Aplicação de termogravimetria acoplada à espectrometria de massas para caracterização de petróleo e determinação da curva de evolução de gás sulfídrico

With the new discoveries of oil and gas, the exploration of fields in various geological basins, imports of other oils and the development of alternative fuels, more and more research labs have evaluated and characterized new types of petroleum and derivatives. Therefore the investment in new techniques and equipment in the samples analysis to determine their physical and chemical properties, their composition, possible contaminants, especification of products, among others, have multiplied in last years, so development of techniques for rapid and efficient characterization is extremely important for a better economic recovery of oil. Based on this context, this work has two main objectives. The first one is to characterize the oil by thermogravimetry coupled with mass spectrometry (TG-MS), and correlate these results with from other types of characterizations data previously informed. The second is to use the technique to develop a methodology to obtain the curve of evaluation of hydrogen sulfide gas in oil. Thus, four samples were analyzed by TG-MS, and X-ray fluorescence spectrometry (XRF). TG results can be used to indicate the nature of oil, its tendency in coke formation, temperatures of distillation and cracking, and other features. It was observed in MS evaluations the behavior of oil main compounds with temperature, the points where the volatilized certain fractions and the evaluation gas analysis of sulfide hydrogen that is compared with the evaluation curve obtained by Petrobras with another methodology

Influência de situações não conformes devidas à colocação do betãode base em lajes com aplicação de endurecedores de superfície

Segundo estudos anteriores, por vezes verificam-se problemas de delaminação e fissuração em pavimentos com a aplicação de endurecedores de superfície, principalmente em condições de vento e/ou calor. Estes fenómenos muitas vezes provêm de outros fatores que não só as condições climatéricas, ou seja, os problemas podem começar no betão de base, associados algumas vezes a situações menos corretas na sua elaboração e aplicação. Por este motivo, nesta dissertação ir-se-á analisar qual a influência do betão de base quando se produz um conjunto de não­conformidades em obra, nomeadamente ao nível da colocação do betão de base. A partir dos resultados obtidos foi possível verificar que nem todas as situações de não­conformidade obtiveram maus resultados na ligação endurecedor/betão. /ABSTRATC: According to previous studies, problems with delamination and cracking in pavements with surface hardener have been found, especially in windy conditions and/or heat. But these phenomenons often come from other factors, problems can start at the concrete base, sometimes associated to situations where there is an incorrect design and implementation and for this reason this thesis will analyze the influence of the concrete base when it produces a set of non-conformities in work, particularly in terms of placement of the concrete base. Based on what has been reported by several companies a set of tests has established. From the obtained results it was verified that not all situations of non-compliance showed poor results in the connection of the surface hardener I concrete.

Protective effect of (-)-epigallocatechin gallate on ultraviolet b-induced skin damage in hairless mice

Purpose: To investigate the protective effect of green tea (-)-epigallocatechin gallate (EGCg) on ultraviolet B (UV-B)-induced skin damages in hairless mice in order to develop a natural sunscreen compound for use in skin care products and cosmetics. Methods: EGCg was dissolved in acetone at concentrations of 1.0, 10.0 and 50.0 mg/mL, and topically applied to the skin of hairless mice at doses of 0.2 mL/cm2, with acetone as control. The mice were then irradiatd m2 UV-B for 30 min daily. EGCg treatment and UV-B irradiation were carried out daily for 28 consecutive days. The mice were then sacrificed and their dorsal skin examined by transmission electron microscopy (TEM) on the 28th day. Results: UV-B irradiation induced severe macroscopic skin damage including chapping, cracking and abnormal desquamation in the treated hairless mice. EGCg showed dose-dependent protective effects against UV-B induced damage on the skin. Treatments with 10.0 and 50.0 mg/mL EGCg alleviated UVB-induced skin damage by suppressing both keratinocyte apoptosis and mitochondrial dysfunction, along with inhibiting the production of melanin pigment. Conclusion: Topical application of green tea EGCg shows dose-dependent protective effect against UV-B-induced damage on hairless mouse skin. Thus, the plant compound can potentially be used as an alternative agent for photoprotection against UV-B exposure.

