Homogalactanas sulfatadas da alga Codium isthmocladum com atividade anticoagulante

Since the first description of sulfated polysaccharides from seaweeds, the biological activities of these compounds have been evaluated under different aspects and experimental procedures. Among the broad biological activities presented by seaweed polysaccharides, anticoagulant action appears as a promising function. In this present study we have obtained sulfated polysaccharides from the green seaweed Codium isthmocladium by proteolytic digestion, followed by separation into five fractions (0.3, 0.5, 0.7, 0.9 and 1.2) by sequential acetone precipitation. The chemical analyses have demonstrated that all fractions are composed mainly by sulfated polysaccharides. The anticoagulant activity of these fractions was determined by activated partial thromboplastin time (aPTT) and prothrombin time test (PT) using citrate normal human plasma. None fraction has shown anticoagulant activity by PT test. Furthermore, all of them have shown anticoagulant activity by aPTT test. These results indicated that the molecular targets of these sulfated polysaccharides are mainly in the intrinsic via of the coagulation cascade. Agarose gel electrophoresis in 1,3-diaminopropane acetate buffer, pH 9.0, stained with 0.1% toluidine blue showed the presence of two or three bands in several fractions while the fraction 0.9 showed a single spot. By anion exchange chromatography, the acid polysaccharides from the 0.9 acetone fraction were separated into two new fractions eluted respectively with 2.0 and 3.0 M NaCl. These compounds showed a molecular weight of 6.4 and 7.4 kDa respectively. Chemical analyses and infrared spectroscopy showed that Gal 1 and Gal 2 are sulfated homogalactans and differ one from the other in degree and localization of sulfate groups. aPPT test demonstrated that fractions 2,0 and 3,0M (Gal1 and Gal 2, respectively) have anticoagulant activity. This is the first time that anticoagulant sulfated homogalatans have been isolated from green algae. To prolong the coagulation time to double the baseline value in the aPTT, the required amount of sulfated galactan 1 (6,3mg) was similar to low molecular heparin Clexane®, whereas only 0,7mg of sulfated galactan 2 was needed to obtain the same effect. Sulfated galactan 2 in high doses (250mg) induces platelet aggregation. These results suggest that these galactans from C. isthmocladum have a potential application as an anticoagulant drug

Adição de superplastificante e anti-segregante à base de CMC em pastas de cimento para Poços de Petróleo

Oil well cementing materials consist of slurries of Special class Portland cement dispersed in water. Admixtures can be used to provide the necessary fluidity, so the material can be efficiently pumped down as well as penetrate porous rocks with controlled filter loss. Construction admixtures can be used to modify the properties of oil well cements provided they can withstand and hold their properties at the higher than ambient temperatures usually encountered in oil fields. In civil construction, superplasticizer play the role of dispersants that reduce the facto r of water cement improve mechanical properties and fluidity of the cement, whereas anti-segregation agents improve the workability of the slurry. In the present study, oil well cement slurries were produced adding both a dispersant and an anti-segregation agent conventionally used in Portland CPII-Z-32 RS cement aiming at materials for primary cementing and squeeze operations. Three basic aspects were evaluated: fluidity, filter loss and the synergetic effect of the admixtures at two temperatures, i.e., 27°C and 56°C, following API RP 10B practical recommendations. The slurries were prepared using admixture concentrations varying from 2.60 Kgf/m3 (0.02 gallft3) to 5.82 Kgf/m3 (0.045 galJft3) BWOC. The density of the slurries was set to 1.89 g/cm3 (15.8 Ib/gal). 0.30 to 0.60% BWOC of a CMC-based anti-segregation agent was added to the cement to control the filter loss. The results showed that the addition of anti-segregation at concentrations above 0.55% by weight of cement resulted in the increased viscosity of the folders in temperatures evaluated. The increasing the temperature of the tests led to a reduction in the performance of anti-segregation. At concentrations of 5.20 kgf/m3 (0,040 gallft3) and 5.82 Kgf/m3 (0,045 gal/ft 3) observed a better performance of the properties evaluated in the proposed system. At low temperature was observed instability in the readings of rheology for all concentrations of anti-segregation. Contents that increasing the concentration of anti¬-segregation is limited concentrations greater than 0.55 % BWOC of the CMC in temperature analyzed. The use of the system with CMC promoted a good performance against the properties evaluated. The principal function of anti¬-segregation was optimized with increasing concentration of superplasticizer, at temperatures above the 2rC. The study of the behaviour of systemic additives, resulting in slurries of cement, which can be optimized face studies of other intrinsic properties in oil fields

