Síntese enzimática de biosurfactante e sua aplicabilidade na indústria do petróleo

Enzymes have been widely used in biosynthesis/transformation of organic compounds in substitution the classic synthetic methods. This work is the first writing in literature of enzymatic synthesis for attainment the biossurfactants, the use glucose sucrose, ricinoleic acid e castor oil as substratum, and as biocatalyst, used immobilized lipase Thermomyces lanuginose, Rhizomucor miehei and the Candida antarctica lipase B; alkaline protease and neutral protease from Bacillus subtillis and yeast Saccharomyces cerevisiaeI. The analysis of HPLC (high performance liquid chromatography) showed that highest conversions were reached of used the alkaline protease from Bacillus subtillis. Laboratory tests, to evaluate the applicability, indicated that the produced biosurfactantes had good stability in presence of salts (NaCl) and temperature (55 e 25°C), they are effective in the reduction of the superficial tension and contac angle, but they have little foaming capacity, when compared with traditional detergents. These results suggest that the prepared surfactants have potential application as wetting agent and perforation fluid stabilizer

Síntese e caracterização de materiais nanoporosos para pirólise catalítica de óleos pesados

The present work reports the study of nanoporous structures, aiming at their use in research directed to the current demand of the petroleum industry to value heavy oil. Initially, two ways were chosen for the synthesis of porous structures from the molecular sieves of type Si-MCM-41. In the first way, the structure MCM-41 is precursory for heteroatom substitutes of silicon, generating catalyst of the type Al-MCM-41 from two different methods of incorporation of the metal. This variation of the incorporation method of Aluminum in the structure of Si-MCM-41 was carried out through the conventional procedure, where the aluminum source was incorporated to the gel of synthesis, and the procedure post-synthesis, where the Aluminum source was incorporated in catalyst after the synthesis of Si-MCM-41. In the second way, the MCM-41 acts as a support for growth of nanocrystals of zeolite embedded in their mesoporous, resulting in hybrid MCM-41/ZSM-5 catalyst. A comparative analysis was carried through characterizations by XRD, FTIR, measures of acidity through n-butylamine adsorption for TGA, SEM-XRF and N2 adsorption. Also crystalline aluminosilicate with zeolitic structure MFI of type ZSM-5 was synthesized without using organic templates. Methodologies to the preparation of these materials are related by literature using conventionally reactants that supply oxides of necessary silicon and aluminum, as well as a template agent, and in some cases co-template. The search for new routes of preparation for the ZSM-5 aimed at, above all, the optimization of the same as for the time and the temperature of synthesis, and mainly the elimination of the use of organic templates, that are material of high cost and generally very toxic. The current study is based on the use of the H2O and Na+ cations playing the role of structural template and charge compensation in the structure. Characterizations by XRD, FTIR, SEM-XRF and N2 adsorption were also conducted for this material in order to compare the samples of ZSM-5 synthesized in the absence of template and those used industrially and synthesized using structuring

Análise dos Processos de Flotação e Oxidação Avançada para o Tratamento de Efluente Modelo da Indústria do Petróleo

The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitablesurfactant was the EO 7 due to the lower reagent consumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min