Conversão térmica e termocatalítica à baixa temperatura do óleo de girassol para obtenção de bio-óleo

The use of biofuels remotes to the eighteenth century, when Rudolf Diesel made the first trials using peanut oil as fuel in a compression ignition engine. Based on these trials, there was the need for some chemical change to vegetable oil. Among these chemical transformations, we can mention the cracking and transesterification. This work aims at conducting a study using the thermocatalytic and thermal cracking of sunflower oil, using the Al-MCM-41 catalyst. The material type mesoporous Al-MCM-41 was synthesized and characterized by Hydrothermical methods of X-ray diffraction, scanning electron microscopy, nitrogen adsorption, absorption spectroscopy in the infrared and thermal gravimetric analysis (TG / DTG).The study was conducted on the thermogravimetric behavior of sunflower oil on the mesoporous catalyst cited. Activation energy, conversion, and oil degradation as a function of temperature were estimated based on the integral curves of thermogravimetric analysis and the kinetic method of Vyazovkin. The mesoporous material Al-MCM-41 showed one-dimensional hexagonal formation. The study of the kinetic behavior of sunflower oil with the catalyst showed a lower activation energy against the activation energy of pure sunflower oil. Two liquid fractions of sunflower oil were obtained, both in thermal and thermocatalytic pyrolisis. The first fraction obtained was called bio-oil and the second fraction obtained was called acid fraction. The acid fraction collected, in thermal and thermocatalytic pyrolisis, showed very high level of acidity, which is why it was called acid fraction. The first fraction was collected bio-called because it presented results in the range similar to petroleum diesel

Pirólise térmica e catalítica de resíduos de vácuo gerados no refino de petróleo

In this study, was used a very promising technique called of pyrolysis, which can be used for obtaining products with higher added value. From oils and residues, since the contribution of heavier oils and residues has intensified to the world refining industry, due to the growing demand for fuel, for example, liquid hydrocarbons in the range of gasoline and diesel. The catalytic pyrolysis of vacuum residues was performed with the use of a mesoporous material belonging the M41S family, which was discovered in the early 90s by researchers Mobil Oil Corporation, allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal arrangement of mesopores with pore diameters between 2 and 10 nm and a high specific surface area, making it very promising for use as a catalyst in petroleum refining for catalytic cracking, and their mesopores facilitate the access of large hydrocarbon molecules. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more positive for application in the petrochemical industry. The mesoporous material of the type Al-MCM41 (ratio Si / Al = 50) was synthesized by hydrothermal method starting from the silica gel, NaOH and distilled water added to the gel pseudobohemita synthesis. Driver was used as structural CTMABr. Removal of organic driver (CTMABr) was observed by TG / DTG and FTIR, but this material was characterized by XRD, which was observed the formation of the main peaks characteristic of mesoporous materials. The analysis of adsorption / desorption of nitrogen this material textural parameters were determined. The vacuum residues (VR's) that are products of the bottom of the vacuum distillation tower used in this study are different from oil fields (regions of Ceará and Rio de Janeiro). Previously characterized by various techniques such as FTIR, viscosity, density, SARA, elemental analysis and thermogravimetry, which was performed by thermal and catalytic degradation of vacuum residues. The effect of AlMCM-41 was satisfactory, since promoted a decrease in certain ranges of temperature required in the process of conversion of hydrocarbons, but also promoted a decrease in energy required in the process. Thus enabling lower costs related to energy expenditure from degradation during processing of the waste

Análisis comparativo de los sistemas de refrigeración en la operación de refinado en empresas petroleras caso Petrobras (Brasil)

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Degradacao termica e catalitica da borra oleosa de Petroleo com materiais nanoestruturados al-mcm-41 e AL-SBA-15

Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ° C in the ratios of heating of 5, 10 and 20 ° C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline

Considerations associated with the testing of external pipeline coatings

Reliable testing methodologies for the assessment of protective coatings are critical for ensuring the integrity and durability of pipeline coatings (such as field joint coatings) and the mitigation of pipeline corrosion. Currently the failure of joint coatings is one of the major concerns in corrosion protection of pipelines, although they represent only approximately 5% of the coated area in a pipeline system. This paper presents an overview of major testing methodologies currently used in the pipeline industry for the selection, testing, and life prediction of coatings, in particular field joint coatings. Particular focus is on the discussion of difficulties and limitations in testing methods for assessing pipeline coating cracking, cathodic disbondment and loss of adhesion. It is shown that there are limitations in current methodologies in evaluating the coating flexibility - a key parameter for avoiding coatings cracking during hydrostatic testing, cyclic pressure operation and field bending. Methodologies for assessing the effect of holidays in coatings on the cathodic disbondment of pipeline coating under excessively negative cathodic protection (CP) voltages also require improvement. Furthermore, methods for understanding the effects of coating wet adhesion on pipeline coating, cracking and disbondment also need attention. Some preliminary results for addressing some of these issues are also presented in this paper.