Desenvolvimento de pastas de cimento flexíveis para poços de petróleo submetidos à injeção de vapor utilizando látex do tipo SBR

Novel cementing materials formulations containing flexible polymeric admixtures have been studied aiming at improving the mechanical behavior of oil well cement slurries submitted to steam injection. However, research activities in this sector are still under development. The steam injected directly into the well causes casing dilation, which after a reduction in temperature, tends to return to its original dimensions, resulting in crack formation and hydraulic isolation loss of the well, which will result in shortening of well life. In this scenario, the objective of the present study was to evaluate the mechanical behavior of Portland-based slurries containing SBR latex, applied in oil well cementing of wells submitted to steam injection. Were formulated slurries with densities of 1.797 g/cm3 (15.0 lb/Gal) and 1.869 g/cm3 (15.6 lb/Gal), containing admixtures with a latex concentration of 0; 66.88; 133.76; 200.64 and 267.52 L/m3 (0, 0.5, 1.0, 1.5 and 2.0 gpc). Tests including rheology, fluid loss control, thickening time, API compressive strength and splitting tensile strength, beyond steam injection simulation. Microstrutural characteristics of the slurries were also performed (XRD, TG, FTIR and SEM). The results showed that increasing the polymer concentration increased in the rheological properties and fluid loss, and a decrease in the elasticity modulus of the cement slurries. The results obtained showed that the slurries can be applied in cementing operations of oil wells submitted to steam injection.

Formulação de grautes leves para a cimentação de poços de petróleo onshore

Grautes are dry mixes with hydraulic characteristics widely used in construction. This material comprises cement, mineral additives and dosed in accordance with the desired properties. The use of grautes in cementing oil wells potentially increases the precision in the composition of the mixture, since it is requires only the addition of the mixing water before its pumping. Such benefit may be availed in cementing wells since the formulations grautes meet the temperature and pressure characteristics typical of wells. The objective of this study is to evaluate the effect of adding different percentages of industrial minerals properties of light grautes for onshore oil wells. For the formulation of the employees were grautes light industrial minerals and waste minerals abundant in the Northeast, in addiction to Portland cement and chemical additives Special class. Grautes were formulated with densities between 1.55 g/cm3 (13.0 lb/gal) and 1.68 g/cm3 (14 lb/gal). Tests results showed that grautes with higher density in the range studied meet the specifications for cementation of shallow wells onshore. The compositions lighter can also be adjusted for applying the material in the cementation of oil wells

Utilização de nanosílica como aditivo estendedor para pastas cimentantes de baixa densidade destinadas à cimentação de poços petrolíferos

Cementing operations are conducted at different times of the well s life and they have high importance, because the functions are fundamental to keep good properties during a long life of the well, such as, maintain the mechanical stability of the well, to promote the isolation hydraulic and support the tubing. In some situations, the rocky zones have low fractures pressures and require the use of lightweight slurries to prevent the hydrostatic pressure in the formation is greater than the pressure of fracture. There are three ways to reduce the density of cement slurries: exterders water additives, microspheres and foamed slurries. The most used extender water additive is sodium bentonite, which is a clay with a good capacity of water absorption and expansion of its volume, the main disadvantage of this additive is the reduction of the strength. Currently, the use of nanoscale particles has received special attention, mainly because they get new functionalities. Following this trend, this paper aims to use a colloidal solution of nano-silica as an exterders water additives for use in oil wells. Slurries were designed with fixed 13lb/gal density and concentration of nano silica 0.1 gpc; 0.4 gpc; 0.7 and 1gpc, the influence of nano-silica was studied at these levels in isolation and combined varying concentrations of CaCl2,. Tests including rheology, stability, strength, thickening time, porosity and permeability. Besides the API tests, microstructural characterizations were performed after 28 days of the slurries, X-ray diffraction (XRD) and scanning electron microscopy (SEM)