Uso da palha de carnaúba em revestimento de dutos

In this work, the plant species Copernicia prunifera (Miller) H. E. Moore (carnauba), naturally occurring which prevails in the northeast region of Brazil was the subject of studies aiming its use as external coating of pipelines used in petroleum industry. The part of the plant worked were the leaves, also called straw, which were coated with resinous material. For this purpose, it was necessary to evaluate the effectiveness of the use of acrylic resins in the straw carnauba coating. The properties of the untreated carnauba straw and chemically treated with sodium hydroxide, hexane and carbon tetrachloride were investigated by ATRFTIR, SEM and thermal analysis. The first two techniques showed that treatment with solvents has caused major changes in the straw surface, while the thermal analysis indicated that the sodium hydroxide caused variations in thermal stability of straw constituents. Water absorption measurements showed that treatments have accelerated the absorption process and the reduction of contact angle values for treated samples with solvents indicated higher hidrophilicity of straw. The tensile tests showed lower values of elastic modulus and tensile strength for treated samples. Furthermore, coatings using pure commercial resins A and B as well as the formulations with clay were applied in straw and they were examined once again through thermal analysis, water absorption measurements, contact angle and mechanical tests. To analyze the effect of heat ageing, samples were subjected to tensile tests again in order to assess its resistance. The results showed that the resins/clay formulations increased thermal stability of straw, they promoted a good impermeabilization and caused significant decrease in the values of elastic modulus and tensile strength. Evaluating the ageing effect on the mechanical properties, it has been showed good recovery to the coated straw with the formulations A 60 and A 80% in modulus and tensile strength values and elongation at break values have remained very close. It is thus concluded that the carnauba straw can be used as a coating of pipelines with significant cost savings, since there is no need for pretreatment for its use and shows itself as a viable biotechnology alternative, contributing to the quality of coatings material and environment preservation.

Síntese e caracterização de poliacrilamidas modificadas para utilização na indústria do petróleo

Modified polyacrylamides with ≅ 0.2 mol % of N,N-dihexylacrylamide and hydrolysis degree from 0 to 25 % were synthesized by micellar copolymerization. The hydrophobic monomer was obtained by the reaction between acryloyl chloride and N,Ndihexylamine and characterized by infrared (IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. The polymer molecular structures were determined through 1H and 13C NMR spectroscopy and the polymers were studied in dilute and semi-dilute regimes by viscometry, rheometry, static light scattering and photon correlation spectroscopy, at the temperature range from 25 to 55 ºC. The data obtained by viscometry showed that the intrinsic viscosity from the hydrolyzed polymers is larger than the precursor polymers at the same ionic strength. The comparison between the charged polymers showed that the polymer with higher hydrolysis degree has a more compact structure in formation water (AFS). The increase of temperature led to an enhanced reduced viscosity to the polymers in Milli-Q water (AMQ), although, in brine, only the unhydrolyzed polymer had an increase in the reduced viscosity with the temperature, and the hydrolyzed derivatives had a decrease in the reduced viscosity. The static light scattering (SLS) analyses in salt solutions evidenced a decrease of weight-average molecular weight (⎯Mw) with the increase of the hydrolysis degree, due to the reduction of the thermodynamic interactions between polymer and solvent, which was evidenced by the decrease of the second virial coefficient (A2). The polymers showed more than one relaxation mode in solution, when analyzed by photon correlation spectroscopy, and these modes were attributed to isolated coils and aggregates of several sizes. The aggregation behavior depended strongly on the ionic strength, and also on the temperature, although in a lower extension. The polymers showed large aggregates in all studied conditions, however, their solutions did not displayed a good increase in water viscosity to be used in enhanced oil recovery (EOR) processes

Utilização de uma coluna de flotação para remoção de compostos orgânicos da água de produção

Innovative technologies using surfactant materials have applicability in several industrial fields, including petroleum and gas areas. This study seeks to investigate the use of a surfactant derived from coconut oil (SCO saponified coconut oil) in the recovery process of organic compounds that are present in oily effluents from petroleum industry. For this end, experiments were accomplished in a column of small dimension objectifying to verify the influence of the surfactant SCO in the efficiency of oil removal. This way, they were prepared emulsions with amount it fastens of oil (50, 100, 200 and 400 ppm), being determined the great concentrations of surfactant for each one of them. Some rehearsals were still accomplished with produced water of the industry of the petroleum to compare the result with the one of the emulsions. According to the experiments, it was verified that an increase of the surfactant concentration does not implicate in a greater oil removal. The separation process use gaseous bubbles formed when a gas stream pass a liquid column, when low surfactant concentrations are used, it occurs the coalescence of the dispersed oil droplets and their transport to the top of the column, forming a new continuous phase. Such surfactants lead to a gas-liquid interface saturation, depending on the used surfactant concentration, affecting the flotation process and influencing in the removal capacity of the oily dispersed phase. A porous plate filter, with pore size varying from 40 to 250 mm, was placed at the base of the column to allow a hydrodynamic stable operation. During the experimental procedures, the operating volume of phase liquid was held constant and the rate of air flow varied in each experiment. The resulting experimental of the study hydrodynamic demonstrated what the capturing of the oil was influenced by diameter of the bubbles and air flow. With the increase flow of 300 about to 900 cm3.min-1, occurred an increase in the removal of oil phase of 44% about to 66% and the removal kinetic of oil was defined as a reaction of 1° order.

