High Carbon Ferro-Chromium by Self-Reducing Process

This paper discusses the effects of temperature, addition of ferro-silicon and fluxing agents for the production of high carbon ferro-chromium by self-reducing process. The use of self-reducing agglomerates for ferro-alloys production is becoming an emerging processing technology due to lowering the electric energy consumption and improving the metal recovery in comparison with traditional ones. The self-reducing pellets were composed by chromite, petroleum coke, cement and small (0.1% - 2%) addition of ferro-silicon. The slag composition was adjusted by addition of fluxing agents. The reduction of pellets was carried out at 1773K (1500 degrees C), 1823K (1550 degrees C) and 1873K (1600 degrees C) by using induction furnace. The products obtained, containing slag and metallic phases, were analyzed by scanning electron microscopy and chemical analyses (XEDS). By increasing temperature from 1773K to 1823K large effect on the reduction time was observed. It decreased from 30 minutes to 10 minutes, for reaching around 0.98 reduction fraction. No significant effect on reduction time was observed when the reduction temperature was increased from 1823K to 1873K. At 1773K, the addition of 2% of ferro-silicon in the pellet resulted in an increasing reaction rate of around 6 times, in comparison with agglomerate without this addition. The addition of fluxing agents (silica and hydrated lime) has effect on reduction time (inverse relationship) and the pellets become less porous after reduction.

Prediction of Crude Oil Properties and Chemical Composition by Means of Steady-State and Time-Resolved Fluorescence

Steady-state and time-resolved fluorescence measurements are reported for several crude oils and their saturates, aromatics, resins, and asphaltenes (SARA) fractions (saturates, aromatics and resins), isolated from maltene after pentane precipitation of the asphaltenes. There is a clear relationship between the American Petroleum Institute (API) grade of the crude oils and their fluorescence emission intensity and maxima. Dilution of the crude oil samples with cyclohexane results in a significant increase of emission intensity and a blue shift, which is a clear indication of the presence of energy-transfer processes between the emissive chromophores present in the crude oil. Both the fluorescence spectra and the mean fluorescence lifetimes of the three SARA fractions and their mixtures indicate that the aromatics and resins are the major contributors to the emission of crude oils. Total synchronous fluorescence scan (TSFS) spectral maps are preferable to steady-state fluorescence spectra for discriminating between the fractions, making TSFS maps a particularly interesting choice for the development of fluorescence-based methods for the characterization and classification of crude oils. More detailed studies, using a much wider range of excitation and emission wavelengths, are necessary to determine the utility of time-resolved fluorescence (TRF) data for this purpose. Preliminary models constructed using TSFS spectra from 21 crude oil samples show a very good correlation (R(2) > 0.88) between the calculated and measured values of API and the SARA fraction concentrations. The use of models based on a fast fluorescence measurement may thus be an alternative to tedious and time-consuming chemical analysis in refineries.

Coalescence of Water Droplets in Crude Oil Emulsions: Analytical Solution

In petroleum refineries, water is used in desalting units to remove the salt contained in crude oil. Typically, 7% of the volume of hot crude oil is water, forming a water-and-oil emulsion. The emulsion flows between two electrodes and is subjected to an electric field. The electrical forces promote the coalescence of small droplets of water dispersed in crude oil, and these form bigger droplets. This paper calculates the forces acting on the droplets, highlighting particularly the mechanisms proposed for droplet-droplet coalescence under the influence of an applied electric field. Moreover, a model is developed in order to calculate the displacement speed of the droplets and the time between droplet collisions. Thus, it is possible to simulate and optimize the process by changing the operational variables (temperature, electrical field, and water quantity). The main advantage of this study is to show that it is feasible to increase the volume of water recycled in desalting processes, thus reducing the use of freshwater and the generation of liquid effluents in refineries.

