrar a pool de gasolinas. Dissertação de Mestrado em Engenharia Química Isomerização de Gasolina Leve O terceiro cenário apresenta um aumento de 4 576 773 € anuais nas receitas e o quarto alcança 11 333 982 € anuais. O investimento inicial total do terceiro cenário é de 28 821 608 € quando o quarto cenário carece de um investimento inicial de apenas 18 028 349 €. Quanto aos custos associados à implementação da unidade estes demonstram-se elevados, o terceiro cenário apresenta um custo de 23 133 429 € enquanto o do quarto cenário é de 13 998 797 €. O quarto cenário apresenta-se assim como a solução mais rentável para o objetivo desta dissertação.

Avaliação económica de um projecto de investimento num sistema de retorno de gases num Terminal Portuário

Dissertação para obtenção do grau de Mestre em Engenharia e Gestão Industrial

Consequence modelling,vulnerability assessment and fuzzy fault tree analysis of hazardous storages in an industrial area

The hazards associated with major accident hazard (MAH) industries are fire, explosion and toxic gas releases. Of these, toxic gas release is the worst as it has the potential to cause extensive fatalities. Qualitative and quantitative hazard analyses are essential for the identitication and quantification of the hazards associated with chemical industries. This research work presents the results of a consequence analysis carried out to assess the damage potential of the hazardous material storages in an industrial area of central Kerala, India. A survey carried out in the major accident hazard (MAH) units in the industrial belt revealed that the major hazardous chemicals stored by the various industrial units are ammonia, chlorine, benzene, naphtha, cyclohexane, cyclohexanone and LPG. The damage potential of the above chemicals is assessed using consequence modelling. Modelling of pool fires for naphtha, cyclohexane, cyclohexanone, benzene and ammonia are carried out using TNO model. Vapor cloud explosion (VCE) modelling of LPG, cyclohexane and benzene are carried out using TNT equivalent model. Boiling liquid expanding vapor explosion (BLEVE) modelling of LPG is also carried out. Dispersion modelling of toxic chemicals like chlorine, ammonia and benzene is carried out using the ALOHA air quality model. Threat zones for different hazardous storages are estimated based on the consequence modelling. The distance covered by the threat zone was found to be maximum for chlorine release from a chlor-alkali industry located in the area. The results of consequence modelling are useful for the estimation of individual risk and societal risk in the above industrial area.Vulnerability assessment is carried out using probit functions for toxic, thermal and pressure loads. Individual and societal risks are also estimated at different locations. Mapping of threat zones due to different incident outcome cases from different MAH industries is done with the help of Are GIS.Fault Tree Analysis (FTA) is an established technique for hazard evaluation. This technique has the advantage of being both qualitative and quantitative, if the probabilities and frequencies of the basic events are known. However it is often difficult to estimate precisely the failure probability of the components due to insufficient data or vague characteristics of the basic event. It has been reported that availability of the failure probability data pertaining to local conditions is surprisingly limited in India. This thesis outlines the generation of failure probability values of the basic events that lead to the release of chlorine from the storage and filling facility of a major chlor-alkali industry located in the area using expert elicitation and proven fuzzy logic. Sensitivity analysis has been done to evaluate the percentage contribution of each basic event that could lead to chlorine release. Two dimensional fuzzy fault tree analysis (TDFFTA) has been proposed for balancing the hesitation factor invo1ved in expert elicitation .

Determinação de dados de equilíbrio líquido-vapor a altas pressões para sistemas de hidrocarbonetos assimétricos