influência da adição de diferentes sais em pastas de cimento portland para cimentação de poços de petróleo

One of the great challenges at present time related with the materials area concerns of products and processes for use in petroleum industry, more precisely related to the Pre-salt area. Progresses were reached in the last years allowing the drilling of the salt layer, with the time reduction for drilling and larger success at the end. For the oil wells companies the preponderant factor is the technology, however, in spite of the progress, a series of challenges is still susceptible to solutions and one of them refers to the slurries preparation for cementing in those areas. Inside of this context, this study had for objective to analyze the influence of the salts NaCl, KCl, CaSO4 and MgSO4 in strength and chemical structure of the hydrated products. As methodology, they were prepared and analyzed cement slurries with varied concentrations of these salts that are commonly found in the saline formations. The salts concentrations used in formulations of the slurries were of 5%, 15% and 30%. The slurries were formulated with specific weight of 15,8 lb / gal and the cement used was Class G. Strength tests were accomplished in samples cured by 24 hours and 28 days. Also were realized crystallographic characterization (XRD) and morphologic (SEM). In agreement with the presented results, it is observed that the largest resistance values are attributed to the slurries with concentration of 15%. There was reduction of the strength values of the slurries formulated with concentration of 30%. Through the characterization microstructural it was possible to note the salts influence in the main cement hydrated products

Efeito da incorporação de diatomita na estabilidade e permeabilidade de compósitos cimentíceos espumados aplicados a poços de petróleo

Lightweight oilwell cement slurries have been recently studied as a mean to improve zonal isolation and sheath-porous formation adherence. Foamed slurries consisting of Portland cement and air-entraining admixtures have become an interesting option for this application. The loss in hydrostatic pressure as a consequence of cement hydration results in the expansion of the air bubbles entrapped in the cement matrix, thus improving the sheath-porous formation contact. Consequently, slurries are able to better retain their water to complete the hydration process. The main objective of the present study was to evaluate the effect of the addition of an air-entraining admixture on the density, stability and permeability of composite slurries containing Portland cement and diatomite as light mineral load. Successful formulations are potential cementing materials for low fracture gradient oilwells. The experimental procedures used for slurry preparation and characterization were based on the American Petroleum Institute and ABNT guidelines Slurries containing a pre-established concentration of the air-entraining admixture and different contents of diatomite were prepared aiming at final densities of 13 to 15 lb/gal. The results revealed that the reduction of 15 to 25% of the density of the slurries did not significantly affect their strength. The addition of both diatomite and the air-entraining admixture increased the viscosity of the slurry providing better air-bubble retention in the volume of the slurry. Stable slurries depicted bottom to top density variation of less than 1.0 lb/gal and length reduction of the stability sample of 5.86 mm. Finally, permeability coefficient values between 0.617 and 0.406 mD were obtained. Therefore, lightweight oilwell cement slurries depicting a satisfactory set of physicochemical and mechanical properties can be formulated using a combination of diatomite and air-entraining admixtures for low fracture gradient oilwells

Desenvolvimento de um sistema misto de pasta à base de geopolímero e cimento portland para correção de perda de circulação

