Avaliação da remoção de sulfeto de hidrogênio do gás natural em uma coluna de absorção

Natural gas, although basically composed by light hydrocarbons, also presents in its composition gaseous contaminants such as CO2 (carbon dioxide) and H2S (hydrogen sulfide). Hydrogen sulfide, which commonly occurs in oil and gas exploration and production activities, besides being among the gases that are responsible by the acid rain and greenhouse effect, can also cause serious harm to health, leading even to death, and damages to oil and natural gas pipelines. Therefore, the removal of hydrogen sulfide will significantly reduce operational costs and will result in oil with best quality to be sent to refinery, thereby resulting in economical, environmental, and social benefits. These factors highlight the need for the development and improvement of hydrogen sulfide sequestrating agents to be used in the oil industry. Nowadays there are several procedures for hydrogen sulfide removal from natural gas used by the petroleum industry. However, they produce derivatives of amines that are harmful to the distillation towers, form insoluble precipitates that cause pipe clogging and produce wastes of high environmental impact. Therefore, the obtaining of a stable system, in inorganic or organic reaction media, that is able to remove hydrogen sulfide without forming by-products that affect the quality and costs of natural gas processing, transport and distribution is of great importance. In this context, the evaluation of the kinetics of H2S removal is a valuable procedure for the treatment of natural gas and disposal of the byproducts generated by the process. This evaluation was made in an absorption column packed with Raschig ring, where natural gas with H2S passes through a stagnant solution, being the contaminant absorbed by it. The content of H2S in natural gas in column output was monitored by an H2S analyzer. The comparison between the obtained curves and the study of the involved reactions have not only allowed to determine the efficiency and mass transfer controlling step of the involved processes but also make possible to effect a more detailed kinetic study and evaluate the commercial potential of each reagent

Self-assembling of phenothiazine compounds investigated by small-angle X-ray scattering and electron paramagnetic resonance spectroscopy

Small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been carried out to investigate the structure of the self-aggregates of two phenothiazine drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), in aqueous solution. In the SAXS studies, drug solutions of 20 and 60 mM, at pH 4.0 and 7.0, were investigated and the best data fittings were achieved assuming several different particle form factors with a homogeneous electron density distribution in respect to the water environment. Because of the limitation of scattering intensity in the q range above 0.15 angstrom(-1), precise determination of the aggregate shape was not possible and all of the tested models for ellipsoids, cylinders, or parallelepipeds fitted the experimental data equally well. The SAXS data allows inferring, however, that CPZ molecules might self-assemble in a basis set of an orthorhombic cell, remaining as nanocrystallites in solution. Such nanocrystals are composed of a small number of unit cells (up to 10, in c-direction), with CPZ aggregation numbers of 60-80. EPR spectra of 5- and 16-doxyl stearic acids bound to the aggregates were analyzed through simulation, and the dynamic and magnetic parameters were obtained. The phenothiazine concentration in EPR experiments was in the range of 5-60 mM. Critical aggregation concentration of TFP is lower than that for CPZ, consistent with a higher hydrophobicity of TFP. At acidic pH 4.0 a significant residual motion of the nitroxide relative to the aggregate is observed, and the EPR spectra and corresponding parameters are similar to those reported for aqueous surfactant micelles. However, at pH 6.5 a significant motional restriction is observed, and the nitroxide rotational correlation times correlate very well with those estimated for the whole aggregated particle from SAXS data. This implies that the aggregate is densely packed at this pH and that the nitroxide is tightly bound to it producing a strongly immobilized EPR spectrum. Besides that, at pH 6.5 the differences in motional restriction observed between 5- and 16-DSA are small, which is different from that observed for aqueous surfactant micelles.

Formação de caudas maxwellianas no Contexto da rotação estelar

In this Thesis, we analyzed the formation of maxwellian tails of the distributions of the rotational velocity in the context of the out of equilibrium Boltzmann Gibbs statistical mechanics. We start from a unified model for the angular momentum loss rate which made possible the construction of a general theory for the rotational decay in the which, finally, through the compilation between standard Maxwellian and the relation of rotational decay, we defined the (_, _) Maxwellian distributions. The results reveal that the out of equilibrium Boltzmann Gibbs statistics supplies us results as good as the one of the Tsallis and Kaniadakis generalized statistics, besides allowing fittings controlled by physical properties extracted of the own theory of stellar rotation. In addition, our results point out that these generalized statistics converge to the one of Boltzmann Gibbs when we inserted, in your respective functions of distributions, a rotational velocity defined as a distribution

Assessment of a high-order finite difference upwind scheme for the simulation of convection-diffusion problems

