Straightforward synthesis of 2,2,4,4,5,7,7-d7-cholestane: a new deuterated standard in petroleum analysis

A short and efficient synthesis of heptadeuterated 2,2,4,4,5,7,7-d7-cholestane (1) from cholesterol (3) is described. The deuterated material will be useful for the analysis of different sources of petroleum in analytical geochemistry laboratories as internal standard for quantification of steranes via gas chromatography-mass spectrometry (GC-MS).

USE OF A LOW-COST TEMPLATE-FREE ZSM-5 FOR ATMOSPHERIC PETROLEUM RESIDUE PYROLYSIS

To understand the physicochemical properties and catalytic activity during the pyrolysis of atmospheric petroleum residue, a template-free ZSM-5 zeolite was synthesized using a direct method without additional seeds or an organic structure director and compared with conventionally synthesized ZSM-5. The crystallinities of the two zeolites were evaluated by XRD and FTIR and were quite similar; however, structural analyses using SEM and argon physisorption revealed that the zeolites diverged in particle diameter and in the external surface area of the micropores. The synthesis procedure without a template incorporated additional aluminum into the crystalline network, according to ICP-AES and TPD NH3 experiments. The catalytic pyrolysis performed over the template-free ZSM-5 generated results comparable to those for pyrolysis performed over the conventional ZSM-5 according to its hydrocarbon distribution. The selectivity to aromatics compounds was exactly the same for both ZSM-5 zeolites, and these values stand out compared to thermal pyrolysis. The template-free ZSM-5 produced 20% of light hydrocarbons (C4-C6), where such compounds are olefins and paraffins of great interest to the petrochemical industry. Therefore, template-free ZSM-5 is promising for industrial use due to its lowered synthesis time, low-cost and significant distribution to light hydrocarbons.

Analyse géographique des investissements internationaux de la China National Petroleum Corporation

Ce mémoire propose une analyse de l’expansion internationale de la China National Petroleum Corporation (CNPC) et des impacts de cette expansion sur la sécurité énergétique de la Chine. Dans le cadre de cette recherche, l’approvisionnement énergétique d’un pays est jugé sécuritaire lorsqu’une quantité suffisante de ressources nécessaires pour combler sa demande en énergie sont présentes, disponibles et accessibles et que son approvisionnement en services énergétiques demeure fiable et abordable. La recherche comporte quatre volets. Le premier volet porte sur les étapes de la restructuration de l’industrie pétrolière chinoise depuis 1949. Celle-ci est analysée au travers des changements dans les modes de gestion des compagnies pétrolières nationales et dans leurs relations avec le gouvernement chinois. Le deuxième volet traite de la diversification et des nouvelles spécialisations de CNPC. Ces aspects sont étudiés dans le cadre d’une analyse du pourcentage de ses actifs dans chaque segment industriel (aval, intermédiaire et amont) obtenus grâce à ses rapports annuels. Le troisième volet aborde la répartition géographique des activités de la compagnie que l’on étudie à l’aide d’une analyse approfondie de près de 150 investissements, acquisitions et contrats réalisés à l’étranger entre 1992 et 2014. Le quatrième volet aborde les impacts des investissements à l’étranger de la compagnie sur la sécurité énergétique de la Chine. Ces impacts sont mesurés par l’entremise d’une analyse des flux pétroliers internationaux vers la Chine que l’on compare à la production de CNPC par pays. Ce mémoire permet de déterminer que l’expansion internationale de CNPC sert d’abord et avant tout les intérêts économiques de la compagnie. Ce sont surtout ses investissements dans la construction d’infrastructures de transport (oléoducs, gazoducs ainsi que les usines et terminaux de liquéfaction de gaz naturel liquéfié) qui apportent des bénéfices directs à la sécurité énergétique de la Chine. La contribution des investissements dans les autres secteurs est beaucoup moins systématique et dépend largement de la période au cours de laquelle ils ont été effectués.