The materials engineering includes processes and products involving several areas of engineering, allowing them to prepare materials that fulfill the needs of various new products. In this case, this work aims to study a system composed of cement paste and geopolymers, which can contribute to solving an engineering problem that directly involves the exploitation of oil wells subject to loss of circulation. To correct it, has been already proposed the use of granular materials, fibers, reducing the drilling fluid or cement paste density and even surface and downhole mixed systems. In this work, we proposed the development of a slurry mixed system, the first was a cement-based slurry and the second a geopolymer-based slurry. The cement-based slurry was formulated with low density and extenders, 12.0 ppg (1.438 g/cm ³), showing great thixotropic characteristics. It was added nano silica at concentrations of 0.5, 1.0 and 1.5 gps (66.88, 133.76 and 200.64 L/m3) and CaCl2 at concentrations of 0.5, 1, 0 and 1.5%. The second system is a geopolymer-based paste formulated from molar ratios of 3.5 (nSiO2/nAl2O3), 0.27 (nK2O/nSiO2), 1.07 (nK2O/nAl2O3) and 13.99 (nH2O/nK2O). Finally, we performed a mixture of these two systems, for their application for correction of circulation lost. To characterize the raw materials, XRD, XRF, FTIR analysis and titration were performed. The both systems were characterized in tests based on API RP10B. Compressive strength tests were conducted after curing for 24 hours, 7 and 28 days at 58 °C on the cement-based system and the geopolymer-based system. From the mixtures have been performed mixability tests and micro structural characterizations (XRD, SEM and TG). The results showed that the nano silica, when combined with CaCl2 modified the rheological properties of the cement slurry and from the concentration of 1.5 gpc (200.64 L / m³) it was possible to obtain stable systems. The system mixture caused a change in the microstructure of the material by favoring the rate of geopolymer formation to hinder the C3S phase hydration, thus, the production of CSH phases and Portlandite were harmed. Through the mixability tests it can be concluded that the system, due to reduced setting time of the mixture, can be applied to plug lost circulation zones when mixed downhole

Estudo do comportamento de pastas compósitas cimento/sílica/poliuretana para poços de petróleo HPHT

Os poços HPHT atravessam zonas anormalmente pressurizadas e com altos gradientes de temperatura. Esses poços apresentam elevadas concentrações de tensões produzidas pelas operações de perfuração e fraturamento hidráulico, flutuações da pressão e temperatura, forças dinâmicas geradas durante a perfuração, formações inconsolidadas, entre outros aspectos, podendo resultar em falhas mecânicas na bainha de cimento. Tais falhas comprometem a estabilidade mecânica do poço e o isolamento das zonas produtoras de óleos e/ou gás. Para que operações corretivas não se façam necessárias, é preciso adequar as pastas às condições de cada poço. Sistemas de pastas de cimento para poços HPHT requerem um bom controle de suas propriedades termo-mecânicas. Visto que a temperaturas superiores a 110 oC (230 oF) o cimento, após alcançar um valor máximo de resistência, inicia um processo de perda de resistência (retrogressão). Para prevenir esse efeito substitui-se parcialmente o cimento Portland por sílica com objetivo de incrementar a reação pozolânica. Esta reação modifica a trajetória do processo natural de hidratação do cimento, o gel de silicato de cálcio hidratado (C-S-H) se converte em várias outras fases com maior resistência. Polímeros também são adicionados para proporcionar maior flexibilidade e agir como barreira à propagação de trincas desenvolvidas sob tensão. O presente trabalho teve como objetivo estudar o comportamento do sistema cimento/sílica/polímero quando submetido às condições de alta temperatura e alta pressão. Foram formuladas pastas de cimento puro, pastas contendo 40 % BWOC de sílica flour e pastas com diferentes concentrações de poliuretana (5 % a 25 %) e 40 % BWOC de sílica flour. O peso específico das pastas foi fixado em 1,87 g/cm3 (15,6 lb/gal). Os resultados demonstram que as resistências da pasta contendo 40% de sílica e das com adição de polímero foram muito superiores a da pasta de cimento puro, não ocorrendo o efeito da retrogressão. As pastas com polímero apresentaram um crescente aumento da tenacidade com o aumento da concentração da mesma, sendo assim capaz de suportar as tensões. Além de se manterem estáveis termicamente acima de 180 ºC. O sistema também apresentou excelentes resultados de filtrado, reologia, água livre, estabilidade e permeabilidade. Sendo assim, o mesmo mostrou ser aplicável a poços HPHT