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação da fissuração por fadiga em tubos durante transporte marítimo

Tubos de aço são transportados diariamente em todo o mundo, por caminhão, trem ou navio. Conseqüentemente, danos de transporte, podem ocorrer com freqüência e regularidade. O tipo de dano particular selecionado para este estudo foi o de trinca por fadiga, o qual é considerado como um dos mais críticos. Neste trabalho foram estudados tubos de aço fabricados de acordo com os requisitos da norma API 5L [1]. Foram efetuadas caracterizações químicas, mecânicas e metalográficas de um tubo com diâmetro 609,6 mm e espessura 15,87 mm grau X-65. A simulação do transporte por navio de tubos de aço foi feita submetendo-se seções de tubo com comprimento igual a 0,1 metro, a ciclos de fadiga por meio de máquina servo-hidráulica. Foi possível concluir que em tubos soldados, a região adjacente ao cordão de solda é a mais crítica, e que quando o posicionamento do tubo na carga é efetuado de maneira que a solda fique apoiada sobre alguma superfície rígida, a ocorrência de trinca por fadiga torna-se possível principalmente se os procedimentos de manuseio, carregamento e transporte não forem executados da maneira como recomendada pelos fabricantes de tubos e pela norma API [2].

Radiografia digital para inspeção de soldas de dutos - melhor sensibilidade

The conventional radiographic technique using industrial radiographic films is with the days finishing. The Digital Radiography is taking place in several sectors, e.g., the medical, aerospace, security, automotive, etc. In addition to representing a technological trend, it has been demonstrated that digital radiography offers a series of benefits in terms of productivity, sensitivity, environmental aspects, image treatment tools, cost reduction, etc. If one weld seam to be inspected is from a serried product, as example a pipe, the best option to be implemented is the Flat Panel Detector with this equipment is possible to reduce the obtaining digital radiographic images in place of films and reducing the inspection cycle time due to its high degree of automation. In the experiments described in this paper this new technique was tested and the results were compared with those obtained by the conventional radiography. The welded specimens were prepared using the submerged-arc welding process and small artificial cracks of the most varied dimensions, present in the specimens, were used to establish a comparison of the sensitivities presented by the techniques employed After conducting several experiments, the digital method presented the highest sensitivity to the wire-type Image Quality Indicator (IQI) and in the detection of small defects, leading to the conclusion that the use of digital radiography using the flat-panel detector offers advantages over the conventional technique [1, 2]. This work was carried out based on the API 5L Edition 2004 [3] and ISO 3183 Edition 2007 [4] specifications.

Digital radiography using digital detector arrays fulfills critical applications for offshore pipelines

Digital radiography in the inspection of welded pipes to be installed under deep water offshore gas and oil pipelines, like a presalt in Brazil, in the paper has been investigated. The aim is to use digital radiography for nondestructive testing of welds as it is already in use in the medical, aerospace, security, automotive, and petrochemical sectors. Among the current options, the DDA (Digital Detector Array) is considered as one of the best solutions to replace industrial films, as well as to increase the sensitivity to reduce the inspection cycle time. This paper shows the results of this new technique, comparing it to radiography with industrial films systems. In this paper, 20 test specimens of longitudinal welded pipe joints, specially prepared with artificial defects like cracks, lack of fusion, lack of penetration, and porosities and slag inclusions with varying dimensions and in 06 different base metal wall thicknesses, were tested and a comparison of the techniques was made. These experiments verified the purposed rules for parameter definitions and selections to control the required digital radiographic image quality as described in the draft international standard ISO/DIS 10893-7. This draft is first standard establishing the parameters for digital radiography on weld seam of welded steel pipes for pressure purposes to be used on gas and oil pipelines.

Photopyroelectric spectroscopy of polyaniline films

Photopyroelectric spectroscopy (PPES), in the 400 < lambda < 900 nm wavelength range, was used to study thermal properties of differently doped polyaniline (PAN) films. The photopyroelectric intensity signal V-n(lambda) and its phase F-n(lambda) were independently measured, as well as the intensity V-n(f) and the phase F-n(f) (f being the chopping frequency) for a given A of the saturation part of the PPES spectrum. Equations of both the intensity and the phase of the PPES signal, taking into account the thermal and the optical characteristics of the PAN films and the pyroelectric detector, were used to fit the experimental results. From the fittings we obtained, with great accuracy, the values of thermal conductivity k and thermal diffusivity coefficient a of PAN films of different doping degrees. It was observed that, in contrast with the strong doping-dependence of the electrical conductivity, the thermal parameters of PAN films remained practically unchanged under doping. This apparent discrepancy is explained by the granular metal model of doped PAN. (C) 2000 John Wiley & Sons, Inc.