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

Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry

Formal verification of PLC programs using the B Method

PLCs (acronym for Programmable Logic Controllers) perform control operations, receiving information from the environment, processing it and modifying this same environment according to the results produced. They are commonly used in industry in several applications, from mass transport to petroleum industry. As the complexity of these applications increase, and as various are safety critical, a necessity for ensuring that they are reliable arouses. Testing and simulation are the de-facto methods used in the industry to do so, but they can leave flaws undiscovered. Formal methods can provide more confidence in an application s safety, once they permit their mathematical verification. We make use of the B Method, which has been successfully applied in the formal verification of industrial systems, is supported by several tools and can handle decomposition, refinement, and verification of correctness according to the specification. The method we developed and present in this work automatically generates B models from PLC programs and verify them in terms of safety constraints, manually derived from the system requirements. The scope of our method is the PLC programming languages presented in the IEC 61131-3 standard, although we are also able to verify programs not fully compliant with the standard. Our approach aims to ease the integration of formal methods in the industry through the abbreviation of the effort to perform formal verification in PLCs

Aplicação do método B ao projeto formal de software embarcado

This work shows a project method proposed to design and build software components from the software functional m del up to assembly code level in a rigorous fashion. This method is based on the B method, which was developed with support and interest of British Petroleum (BP). One goal of this methodology is to contribute to solve an important problem, known as The Verifying Compiler. Besides, this work describes a formal model of Z80 microcontroller and a real system of petroleum area. To achieve this goal, the formal model of Z80 was developed and documented, as it is one key component for the verification upto the assembly level. In order to improve the mentioned methodology, it was applied on a petroleum production test system, which is presented in this work. Part of this technique is performed manually. However, almost of these activities can be automated by a specific compiler. To build such compiler, the formal modelling of microcontroller and modelling of production test system should provide relevant knowledge and experiences to the design of a new compiler. In ummary, this work should improve the viability of one of the most stringent criteria for formal verification: speeding up the verification process, reducing design time and increasing the quality and reliability of the product of the final software. All these qualities are very important for systems that involve serious risks or in need of a high confidence, which is very common in the petroleum industry

Sistema integrado para tomada de decisão espacial em situações de derramamento de óleo no litoral norte do Estado do RN

The northern coast of Rio Grande do Norte State (RN) shows areas of Potiguar basin with high activity in petroleum industry. With the goal of avoiding and reducing the accident risks with oil it is necessary to understand the natural vulnerability, mapping natural resources and monitoring the oil spill. The use of computational tools for environmental monitoring makes possible better analyses and decisions in political management of environmental preservation. This work shows a methodology for monitoring of environment impacts, with purpose of avoiding and preserving the sensible areas in oil contact. That methodology consists in developing and embedding an integrated computational system. Such system is composed by a Spatial Decision Support System (SDSS). The SDSS shows a computational infrastructure composed by Web System of Geo-Environmental and Geographic Information - SWIGG , the System of Environmental Sensibility Maps for Oil Spill AutoMSA , and the Basic System of Environmental Hydrodynamic ( SisBAHIA a System of Modeling and Numerical Simulating SMNS). In a scenario of oil spill occurred coastwise of Rio Grande do Norte State s northern coast, the integration of such systems will give support to decision agents for managing of environmental impacts. Such support is supplied through a system of supporting to spatial decisions