Relative proportions of polycyclic aromatic hydrocarbons differ between accumulation bioassays and chemical methods to predict bioavailability

Chemical methods to predict the bioavailable fraction of organic contaminants are usually validated in the literature by comparison with established bioassays. A soil spiked with polycyclic aromatic hydrocarbons (PAHs) was aged over six months and subjected to butanol, cyclodextrin and tenax extractions as well as an exhaustive extraction to determine total PAH concentrations at several time points. Earthworm (Eisenia fetida) and rye grass root (Lolium multiflorum) accumulation bioassays were conducted in parallel. Butanol extractions gave the best relationship with earthworm accumulation (r2 ≤ 0.54, p ≤ 0.01); cyclodextrin, butanol and acetone–hexane extractions all gave good predictions of accumulation in rye grass roots (r2 ≤ 0.86, p ≤ 0.01). However, the profile of the PAHs extracted by the different chemical methods was significantly different (p < 0.01) to that accumulated in the organisms. Biota accumulated a higher proportion of the heavier 4-ringed PAHs. It is concluded that bioaccumulation is a complex process that cannot be predicted by measuring the bioavailable fraction alone. The ability of chemical methods to predict PAH accumulation in Eisenia fetida and Lolium multiflorum was hindered by the varied metabolic fate of the different PAHs within the organisms.

Bile metabolites of polycyclic aromatic hydrocarbons (PAHs) in European eels Anguilla anguilla from United Kingdom estuaries

A total of 94 European eels (Anguilla anguilla) were collected from five estuaries in the UK. The deconjugated metabolites of polycyclic aromatic hydrocarbons (PAHs) in the bile of the eels were separated using HPLC. Six PAH metabolites were identified: 1-hydroxy (1-OH) metabolites of phenanthrene, pyrene and chrysene; and the 1-OH, 3-OH and 7,8 dihydrodiol metabolites of benzo[a]pyrene (BaP). The mean concentration of the six metabolites was greatest in eels from the Tyne (49 muM) followed by the Wear (33 muM), Tees (19 muM), Thames (4 muM) and Severn (2 muM) estuaries. Although 1-OH pyrene was always the dominant compound, there were significant differences (P<0.05) between sites and between estuaries for some metabolites. Normalising the molar concentration of the bile metabolites to the bile biliverdin absorbance reduced sample variation. When the metabolites identified were-each expressed as a percentage of the total detected, the metabolite profile was characteristic for each estuary. (C) 2002 Elsevier Science B.V. All rights reserved.

Detection of polycyclic aromatic hydrocarbons using quartz crystal microbalances

A chemically coated piezoelectric sensor has been developed for the determination of PAHs in the liquid phase. An organic monolayer attached to the surface of a gold electrode of a quartz crystal microbalance (QCM) via a covalent thiol-gold link complete with an ionically bound recognition element has been produced. This study has employed the PAH derivative 9-anthracene carboxylic acid which, once bound to the alkane thiol, functions as the recognition element. Binding of anthracene via pi-pi interaction has been observed as a frequency shift in the QCM with a detectability of the target analyte of 2 ppb and a response range of 0-50 ppb. The relative response of the sensor altered for different PAHs despite pi-pi interaction being the sole communication between recognition element and analyte. It is envisaged that such a sensor could be employed in the identification of key marker compounds and, as such, give an indication of total PAH flux in the environment.

Effects of biochar and the earthworm Eisenia fetida on the bioavailability of polycyclic aromatic hydrocarbons and potentially toxic elements

Polycyclic aromatic hydrocarbons (PAHs) and potentially toxic elements (PTEs) were monitored over 56 days in calcareous contaminated-soil amended with either or both biochar and Eisenia fetida. Biochar reduced total (449 to 306mgkg(-1)) and bioavailable (cyclodextrin extractable) (276 to 182mgkg(-1)) PAHs, PAH concentrations in E. fetida (up to 45%) but also earthworm weight. Earthworms increased PAH bioavailability by >40%. Combined treatment results were similar to the biochar-only treatment. Earthworms increased water soluble Co (3.4 to 29.2mgkg(-1)), Cu (60.0 to 120.1mgkg(-1)) and Ni (31.7 to 83.0mgkg(-1)) but not As, Cd, Pb or Zn; biochar reduced water soluble Cu (60 to 37mgkg(-1)). Combined treatment results were similar to the biochar-only treatment but gave a greater reduction in As and Cd mobility. Biochar has contaminated land remediation potential, but its long-term impact on contaminants and soil biota needs to be assessed.