Algorítmo evolucionário para a distribuição de produtos de petróleo por redes de polidutos

The distribution of petroleum products through pipeline networks is an important problem that arises in production planning of refineries. It consists in determining what will be done in each production stage given a time horizon, concerning the distribution of products from source nodes to demand nodes, passing through intermediate nodes. Constraints concerning storage limits, delivering time, sources availability, limits on sending or receiving, among others, have to be satisfied. This problem can be viewed as a biobjective problem that aims at minimizing the time needed to for transporting the set of packages through the network and the successive transmission of different products in the same pipe is called fragmentation. This work are developed three algorithms that are applied to this problem: the first algorithm is discrete and is based on Particle Swarm Optimization (PSO), with local search procedures and path-relinking proposed as velocity operators, the second and the third algorithms deal of two versions based on the Non-dominated Sorting Genetic Algorithm II (NSGA-II). The proposed algorithms are compared to other approaches for the same problem, in terms of the solution quality and computational time spent, so that the efficiency of the developed methods can be evaluated

Um estudo algorítmico de problemas logísticos na indústria de petróleo e gás natural

This work consists on the study of two important problems arising from the operations of petroleum and natural gas industries. The first problem the pipe dimensioning problem on constrained gas distribution networks consists in finding the least cost combination of diameters from a discrete set of commercially available ones for the pipes of a given gas network, such that it respects minimum pressure requirements at each demand node and upstream pipe conditions. On its turn, the second problem the piston pump unit routing problem comes from the need of defining the piston pump unit routes for visiting a number of non-emergent wells in on-shore fields, i.e., wells which don t have enough pressure to make the oil emerge to surface. The periodic version of this problem takes into account the wells re-filling equation to provide a more accurate planning in the long term. Besides the mathematical formulation of both problems, an exact algorithm and a taboo search were developed for the solution of the first problem and a theoretical limit and a ProtoGene transgenetic algorithm were developed for the solution of the second problem. The main concepts of the metaheuristics are presented along with the details of their application to the cited problems. The obtained results for both applications are promising when compared to theoretical limits and alternate solutions, either relative to the quality of the solutions or to associated running time

Simulação de Fluxo no Meio Poroso Utilizando o Fluent

The complexity of the Phenomenon of fluid flow in porous way causes a difficulty in its explicit description. Different in the cases where the flow is given through a pipe, where it is possible to measure the length and diameter of the pipe and to determine their ability to flow as a function of pressure, which is a complicated task in porous way. However, we try to approach clearly the equations used to conjecture the behavior of fluid flow in porous way. We made use of the Gambit to create a fractal geometry with the fluent we give the contour´s conditions we would want to analyze the data. The triangular mesh was created; it makes interactions with the discs of different rays, as barriers putted in the geometry. This work presents the results of a simulation with a flow of viscous fluids (oilliquid). The oil flows in a porous way constructed in 2D. The behavior evaluation of the fluid flow inside the porous way was realized with graphics, images and numerical results used for different datas analysis. The study was aimed in relation at the behavior of permeability (k) for different fractal dimensions. Taking into account the preservation of porosity and increasing the fractal distribution of the discs. The results showed that k decreases when we increase the numbers of discs, although the porosity is the same for all generations of the first simulation, in other words, the permeability decreases when we increase the fractality. Well, there are strong turbulence in the flow each time we increase the number of discs and this hinders the passage of the same to the exit. These results permitted to put in evidence how the permeability (k) is affected in a porous way with obstacles distributed in a diversified form. We also note that k decreases when we increase the pressure variation (P) within geometry. So, in front of the results and the absence of bibliographic subsidies about other theories, the work realized here can possibly by considered the unpublished form to explain and reflect on how the permeability is changed when increasing the fractal dimension in a porous way

Dois testes de imageamento com GPR em problemas de controle ambiental em regiões tropicais: migração de dunas e localização de dutos de óleo enterrados