Avaliação de floculante natural à base de Moringa oleifera no tratamento de água produzida na indústria do petróleo: aplicação da técnica combinada floculação/flotação

The principal effluent in the oil industry is the produced water, which is commonly associated to the produced oil. It presents a pronounced volume of production and it can be reflected on the environment and society, if its discharge is unappropriated. Therefore, it is indispensable a valuable careful to establish and maintain its management. The traditional treatment of produced water, usualy includes both tecniques, flocculation and flotation. At flocculation processes, there are traditional floculant agents that aren’t well specified by tecnichal information tables and still expensive. As for the flotation process, it’s the step in which is possible to separate the suspended particles in the effluent. The dissolved air flotation (DAF) is a technique that has been consolidating economically and environmentally, presenting great reliability when compared with other processes. The DAF is presented as a process widely used in various fields of water and wastewater treatment around the globe. In this regard, this study was aimed to evaluate the potential of an alternative natural flocculant agent based on Moringa oleifera to reduce the amount of oil and grease (TOG) in produced water from the oil industry by the method of flocculation/DAF. the natural flocculant agent was evaluated by its efficacy, as well as its efficiency when compared with two commercial flocculant agents normally used by the petroleum industry. The experiments were conducted following an experimental design and the overall efficiencies for all flocculants were treated through statistical calculation based on the use of STATISTICA software version 10.0. Therefore, contour surfaces were obtained from the experimental design and were interpreted in terms of the response variable removal efficiency TOG (total oil and greases). The plan still allowed to obtain mathematical models for calculating the response variable in the studied conditions. Commercial flocculants showed similar behavior, with an average overall efficiency of 90% for oil removal, however it is the economical analysis the decisive factor to choose one of these flocculant agents to the process. The natural alternative flocculant agent based on Moringa oleifera showed lower separation efficiency than those of commercials one (average 70%), on the other hand this flocculant causes less environmental impacts and it´s less expensive

O objetivo constitucional de desenvolvimento e o instrumento jurídico-normativo do conteúdo local na indústria petrolífera

On the petroleum industry, the State developed the Local Content police as a regulatory action to guarantee the preference of the national supply industry. Observing that, this paper will analyze the Local Content police aware of the constitutional goal of development as wright in the Constituição Federal de 1988. For it, will be used the hypothetical-deductive method for identifying the Local Content police as State strategy of development turn it in the object of critics in a dialectic way of thinking to in the final, present a conclusion about the police. As result was saw that the existent structure of the police at Brazil is inefficient, claiming for a rebuilt. For conclusion, is said that because of the inadequate construction of the Local Content police created inside of the Agência Nacional do Petróleo – ANP, the efficiency of the full potential of the police is been stopped, something that can be only corrected although a re-make of the police

Aplicação do Na2S2O8, H2O2 e ferro na remediação de solos (latossolo e areia destrófica) contaminados com diesel