A novel continuous time representation for the scheduling of pipeline systems with pumping yield rate constraints

Pipeline systems play a key role in the petroleum business. These operational systems provide connection between ports and/or oil fields and refineries (upstream), as well as between these and consumer markets (downstream). The purpose of this work is to propose a novel MINLP formulation based on a continuous time representation for the scheduling of multiproduct pipeline systems that must supply multiple consumer markets. Moreover, it also considers that the pipeline operates intermittently and that the pumping costs depend on the booster stations yield rates, which in turn may generate different flow rates. The proposed continuous time representation is compared with a previously developed discrete time representation [Rejowski, R., Jr., & Pinto, J. M. (2004). Efficient MILP formulations and valid cuts for multiproduct pipeline scheduling. Computers and Chemical Engineering, 28, 1511] in terms of solution quality and computational performance. The influence of the number of time intervals that represents the transfer operation is studied and several configurations for the booster stations are tested. Finally, the proposed formulation is applied to a larger case, in which several booster configurations with different numbers of stages are tested. (C) 2007 Elsevier Ltd. All rights reserved.

Improved moisture and hydrocarbons barrier of epoxy resin-based coating

To improve the surface characteristics of epoxy resin coatings, a treatment by fluorine-containing plasma was used to develop a coating with low surface free energy and improved chemical resistance. Through the coating analysis it was possible to verify information about the CF(n) bond formation and the fluorination depth. The best plasma process parameters presented the best fluorination depth, 90 nm, and fluorine concentration was nearly 30%. The improvement in contact angle of water was 50% and of raw petroleum was 130%. Salt spray test proves that the coating fluorination decreases the chance of substrate corrosion.

Use of otoliths and eye lenses for measuring trace-metal incorporation in fishes: a biogeographic study

The otoliths and lenses of the temperate damselfish Parma microlepis (Gunther) (Pomacentridae) showed similar differences in trace-metal profile for selected locations along the coast of New South Wales, Australia. Otoliths and lenses displayed a differential ability to accumulate metals. Metal concentrations were ranked differently in the two structures (e.g. Sr > Ba > Pb > Rb > Hg in otoliths, and Hg > Sr similar or equal to Rb > Pb > Ba in lenses), and where similar metals were accumulated, they were accumulated at vastly different concentrations (e.g. Ba concentrations in otoliths are a thousand-fold greater than in lenses). Analyses of the otoliths and lenses of P. microlepis from locations close to Sydney and up to 100 kill from the city were able to distinguish amongst these locations with respect to a number of metals, namely Ba, Mn and Hg. Multivariate analyses of otolith and lens data gave similar results among locations (agreement was obtained for Ii out of 15 pair-wise comparisons), and differences were attributable to the differential ability of the two structures to accumulate metals such as Mn and Hg. Trace-metal differences between locations were found to coincide with the proximity of sewage (including industrial waste) and petroleum storage facilities to the different locations.

Analysis of pore-fluid pressure gradient and effective vertical-stress gradient distribution in layered hydrodynamic systems

A theoretical analysis is carried out to investigate the pore-fluid pressure gradient and effective vertical-stress gradient distribution in fluid saturated porous rock masses in layered hydrodynamic systems. Three important concepts, namely the critical porosity of a porous medium, the intrinsic Fore-fluid pressure and the intrinsic effective vertical stress of the solid matrix, are presented and discussed. Using some basic scientific principles, we derive analytical solutions and explore the conditions under which either the intrinsic pore-fluid pressure gradient or the intrinsic effective vertical-stress gradient can be maintained at the value of the lithostatic pressure gradient. Even though the intrinsic pore-fluid pressure gradient can be maintained at the value of the lithostatic pressure gradient in a single layer, it is impossible to maintain it at this value in all layers in a layered hydrodynamic system, unless all layers have the same permeability and porosity simultaneously. However, the intrinsic effective vertical-stress gradient of the solid matrix can be maintained at a value close to the lithostatic pressure gradient in all layers in any layered hydrodynamic system within the scope of this study.