Formulação e caracterização de pastas espumadas por incorporação de ar e estabilizantes minerais

Cementing operations may occur at various stages of the life cycle of an oil well since its construction until its definitive abandonment. There are some situations in which the interest zones are depleted or have low fracture pressure. In such cases, the adoption of lowdensity cement slurries is an efficient solution. To this end, there are basically three ways to reduce the density of cement slurries: using microspheres, water extending additives or foamed cement. The objective of this study is to formulate, to study and to characterize lowdensity foamed cement, using an air entrainment surfactant with vermiculite or diatomite as water extenders and stabilizers. The methodology consists on preparation and evaluation of the slurries under the American Petroleum Institute (API) and the Brazilian Association of Technical Standards (ABNT) guidelines. Based on calculated densities between 13 and 15 ppg (1.559 and 1.799 g/cm3), the slurries were prepared with fixed surfactant concentration, varying the concentrations of vermiculite and diatomite and were compared with the base slurries. The results of plastic viscosity, yield point and gel strength and the compressive strength for 24 h showed that the slurries presented suitable rheology and mechanical strength for cementing operations in oil wells, and had their densities reduced between 8.40 and 11.89 ppg (1.007 and 1.426 g/cm3). The conclusion is that is possible, under atmospheric conditions, to obtain light weighted foamed cement slurries with satisfactory rheological and mechanical properties by means of air entrainment and mineral additions with extenders and stabilizers effects. The slurries have great potential for cementing operations; applicability in deep wells, in low fracture gradient formations and in depleted zones and bring cost savings by reducing the cementing consumption

Desenvolvimento de pastas leves utilizando incorporadores de ar para aplicação em poços de petróleo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Estudo da formulação de pré-misturas secas para a cimentação de poços em terra

An economical solution for cementing oil wells is the use of pre-prepared dry mixtures containing cement and additives. The mixtures may be formulated, prepared and transported to the well where is added water to be pumped.Using this method, becomes dispensable to prepare the cement mixes containing additives in the cementing operation, reducing the possibility of error. In this way, the aim of this work is to study formulations of cement slurries containing solid additives for primary cementing of oil wells onshore for typical depths of 400, 800 and 1,200 meters. The formulations are comprised of Special Class Portland cement, mineral additions and solids chemical additives.The formulated mixtures have density of 1.67 g / cm ³ (14.0 lb / gal). Their optimization were made through the analysis of the rheological parameters, fluid loss results, free water, thickening time, stability test and mechanical properties.The results showed that mixtures are in conformity the specifications for cementing oil wells onshore studied depths

Efeito da adição de microfibras de lã de vidro na tenacidade à ruptura de pastas de cimento para poços de petróleo

Although there are a wide variety of additives that act in fresh state, to adjust the properties of cement, there is also a search by additions that improve the tenacity of the cement in the hardened state. This, in turn, can often be increased by inserting fibers, which act on the deflection of microcracks. This study aimed to use a microfiber glass wool (silica-based) as an additive reinforcing the cement matrix, improving the rupture tenacity, in order to prevent the propagation of microcracks in the cement sheath commonly found in oil wells submitted to high temperatures. The fibers were added at different concentrations, 2 to 5% (BWOC) and varied average sizes, grinding for 90 s, 180 s, 300 s, 600 s. The cement slurries were made with a density of 1,90 g/ cm3 (15,6 lb/gal), using Portland cement CPP- Special Class as the hydraulic binder and 40% silica flour. The characterization of the fiber was made by scanning electron microscopy (SEM), particle size by sieving, X-ray fluorescence (XRF), X-ray diffraction (XRD) and thermogravimetry (TG / DTG). Were performed technological tests set by the API (American Petroleum Institute) by rheology, stability, free water, compressive strength, as well as testing rupture energy, elastic modulus and permeability. The characterization results showed good thermal stability of the microfiber glass wool for application in oil wells submitted to steam injection and, also, that from the particle size data, it was possible to suggest that microfibers milled up to 300 s, are ideal to act as reinforcement to the cement slurries. The rheological parameters, there was committal of plastic viscosity when larger lengths were inserted of microfiber (F90). The values obtained by free water and stability were presented according to API. The mechanical properties, the incorporation of microfiber to the cement slurries gave better rupture tenacity, as compared to reference cement slurries. The values of compressive strength, elastic modulus and permeability have been maintained with respect to the reference cement slurries. Thus, cement slurries reinforced with microfiber glass wool can ensure good application for cementing oil wells submitted to steam injection, which requires control of microcracks, due to the thermal gradients