Crude oil is a complex liquid mixture of organic and inorganic compounds that are dominated by hydrocarbons. It is a mixture of alkanes from the simplest to more complex aromatic compounds that are present derivatives such as gasoline, diesel, alcohol, kerosene, naphtha, etc.. These derivatives are extracted from any oil, however, only with a very high quality, in other words, when the content of hydrocarbons of low molecular weight is high means that production of these compounds is feasible. The American Petroleum Institute (API) developed a classification system for the various types of oil. In Brazil, the quality of most of the oil taken from wells is very low, so it is necessary to generate new technology to develop best practices for refining in order to produce petroleum products of higher commercial value. Therefore, it is necessary to study the thermodynamic equilibrium properties of its derivative compounds of interest. This dissertation aims to determine vapor-liquid equilibrium (VLE) data for the systems Phenilcyclohexane - CO2, and Cyclohexane - Phenilcyclohexane - CO2 at high pressure and temperatures between 30 to 70oC. Furthermore, comparisons between measured VLE experimental data from this work and from the literature in relation to the Peng- Robinson molecular thermodynamic model, using a simulation program SPECS IVCSEP v5.60 and two adjustable interaction parameters, have been performed for modeling and simulation purposes. Finally, the developed apparatus for determination of phase equilibrium data at high pressures is presented

Estudo da cristalização de parafinas em sistemas solventes/tensoativos/água

The WAT is the temperature at the beginning of the appearance of wax crystals. At this temperature the first wax crystals are formed by the cooling systems paraffin / solvents. Paraffins are composed of a mixture of saturated hydrocarbons of high molecular weight. The removal of petroleum from wells and the production lines means a surcharge on produced oil, thus solubilize these deposits formed due to modifications of thermodynamics has been a constant challenge for companies of oil exploration. This study combines the paraffin solubilization by microemulsion systems, the determination of WAT systems paraffin / solvent and performance of surfactant in reducing the crystallization. We used the methods: rheological and the photoelectric signal, validating the latter which was developed to optimize the data obtained due to sensitivity of the equipment used. Methods developed for description of wax precipitation are often in poor agreement with the experimental data, they tend to underestimate the amount of wax at temperatures below the turbidity point. The Won method and the Ideal solution method were applied to the WAT data obtained in solvent systems, best represented by the second interaction of Won method using the solvents naphtha, hexane and LCO. It was observed that the results obtained by WAT photoelectric signal when compared with the viscosity occur in advance, demonstrating the greatest sensitivity of the method developed. The ionic surfactant reduced the viscosity of the solvent systems as it acted modifying the crystalline structure and, consequently, the pour point. The curves show that the WAT experimental data is, in general, closer to the modeling performed by the method of Won than to the one performed by the ideal solution method, because this method underestimates the curve predicting the onset of paraffin hydrocarbons crystallization temperature. This occurs because the actual temperature measured was the crystallization temperature and the method proposes the fusion temperature measurement.

Obtenção de novos derivados de ß-naftol e cardanol hidrogenado e avaliação dos seus efeitos antioxidativos em gasolina automotiva

The chemical nature of the hidrocarbons found in gasoline directly affects the formation of oxidation complexes known as gums. Such complexes are slightly soluble in gasoline and their formation is delayed with the use of inhibitors, known as antioxidants. In this study, a synthetic compound (βnaphtol) and a natural subproduct (hydrogenated cardanol, derived from cashewnut shell liquid CNSL) have been used in order to generate novel antioxidant substances. These compounds were submitted to chemical reactions including alkylation, nitration and reduction, with the purpose of forming the following derivatives: 6(Nethyl,Nethylamino)βnaphtol (AO1); 6(Nethyl,Ndiethylamino)βnaphtol (AO2); aminoβnaphtol (AO3); 2(Nethyl,Nethylamino)pentadecylphenol (AOC1), 2(Nethyl,Ndiethylamino)pentadecylphenol (AOC2) and aminopentadecylphenol (AOC3). The derivatives were subjected to accelerated oxidative stability assays (Potential Gum and Induction Period) and to storage assays (Washed Gum and ASTM Color) during six months, with naphtha provided by the petroleum refinery RPBC (Refinaria Presidente Bernardes de Cubatão, in Brazil). The results for the derivatives were compared to those for commercial additives [DBPC (2,6ditbutyl4methylpcresol) and PDA (N,N disecbutylpphenylenediamine)], which were also added to the naphtha produced at RPBC at the moment of sampling. From all tested antioxidants, the novel antioxidant AOC1 (derived from hydrogenated cardanol) yielded a better global performance. During the period of time in which the naphtha was stored, an examination of this material was carried out in parallel, using the mass spectrometry technique. This study allowed to monitor the formation of a triolefinic compound, as well as the observation of subsequent formation and rupture of the olefinic constituents. As an eventual result from these experimental investigations, a reaction route leading to gum formation has been suggested

Modelagem matemática do processo industrial de coqueamento retardado.