Emission of polycyclic aromatic hydrocarbons from gasohol and ethanol vehicles

The exhaust emission of the polycyclic aromatic hydrocarbons (PAHs) considered toxic to human health were investigated on two spark ignition light duty vehicles, one being gasohol (Gasohol, in Brazil, is the generic denomination for mixtures of pure gasoline plus 20-25% of anhydrous ethyl alcohol fuel (AEAF).)-fuelled and the other a flexible-fuel vehicle fuelled with hydrated ethanol. The influence of fuel type and quality, aged lubricant oil type and use of fuel additives on the formation of these compounds was tested using standardized tests identical to US FTP-75 cycle. PAH sampling and chemical analysis followed the basic recommendations of method TO-13 (United States. Environmental Protection Agency, 1999. Compendium Method TO-13A - Determination of polycyclic Aromatic hydrocarbons (PAH) in Ambient Air Using Gas Chromatography/Mass Spectrometry (CG/MS). Center for environmental research information, Cincinnati, p. 78), with the necessary modification for this particular application. Results showed that the total PAH emission factor varied from 41.9 mu g km(-1) to 612 mu g km(-1) in the gasohol vehicle, and from 11.7 mu g km(-1) to 27.4 mu g km(-1) in the ethanol-fuelled vehicle, a significant difference in favor of the ethanol vehicle. Generally, emission of light molecular weight PAHs was predominant, while high molecular weights PAHs were not detected. In terms of benzo(a)pyrene toxicity equivalence, emission factors varied from 0.00984 mu g TEQ km(-1) to 4.61 mu g TEQ km(-1) for the gasohol vehicle and from 0.0117 mu g TEQ km(-1) to 0.0218 mu g TEQ km(-1) in the ethanol vehicle. For the gasohol vehicle, results showed that the use of fuel additive causes a significant increase in the emission of naphthalene and phenanthrene at a confidence level of 90% or higher; the use of rubber solvent on gasohol showed a reduction in the emission of naphthalene and phenanthrene at the same confidence level; the use of synthetic oil instead of mineral oil also contributed significantly to a decrease in the emission of naphthalene and fluorene. In relation to the ethanol vehicle, the same factors were tested and showed no statistically significant influence on PAH emission. (c) 2008 Elsevier Ltd. All rights reserved.

Determination of anthropogenic and biogenic compounds on atmospheric aerosol collected in urban, biomass burning and forest areas in Sao Paulo, Brazil

This study was conducted at three sites of different characteristics in Sao Paulo State Sao Paulo (SPA), Piracicaba (PRB) and Mate Atlantica Forest (MAT) PM(10), n-alkanes. pristane and phytane, PAHs, water-soluble ions and biomass burning tracers like levoglucosan and retene, were determined in quartz fiber filters. Samplings occurred on May 8th to August 8th, 2007 at the MAT site; on August 15th to 29th in 2007 and November 10th to 29th in 2008 at the PRB site and, March 13th to April 4th in 2007 and August 7th to 29th in 2008 at the SPA site Aliphatic compounds emitted biogenically were less abundant at the urban sites than at the forest site, and its distribution showed the influence of tropical vascular plants Air mass transport front biomass burning regions is likely to impact the sites with specific molecular markers The concentrations of all species were variable and dependent of seasonal changes In the most dry and polluted seasons, n-alkane and canon total concentrations were similar between the megacity and the biomass burning site PAHs and inorganic ion abundances were higher at Sao Paulo than Piracicaba, yet, the site influenced by biomass burning seems lobe the most impacted by the organic anion abundance in the atmosphere Pristane and phytane confirm the contamination by petroleum residues at urban sites, at the MAT site, biological activity and long range transport of pollutants might influence the levels of pristane (C) 2010 Elsevier B V All rights reserved

Gestão pela qualidade total no serviço de recursos humanos da Petrobrás: uma avaliação de sua implantação

Este trabalho procurou avaliar a implantação de Gestão pela Qualidade Total - GQT no Serviço de Recursos Humanos - SEREC da Petrobrás, através de uma pesquisa de campo, dentro de um contexto historicista. O problema identificado para a pesquisa foi: quais as possibilidades e dificuldades da implantação da Gestão pela Qualidade Total no SEREC ? Com o intuito de melhor subsidiar a pesquisa, foram estudados os conceitos acerca da formação do petróleo, do gás natural e do xisto; foram resumidamente explicadas cada uma das principais atividades desenvolvidas pela Petrobrás; foram aborbados alguns aspectos históricos que envolveram a sua origem. Em seguida estudou-se a evolução da função RH na Petrobrás, desde a sua criação até o final de 1995. Trataram-se os aspectos que envolveram a implantação da GQT no SEREC, inicialmente percorrendo os princípios e acontecimentos que nortearam sua implantação na Petrobrás-holding. Ao final, analisou-se a pesquisa de campo.