Weathering of hydrocarbons in mangrove sediments: testing the effects of using dispersants to treat oil spills

This field study was a combined chemical and biological investigation of the relative effects of using dispersants to treat oil spills impacting mangrove habitats. The aim of the chemistry was to determine whether dispersant affected the short- or long-term composition of a medium range crude oil (Gippsland) stranded in a tropical mangrove environment in Queensland, Australia. Sediment cores from three replicate plots of each treatment (oil only and oil plus dispersant) were analyzed for total hydrocarbons and for individual molecular markers (alkanes, aromatics, triterpanes, and steranes). Sediments were collected at 2 days, then 1, 7, 13 and 22 months post-spill. Over this time, oil in the six treated plots decreased exponentially from 36.6 +/- 16.5 to 1.2 +/- 0.8 mg/g dry wt. There was no statistical difference in initial oil concentrations, penetration of oil to depth, or in the rates of oil dissipation between oiled or dispersed oil plots. At 13 months, alkanes were >50% degraded, aromatics were similar to 30% degraded based upon ratios of labile to resistant markers. However, there was no change in the triterpane or sterane biomarker signatures of the retained oil. This is of general forensic interest for pollution events. The predominant removal processes were evaporation (less than or equal to 27%) and dissolution (greater than or equal to 56%), with a lag-phase of 1 month before the start of significant microbial degradation (less than or equal to 7%). The most resistant fraction of the oil that remained after 7 months (the higher molecular weight hydrocarbons) correlated with the initial total organic carbon content of the soil. Removal rate in the Queensland mangroves was significantly faster than that observed in the Caribbean and was related to tidal flushing. (C) 1999 Elsevier Science Ltd. All rights reserved.

Experiments and modelling of phenanthrene biodegradation in the aqueous phase by a mixed culture

Pollution by polycyclic aromatic hydrocarbons(PAHs) is widespread due to unsuitable disposal of industrial waste. They are mostly defined as priority pollutants by environmental protection authorities worldwide. Phenanthrene, a typical PAH, was selected as the target in this paper. The PAH-degrading mixed culture, named ZM, was collected from a petroleum contaminated river bed. This culture was injected into phenanthrene solutions at different concentrations to quantify the biodegradation process. Results show near-complete removal of phenanthrene in three days of biodegradation if the initial phenanthrene concentration is low. When the initial concentration is high, the removal rate is increased but 20%-40% of the phenanthrene remains at the end of the experiment. The biomass shows a peak on the third day due to the combined effects of microbial growth and decay. Another peak is evident for cases with a high initial concentration, possibly due to production of an intermediate metabolite. The pH generally decreased during biodegradation because of the production of organic acid. Two phenomenological models were designed to simulate the phenanthrene biodegradation and biomass growth. A relatively simple model that does not consider the intermediate metabolite and its inhibition of phenanthrene biodegradation cannot fit the observed data. A modified Monod model that considered an intermediate metabolite (organic acid) and its inhibiting reversal effect reasonably depicts the experimental results.

Caracterização morfodinâmica do litoral Norte Fluminense, RJ, Brasil

A morfologia das praias é reflexo da ação hidrodinfunica com o tipo de sedimento disponível. Esta interação se dá a partir da base de ação das ondas, tornando-se mais efetiva na zona de arrebentação onde a energia é dissipada, originando na zona de surfe que se estende em direção à linha de costa até Q limite do espraiamento na face de praia. O objetivo deste trabalho é apresentar as características morfodinâmicas do litoral NE do Estado do Rio de Janeiro, baseando-se na análise da variação espaço Hemporal de perfis de praia, na morfologia da plataforma continental e em fotos aéreas. Os perfis de praia foram levantados durante cinco anos pela PETROBRÁS S/A, em oito estações ao longo do litoral. O comportamento morfodinâmico distinto de setores do litoral estudado é função do padrão de ondas e direção da linha de costa, morfologia da plataforma interna controlando a extensão da zona de surfe e o número de zonas de arrebentação, características dos sedimentos e gradiente da face de praia. Foram reconhecidos quatro compartimentos morfodinâmicos distintos, com base na morfologia dos perfis praiais e plataforma interna, no índice de mobilidade da linha de praia, granulometria x gradiente da face de praia e o parâmetro Q. Os quatro compartimentos são: Atafona/Foz do Rio Paraíba do Sul - estágio morfodinâmico intermediário a dissipativo, com o maior índice de mobilidade e elevada taxa de erosão; Sul de Atafona-Cabo de São Tomé - estágio intermediário a refletivo com baixo índice de mobilidade da praia; Cabo de São Tomé - estágio refletivo a intermediário com alto índice de mobilidade da praia; Cabo de São Tomé-Cabiúnas - estágio refletivo com baixo índice de mobilidade.