A unidade de coqueamento retardado é um processo térmico de conversão, utilizado pelas refinarias, para converter cargas residuais em produtos de baixo peso molecular e com alto valor agregado (gases, nafta e gasóleo) e coque verde de petróleo. Um pequeno aumento no rendimento líquido da unidade de coqueamento retardado proporciona benefícios económicos consideráveis, especialmente no destilado líquido. A concorrência no mercado, as restrições sobre as especificações do produto e gargalos operacionais exigem um melhor planejamento da produção. Portanto, o desenvolvimento de novas estratégias e modelos matemáticos, focados em melhores condições de operação do processo industrial e formulações de produtos, é essencial para alcançar melhores rendimentos e um acompanhamento mais preciso da qualidade do produto. Este trabalho tem como objetivo o desenvolvimento de modelo matemático do conjunto forno-reator do processo de coqueamento, a partir de informações obtidas em uma planta industrial. O modelo proposto é baseado na caracterização da carga e dos produtos em pseudocomponentes, modelos cinéticos de grupos e condições de equilíbrio liquido-vapor. Além disso, são discutidos os principais desafios para o desenvolver o modelo matemático do forno e do reator, bem como a caracterização rigorosa do resíduo de vácuo e dos produtos para determinar os parâmetros que afetam a morfologia do coque e a zona de reação no interior do reator de coque.

Ethanol dehydration via azeotropic distillation with gasoline fraction mixtures as entrainers: A pilot-scale study with industrially produced bioethanol and naphta

Various hydrocarbons (n-hexane, cyclohexane, toluene, isooctane) and mixtures of them (binary, ternary or quaternary), as well as two different types of industrially produced naphtha (one obtained by direct distillation and the other from a catalytic cracking process), have been tested as candidate entrainers to dehydrate ethanol. The tests were carried out in an azeotropic distillation column on a semi pilot plant. The results show that it is possible to dehydrate bioethanol using naphtha as entrainer, obtaining as a result a fuel blend with negligible water content and ready for immediate use in motor vehicles.

The steam reforming of hydrocarbons with special reference to methane

From an examination of the literature relating to the catalytic steam reforming of hydrocarbons, it is concluded that the kinetics of high pressure reforming, particularly steam-methane reforming, has received relatively little attention. Therefore because of the increasing availability of natural gas in the U.K., this system was considered worthy of investigation. An examination of the thermodynamics relating to the equilibria of steam-hydrocarbon reforming is described. The reactions most likely to have influence over the process are established and from these a computer program was written to calculate equilibrium compositions. A means of presenting such data in a graphica1 form for ranges of the operating variables is given, and also an operating chart which may be used to quickly check feed ratios employed on a working naphtha reforming plant is presented. For the experimental kinetic study of the steam-methane system, cylindrical pellets of ICI 46-1 nickel catalyst were used in the form of a rod catalyst. The reactor was of the integral type and a description is given with the operating procedures and analytical method used. The experimental work was divided into two parts, qualitative and quantitative. In the qualitative study the various reaction steps are examined in order to establish which one is rate controlling. It is concluded that the effects of film diffusion resistance within the conditions employed are negligible. In the quantitative study it was found that at 250 psig and 6500C the steam-methane reaction is much slower than the CO shift reaction and is rate controlling. Two rate mechanisms and accompanying kinetic rate equations are derived, both of which represent 'chemical' steps in the reaction and are considered of equal merit. However the possibility of a dual control involving 'chemical' and pore diffusion resistances is also expressed.