An enhanced method for determining the maximum strain a pipeline coating could tolerate

An enhanced mandrel bend testing method has been proposed for the evaluation of the maximum strain level that could be tolerated by an organic coating, and for the understanding of localised coating deformation and cracking behaviours under nonuniform mechanical strains. The aim is to develop a practical method that is suitable for selecting pipeline coatings in order to ensure that the selected coatings have sufficient flexibility to meet the high strain demand during the construction, hydrostatic testing and operation of high pressure pipelines. Two new mandrel bend testing setups have been designed by employing either centre or end clamps in order to improve the uniformity of strain distributions over coated steel coupons, and by using strain gauges to perform in situ measurements of local strains. A series of tests have been carried out to evaluate the new method for testing the flexibility of selected epoxy based pipeline industry coatings. Preliminary computational simulation has also been carried out for assisting the interpretation of mandrel bending test results.

Free and restrained shrinkage behaviours of OPC and slag concretes with admixed polypropylene fibres

This paper presents the results of an investigation that studied the effects of admixed polypropylene (PP) fibres on the long-term drying shrinkage of hardened concrete. Five concrete mixtures, made with 100% Ordinary Portland Cement (OPC) as the binder and containing different volume fractions of PP fibre (0%, 0.05%, 0.1%, 0.2% and 0.5%) were tested. Also, three concrete mixtures were made with 65 % slag-blended cement binder incorporating 0% and 0.2% volume fraction of PP. The results show higher water loss and higher drying shrinkages in concretes that incorporate PP fibres than concrete without fibre. The results of early age cracking tendency of slag concrete, with and without fibre, under fully restrained and drying conditions, show that that PP fibre concrete had higher cracking tendency than concrete without fibre. Higher cracking tendency of PP fibre concrete was due to higher drying shrinkage and elastic moduli.

Microstructure and hardness characterisation of laser coatings produced with a mixture of AISI 420 stainless steel and Fe-C-Cr-Nb-B-Mo steel alloy powders

Fe-C-Cr-Nb-B-Mo alloy powder and AISI 420 SS powder are deposited using laser cladding to increase the hardness for wear resistant applications. Mixtures from 0 to 100 wt.% were evaluated to understand the effect on the elemental composition, microstructure, phases, and microhardness. The mixture of carbon, boron and niobium in the Fe-C-Cr-Nb-B-Mo alloy powder introduces complex carbides into a Fe-based matrix of AISI 420 SS which increases its hardness. Hardness increased linearly with increasing Fe-C-Cr-Nb-B-Mo alloy, but substantial micro-cracking was observed in the clad layer at additions of 60 wt.% and above; related to a transition from a hypoeutectic alloy containing α-Fe/α' dendrites with an (Fe,Cr)2B and γ-Fe eutectic to primary and continuous carbo-borides M2B (where M represents Fe and Cr) and M23(B,C)6 carbides (where M represents Fe, Cr, Mo) with MC particles (where M represents Nb and Mo). The highest average hardness, for an alloy without micro-cracking, of 952 HV was observed in a 40 wt.% alloy. High stress abrasive scratch testing was conducted on all alloys at various loads (500, 1500, 2500 N). Alloy content was found to have a strong effect on the wear mode and the abrasive wear rate, and the presence of micro-cracks was detrimental to abrasive wear resistance.