Estudo da Influencia de antioxidantes na avaliacao da estabilidade oxidativa de biodiesel pelo metodo petroOXY

O uso do biodiesel como um substituto total ou parcial do diesel de petróleo é significativo, entretanto a sua baixa estabilidade oxidativa é um ponto desfavorável. Portanto o uso de antioxidantes é viável desde que diminuam a velocidade de degradação promovido pela oxidação. Mas a ação de um antioxidante está relacionada com a composição química do biodiesel ao qual é adicionado. Considerando a importância e o crescimento da indústria de biodiesel, a necessidade de utilização de antioxidantes, e a busca por novas fontes como matérias primas, faz-se necessário estudar a eficiência de antioxidantes para o aumento da vida útil do biodiesel, além de avaliar novas culturas com potencial de produção como o pinhão manso (Jatropha curcas L.) e nabo forrageiro (Raphanus sativus L.). O objetivo deste trabalho foi avaliar os antioxidantes BHT (butilhidroxitolueno), PA (ácido pirogálico) e PG (galato de propila), em concentrações de 50, 200, 500, 1000 e 2000 mg/kg, nos biodiesel de pinhão manso, nabo forrageiro e soja, empregando a metodologia PetroOXY, ensaio acelerado de oxidação, para a determinação do seu período de indução. Os biodieseis foram obtidos através de reações de transesterificação, utilizando rota metílica, com rendimentos superiores a 80% e foram caracterizados através de alguns parâmetros físico-químicos. Foi observada a eficiência do uso de antioxidantes no aumento da vida útil do biodiesel. E com o aumento da concentração houve um aumento do período de indução. A eficiência do BHT foi sempre crescente com o aumento da concentração para todos os biodieseis enquanto que para o PG e PA houve uma diminuição da eficiência na maior concentração. A metodologia usada para avaliação da estabilidade oxidativa, PetroOXY, mostrou-se eficaz, de boa repetibilidade e reprodutibilidade, além de ser mais rápida e completa que o método Rancimat. Na concentração mais elevada, 2000 mg/kg, o melhor desempenho foi para o BHT, nas concentrações inferiores a 2000 mg/kg, a melhor eficiência foi para o PA ~ PG, nos três biodieseis estudados, soja, nabo forrageiro e pinhão manso.

Estudo da cristalização de parafinas por espectroscopia de RMN em temperaturas variáveis

A cristalização e formação de depósitos parafínicos é um problema operacional crítico na indústria do petróleo em todo o mundo e provoca grandes perdas econômicas na recuperação do óleo. São muitos os estudos que têm sido realizados para desenvolver modelos termodinâmicos de predição da precipitação de parafinas, sendo que boa parte deles utilizam a ressonância magnética nuclear (RMN) em alto ou baixo campo magnético juntamente com outras técnicas como calorimetria exploratória diferencial (DSC), análise elementar e cromatografia gasosa para caracterizar a fase sólida formada a partir do petróleo. Este trabalho busca um maior entendimento da cristalização de ceras parafínicas por meio de experimentos de espectroscopia de RMN de 1H e 13C conduzidos em temperaturas variáveis, o que pode auxiliar na previsão e remediação dos problemas causados pela sua deposição nas linhas de escoamento da produção. Para isso, o estudo desse fenômeno foi conduzido inicialmente em amostras de parafina comercial e, posteriormente, em uma amostra de petróleo parafínico com variação de temperatura sem extrair a fase sólida, garantindo a não interferência de solventes que podem influenciar no processo de cristalização. A metodologia desenvolvida demonstrou ser útil para determinar a temperatura inicial de aparecimento de cristais (TIAC), sendo obtida uma boa concordância com os resultados de DSC para a parafina comercial e petróleo. O registro de espectros em diferentes temperaturas permitiu também a identificação das variações de intensidade e largura de linha dos sinais associados aos diferentes grupos químicos presentes nos materiais estudados.