Environmental liabilities from accidents in the retail petroleum industry, especially in urban areas, have represented a serious problem whose impact reaches the underground, people's health and even economic losses with the remediation process. In U.S.A. are estimated hundreds of billions of dollars invested in soil remediation processes. The results of the reports and investigative reports of liabilities in fuel stations distributed in the urban area of Natal-RN were used to estimate the local scenario of contamination. This database has been possible to determine the main contaminants (BTEX, PAHs, TOC), affected neighborhoods and types of potentially more impacted soils. Experiments were carried out in order to reverse contamination of this scenario, where the soil type was a factor in the planning, because it influences directly on the effectiveness of remediation techniques studied: Oxidation by hydrogen peroxide and oxidation by sodium persulphate. These oxidants are activated forming free radicals (HO•-, SO4 •-, HO2 • , O2 •-, S2O8 -2, etc) responsible for to mineralize the hydrocarbons and other organic compounds (releasing O2 e CO2). In the activation process, the ferrous ions (II) and ferric (III) were studied as well as hydrogen peroxide activation technique with sodium persulfate, the latter being presented the best efficiency among all the study, when activated with Fe+3. In addition to defining the most efficient technique, the aim of this study was to evaluate the influence of different soils among oxidative techniques, characterizing the effect of the concentration of these oxidants and also the concentration of the catalysts. Exists in most scenarios evaluated the presence of intrinsic total iron soil matrix. The so-called latosols present microaggregates reddish indicating the presence of these reactive species like iron and clayey aspect. The kinetic study was conducted by experimental design and monitoring of the percentage of total carbon (SSM-5000A) in the solid and liquid phases, knowing that 82.4% of the diesel molecule is carbon. Yet organic carbon and pH of liquid samples were analyzed for technical, characterizing the influence of soil type and its operating condition. The Fenton-like technique H2O2 e Fe+2 presented satisfactory oxidation, including sandy soil, but well below the best result. The sodium persulphate only activated with temperature, even in the most favorable soil, did not provide good efficiency. The best technique in the study had the concentration profile with 2,2x10- 1mol.L-1 of Na2S2O8 activated with 6,53x10-1mol.L-1 of H2O2 and 2,5x10-2 Fe3+mol.L-1 which reduced in less than a day 96 contamination in red soil, initially with 66,667 mg of diesel per kg of clean soil

Os limites constitucionais ao exercício de direito de patente e seus reflexos na indústria do petróleo, gás natural e biocombustíveis

This dissertation deals with the constitutional limits on the exercise of patent rights and its effects on the oil, natural gas and biofuels. Held with the support of ANP / PETROBRAS, It seeks to show how the law will limit the exercise of industrial property, based on a reinterpretation of private law by the constitutional development perspective . Today it is a fact that Petrobras, a Brazilian joint venture, has the latest technology in various sectors of the oil industry, and is one of the highest investments in developing new technologies. The overall objective of this thesis is to establish the relationship between the public interest of the Petroleum Industry, Natural Gas and Biofuels and constitutional limits to the free exercise of patent rights, then confirm or refute our hypothesis that Article 71 on Industrial Property Law is contrary to the existing objectives in Article 3 of the Constitution of the Federative Republic of Brazil. The research aims to examine the relevant aspects of the legal nature attributed to IPGN constitutionally confronting the constitutional limits on the free exercise of patent rights, with the purpose to outline the state of the performance limits in the regulation of the economy, in particular the application of feasibility limitations on the right of property in favor of national interest on the strategic energy industry. The aim is to confront the fundamental rights to property and economic development, against the public interest, limiting these first. As to the objectives, the research will be theoretical and descriptive and harvest of industrial property, respect the possible impact of regulatory standards and limiting the right of ownership in the oil industry. To establish how the state will mitigate the intellectual property right, we discuss, at first, a definition of public interest from the general theory of state and sovereign character in order to establish a new concept of national interest and popular interest, which will in turn the definition of our concept of public interest. In the second phase, will be addressed the issue of industrial property rights and how to will be free exercise thereof, in the constitutional sphere, infra, and demonstrating the use of industrial property rights with examples of market and IPGN . After situating the industrial property rights in the constitution and national legislation, establish their relationship with the national and regional development, will be addressed in this chapter in particular the patent law, as most usual form of intellectual property protection in IPGN. Used a study highlighting the number of patents in the area of the analyzed industry, demonstrating with hard data the importance of a sector for industrial development. The relationship between the social function of intellectual property and the constitutional objective of development was characterized to demonstrate the strategic nature of oil to Brazil in the national and international scene, and put into question the hypothesis of the research which provides that even with large investments the lack of legal certainty in the sector turns out not to have a considerable volume of investment as it could.