Because the penetration depth of Ground Penetrating Radar (GPR) signals is very limited in high conductive soils, the usefullness of this method in tropical regions is not yet completly known. The main objective of this researh is to test the usefullness of the method in Brazil. Two typical problems where GPR has been used in Europe and North American were choosed for this test: the first one is to characterize the internal structures of a sand body and the second problem is the localization of old buried pipes lines. The first test was done near the city of São Bento do Norte, in the northern coast of Rio Grande do Norte state, NE Brazil. In this region, there is a sand dune that is migrating very fast in the direction of adjacent settling areas. To characterize the internal structure of the dune and its relationship to the prevailing wind direction, as a preliminary step to understand the dune migration, GPR profiles using the 400 MHz frequency were performed in E-W, N-S, NE-SW, and SE-NW directions over the sand dune intersecting at the top of the dune. The practical resolution of the GPR data is around 30 cm; this was sufficient to distinguish individual foresets inside the dune. After applying the elevation correction to the data, we identified that dips of bedding structures are smallest for the N-S profile, which is perpendicular to the dominant wind direction, largest for the E-W profile, and intermediate for the SW-NE and SE-NW profiles. Foresets in the E-W profile dip with angles varying from 2 to 6 degrees. In the E-W profile, the water table and a horizontal truncation interface separating two generations of dunes were identified, as well as an abrupt directional change in the foreset patterns associated to a lateral contact between two dune generations, the older one extending to the west. The used high frequency of 400 Mhz does not allow a penetration deep enough to map completely these internal contacts. The second test was done near Estreito, a small town near Carnaúbais city, also in Rio Grande do Norte state. In this locality, there are several old pipe lines buried in area covered by plantations where digging should be minimized. Several GPR profiles using the 400 and 200 MHz frequency were performed trying to intercept perpendicularly the possible pipe lines. Because of the high conductivity of the soil, the raw original data can hardly be use to identify the pipe lines. However, after an adequate processing over the 200 MHz profiles, six pipe lines were identified. As a global result of the tests, GPR can be very usefull if the conductivity of the ground is low or, in the case of medium conductivities of the soils, if adequate processing is performed

Transition to turbulence in the Reynolds' experiment

In this study we simulate numerically the Reynolds' experiment for the transition from laminar to turbulent flow in a pipe. We present a discussion of the results from a dynamical systems perspective when a control parameter, the Reynolds number, is increased. The Landau scenario, where the transition is described by the excitation of infinite oscillatory modes within the fluid, is not observed. Instead what happens is best explained by the Ruelle-Takens scenario in terms of strange attractors. The Lyapunov exponent and fractal dimension for the attractor are calculated together with a measure of complex behaviour called the Lempel-Ziv complexity. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Caracterização química e mineralógica da incrustação em rede de ferro fundido e potencial de recuperação da capacidade hidráulica

The purpose of this work was to characterize chemical and mineralogical the water supply networks and to assess the hydraulic recovery on high-degraded pipe. Thus, the resistance (by pitometric essays), chemical analyses (ICP-MS and ICP-ES), mineralogical analysis (petrographic thin sections, X-ray difractometry and scanning electronic microscopy), hardness (Mohs scale) and simulations for pipe's change and rehabilitations scenarios were investigated (from Scenario 1 to 4). The results showed that the high-degraded pipe had a limited recovery (from 3,9 to 14,0 m(0,367).s(-1)). The deposits were formed by oxide and hydroxide of iron (magnetite and goethite), which are materials of high hardness (6 on Mohs scale). The simulations indicated the required power ratio (C-i/C-1) around 86.00, 1.00 and 0.02% in relation to present scenario.

Teor de fósforo e pH no bulbo molhado, com diferentes freqüências de fertirrigação, utilizando ácido fosfórico

A aplicação de fertilizantes fosfatados, tais como superfosfofato simples, superfosfofato triplo e monofosfato de amônio, via gotejamento, pode apresentar incrustações nas canalizações e obstruções de emissores. No presente trabalho, realizado na UNESP/Jaboticabal - SP, estudaram-se a distribuição do fósforo e a sua influência sobre o pH e a umidade em Latossolo Vermelho, fertirrigado durante um mês, com cinco aplicações semanais de ácido fosfórico. Utilizaram-se quatro repetições e oito tratamentos, constituídos da combinação de doses de P2O5 (0 e 50 kg ha-1) e freqüências de aplicação de 1; 3; 5 e 7 dias. Pelos resultados obtidos, observou-se que a freqüência de irrigação ou de fertirrigação não influenciou na distribuição final da umidade no bulbo molhado; aplicando-se o ácido fosfórico, o pH do solo até 30 cm do gotejador e até 40 cm em profundidade foi reduzido, atingindo valor de 3,6, e o teor de fósforo foi maior nessa mesma porção do bulbo, ultrapassando 1.500 mg dm-3. Isso permite indicar que o ácido fosfórico pode ser utilizado em irrigação localizada, com controle do pH do solo, pois sua redução influencia no desenvolvimento das culturas e, conseqüentemente, na produtividade.