O planejamento econômico no Brasil: considerações críticas

In the past thirty years, a series of plans have been developed by successive Brazilian governments in a continuing effort to maximize the nation's resources for economic and social growth. This planning history has been quantitatively rich but qualitatively poor. The disjunction has stimulated Professor Mello e Souza to address himself to the problem of national planning and to offer some criticisms of Brazilian planning experience. Though political instability has obviously been a factor promoting discontinuity, his criticisms are aimed at the attitudes and strategic concepts which have sought to link planning to national goals and administration. He criticizes the fascination with techniques and plans to the exclusion of proper diagnosis of the socio-political reality, developing instruments to coordinate and carry out objectives, and creating an administrative structure centralized enough to make national decisions and decentralized enough to perform on the basis of those decisions. Thus, fixed, quantified objectives abound while the problem of functioning mechanisms for the coordinated, rational use of resources has been left unattended. Although his interest and criticism are focused on the process and experience of national planning, he recognized variation in the level and results of Brazilian planning. National plans have failed due to faulty conception of the function of planning. Sectorial plans, save in the sector of the petroleum industry under government responsibility, ha e not succeeded in overcoming the problems of formulation and execution thereby repeating old technical errors. Planning for the private sector has a somewhat brighter history due to the use of Grupos Executivos which has enabled the planning process to transcend the formalism and tradition-bound attitudes of the regular bureaucracy. Regional planning offers two relatively successful experiences, Sudene and the strategy of the regionally oriented autarchy. Thus, planning history in Brazil is not entirely black but a certain shade of grey. The major part of the article, however, is devoted to a descriptive analysis of the national planning experience. The plans included in this analysis are: The Works and Equipment Plan (POE); The Health, Food, Transportation and Energy Plan (Salte); The Program of Goals; The Trienal Plan of Economic and Social Development; and the Plan of Governmental Economic Action (Paeg). Using these five plans for his historical experience the author sets out a series of errors of formulation and execution by which he analyzes that experience. With respect to formulation, he speaks of a lack of elaboration of programs and projects, of coordination among diverse goals, and of provision of qualified staff and techniques. He mentions the absence of the definition of resources necessary to the financing of the plan and the inadequate quantification of sectorial and national goals due to the lack of reliable statistical information. Finally, he notes the failure to coordinate the annual budget with the multi-year plans. He sees the problems of execution as beginning in the absence of coordination between the various sectors of the public administration, the failure to develop an operative system of decentralization, the absence of any system of financial and fiscal control over execution, the difficulties imposed by the system of public accounting, and the absence of an adequate program of allocation for the liberation of resources. He ends by pointing to the failure to develop and use an integrated system of political economic tools in a mode compatible with the objective of the plans. The body of the article analyzes national planning experience in Brazil using these lists of errors as rough model of criticism. Several conclusions emerge from this analysis with regard to planning in Brazil and in developing countries, in general. Plans have generally been of little avail in Brazil because of the lack of a continuous, bureaucratized (in the Weberian sense) planning organization set in an instrumentally suitable administrative structure and based on thorough diagnoses of socio-economic conditions and problems. Plans have become the justification for planning. Planning has come to be conceived as a rational method of orienting the process of decisions through the establishment of a precise and quantified relation between means and ends. But this conception has led to a planning history rimmed with frustration, and failure, because of its rigidity in the face of flexible and changing reality. Rather, he suggests a conception of planning which understands it "as a rational process of formulating decisions about the policy, economy, and society whose only demand is that of managing the instrumentarium in a harmonious and integrated form in order to reach explicit, but not quantified ends". He calls this "planning without plans": the establishment of broad-scale tendencies through diagnosis whose implementation is carried out through an adjustable, coherent instrumentarium of political-economic tools. Administration according to a plan of multiple, integrated goals is a sound procedure if the nation's administrative machinery contains the technical development needed to control the multiple variables linked to any situation of socio-economic change. Brazil does not possess this level of refinement and any strategy of planning relevant to its problems must recognize this. The reforms which have been attempted fail to make this recognition as is true of the conception of planning informing the Brazilian experience. Therefore, unworkable plans, ill-diagnosed with little or no supportive instrumentarium or flexibility have been Brazil's legacy. This legacy seems likely to continue until the conception of planning comes to live in the reality of Brazil.