Degradação fotoquímica de hidrocarbonetos da gasolina em efluentes aquosos

Photo-oxidation processes of toxic organic compounds have been widely studied. This work seeks the application of the photo-Fenton process for the degradation of hydrocarbons in water. The gasoline found in the refinery, without additives and alcohol, was used as the model pollutant. The effects of the concentration of the following substances have been properly evaluated: hydrogen peroxide (100-200 mM), iron ions (0.5-1 mM) and sodium chloride (200 2000 ppm). The experiments were accomplished in reactor with UV lamp and in a falling film solar reactor. The photo-oxidation process was monitored by measurements of the absorption spectra, total organic carbon (TOC) and chemical oxygen demand (COD). Experimental results demonstrated that the photo-Fenton process is feasible for the treatment of wastewaters containing aliphatic hydrocarbons, inclusive in the presence of salts. These conditions are similar to the water produced by the petroleum fields, generated in the extraction and production of petroleum. A neural network model of process correlated well the observed data for the photooxidation process of hydrocarbons

Determinação de dados de equilíbrio de fases para sistemas aquosos com eletrólitos

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer s ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Avaliação de diferentes processos oxidativos avançados no tratamento de resíduos de petróleo

The petroleum industry deals with problems which are difficult to solve because of their relation to environmental issues. This is because amounts of residue are generated which vary in type and danger level. The soil contamination by non aqueous liquid phase mixtures, specifically hydrocarbon petroleum has been a reason for great concern, mainly the aromatic and polycyclic aromatic, which present risk to human health due to its carcinogenic and mutagenic character. The Advanced Oxidative Processes (AOP) are efficient technologies for destruction of organic compounds of difficult degradation and, often, they are present in low concentrations. They can be considered clean technologies, because there is no formation of solid by-products or the transfer of pollutor phases. This work focuses on the study of the degradation of petroleum industrial waste, by Advanced Oxidation Processes. Treatments tackling petroleum residues, contaminated soil, and water occurring in the production of petroleum reached the following Polycyclic Aromatic Hydrocarbons (PAH) degradation levels: solid residues 100% in 96 treatment hours; water residue - 100% in 6 treatment hours; soil contamination (COT degradation) - 50.3% in 12 treatment hours. AOP were effective in dealing with petroleum residues thus revealing themselves to be a promising treatment alternative

Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Degradação eletroquímica de benzeno, tolueno e xileno via oxidação eletroquímica utilizando eletrodo Ti/Pt

This work is directed to the treatment of organic compounds present in produced water from oil using electrochemical technology. The water produced is a residue of the petroleum industry are difficult to treat , since this corresponds to 98 % effluent from the effluent generated in the exploration of oil and contains various compounds such as volatile hydrocarbons (benzene, toluene, ethylbenzene and xylene), polycyclic aromatic hydrocarbons (PAHs), phenols, carboxylic acids and inorganic compounds. There are several types of treatment methodologies that residue being studied, among which are the biological processes, advanced oxidation processes (AOPs), such as electrochemical treatments electrooxidation, electrocoagulation, electrocoagulation and eletroredution. The electrochemical method is a method of little environmental impact because instead of chemical reagents uses electron through reactions of oxide-reducing transforms toxic substances into substances with less environmental impact. Thus, this paper aims to study the electrochemical behavior and elimination of the BTX (benzene, toluene and xylene) using electrode of Ti/Pt. For the experiment an electrochemical batch system consists of a continuous source, anode Ti/Pt was used, applying three densities of current (1 mA/cm2, 2,5 mA/cm2 and 5 mA/cm2). The synthetic wastewater was prepared by a solution of benzene, toluene and xylene with a concentration of 5 ppm, to evaluate the electrochemical behavior by cyclic voltammetry and polarization curves, even before assessing the removal of these compounds in solution by electrochemical oxidation. The behavior of each of the compounds was evaluated by the use of electrochemical techniques indicate that each of the compounds when evaluated by cyclic voltammetry showed partial oxidation behavior via adsorption to the surface of the Ti/Pt electrode. The adsorption of each of the present compounds depends on the solution concentration but there is the strong adsorption of xylene. However, the removal was confirmed by UV-Vis, and analysis of total organic carbon (TOC), which showed a percentage of partial oxidation (19,8 % - 99,1 % TOC removed), confirming the electrochemical behavior already observed in voltammetry and cyclic polarization curves