Simulation of progressive damage in composites using the enhanced embedded element technique

Analysis of complex composite structures requires a fine contiguous mesh of threedimensional (3D) solid elements. The embedded element technique is a promising technique for predicting stiffness and stress. This paper presents a new method for enhancing the embedded element with continuum damage mechanics methods for predicting the evolution of damage in fiber reinforced composite structures. Comparison of the model prediction with experimental results reveals an excellent correlation between the tensile strength of quasi-isotropic laminate with an open hole. The embedded element technique allows the fiber reinforcement and matrix domains to be meshed independently and failure is evaluated separately in each domain. The enhanced embedded element approach allows the failure modes to be observed, specifically, the evolution of matrix cracking and fiber rupture. Compared to the traditional contiguous mesh finite element method, the present modelling technique demonstrates a clear advantage in predicting the experimentally observed failure modes and accurate characterisation of intralaminar fracture.

Crack damage in polymers and composites: a review

Polymer-based materials are extensively used in various applications such as aircrafts, civilian structures, oil and gas platforms and electronics. They are, however, inherently damage prone and over time, the formation of cracks and microscopic damages influences the thermo-mechanical and electrical properties, which eventually results in the total failure of the materials. This paper provides an overview of the principal causes of cracking in polymer and composites and summarizes the recent progress in the development of non-destructive techniques in crack detection. Furthermore, recent progress in the development of bio-inspired self-healing methods in autonomic repair is discussed.

In situ measurement of pipeline coating integrity and corrosion resistance losses under simulated mechanical strains and cathodic protection

A novel experimental assembly consisting of a specially designed tensile testing rig and a standard electrochemical flat cell has been designed for simulating buried high pressure pipeline environmental conditions in which a coating gets damaged and degrades under mechanical strain, and for studying the influence of mechanically induced damages such as the cracking of a coating on its anti-corrosion property. The experimental assembly is also capable of applying a cathodic protection (CP) potential simultaneously with the mechanical strain and environmental exposure. The influence of applied mechanical strain as well as extended exposure to the corrosive environment, coupled with the application of CP, has been investigated based on changes in electrochemical impedance spectroscopy (EIS). Preliminary results show that the amplitude of the coating impedance decreases with an increase in the applied strain level and the length of environmental exposure. The EIS characteristics and changes are found to correlate well with variations in coating cracking and degradation features observed on post-test samples using both optical microscopy and scanning electron microscopy. These results demonstrate that this new experimental method can be used to simulate and examine coating behaviour under the effects of complex high pressure pipeline mechanical, electrochemical and environmental conditions.

Developing an Enhanced Model for Combined Heat and Air Infiltration Energy Simulation

The need for efficient, sustainable, and planned utilization of resources is ever more critical. In the U.S. alone, buildings consume 34.8 Quadrillion (1015) BTU of energy annually at a cost of $1.4 Trillion. Of this energy 58% is utilized for heating and air conditioning. Several building energy analysis tools have been developed to assess energy demands and lifecycle energy costs in buildings. Such analyses are also essential for an efficient HVAC design that overcomes the pitfalls of an under/over-designed system. DOE-2 is among the most widely known full building energy analysis models. It also constitutes the simulation engine of other prominent software such as eQUEST, EnergyPro, PowerDOE. Therefore, it is essential that DOE-2 energy simulations be characterized by high accuracy. Infiltration is an uncontrolled process through which outside air leaks into a building. Studies have estimated infiltration to account for up to 50% of a building’s energy demand. This, considered alongside the annual cost of buildings energy consumption, reveals the costs of air infiltration. It also stresses the need that prominent building energy simulation engines accurately account for its impact. In this research the relative accuracy of current air infiltration calculation methods is evaluated against an intricate Multiphysics Hygrothermal CFD building envelope analysis. The full-scale CFD analysis is based on a meticulous representation of cracking in building envelopes and on real-life conditions. The research found that even the most advanced current infiltration methods, including in DOE-2, are at up to 96.13% relative error versus CFD analysis. An Enhanced Model for Combined Heat and Air Infiltration Simulation was developed. The model resulted in 91.6% improvement in relative accuracy over current models. It reduces error versus CFD analysis to less than 4.5% while requiring less than 1% of the time required for such a complex hygrothermal analysis. The algorithm used in our model was demonstrated to be easy to integrate into DOE-2 and other engines as a standalone method for evaluating infiltration heat loads. This will vastly increase the accuracy of such simulation engines while maintaining their speed and ease of use characteristics that make them very widely used in building design.