Efeito da adição de cargas minerais leves na resistência mecânica de grautes para cimentação de poços offshore

The preparation of cement slurries for offshore well cementing involves mixing all solid components to be added to the mixing water on the platform. The aim of this work was to study the formulation of pre-prepared dry mixtures, or grouts, for offshore oilwell cementing. The addition of mineral fillers in the strength of lightweight grouts applied for depths down to 400 m under water depths of 500 m was investigated. Lightweight materials and fine aggregates were selected. For the choice of starting materials, a study of the pozzolanic activity of low-cost fillers such as porcelain tile residue, microsilica and diatomaceous earth was carried out by X-ray diffraction and mechanical strength tests. Hardened grouts containing porcelain tile residue and microsilica depicted high strength at early ages. Based on such preliminary investigation, a study of the mechanical strength of grouts with density 1.74 g/cm3 (14.5 lb/gal) cured initially at 27 °C was performed using cement, microsilica, porcelain tile residue and an anti-foaming agent. The results showed that the mixture containing 7% of porcelain tile residue and 7% of microsilica was the one with the highest compressive strength after curing for 24 hours. This composition was chosen to be studied and adapted for offshore conditions based on testes performed at 4 °C. The grout containing cement, 7% of porcelain tile residue, 7% of active silica and admixtures (CaCl2), anti-foaming and dispersant resulted satisfactory rheology and mechanical strength after curing for 24 hours of curing

Mutagênese induzida por flavonóides presentes do decocto das cascas da aroeira (Schinus terebinthifolius, Raddi)

The decoction of Brazilian pepper tree barks (Schinus terebinthifolius, Raddi), is used in medicine as wound healing and antiinflamatory. Once extracts from this plant are used for acceleration of scar s process, it is important to study their mutagenic and genotoxic potential. In previous works in our laboratory, it was observed mutagenicity caused by the decoction when in high concentrations. Among the chemical compounds of this plant that could be able to induce mutation, the flavonoids were the only group that was referred to have either an oxidant or antioxidant potential. The flavonoids were isolated, purified and quantified by adsorptive column chromatography under silica gel, bacterial and in vitro genotoxic tests were realized to determine if the flavonoids were the responsible agents for this mutagenicity found. The tests realized with plasmidial DNA were indicative that the flavonoids are probably genotoxic, due to the presence of correlation between increase of the flavonoid concentration and in plasmidial DNA double strand breakage visualized in agarose gel, as well as they were capable to generated abasic sites shown by the in vitro treatment with exonuclease III. The same tests with plasmidial DNA in the presence of copper [10 µM] and of a Tris-HCl pH 7.5 [10 µM] buffer were realized with the isolated flavonoids to determine if there would be or not participation of reactive oxygen species (ROS). The transformation of plasmidial DNA in different bacterial strains proficient and deficient in DNA repair enzymes in the presence or not of a Tris-HCl buffer, suggests that the enzymes that repair oxidative lesions are necessary to repair the lesions generated by the flavonoids and that ROS are generated and are necessary to promote the lesions. Bacterial tests with Escherichia coli strains of the CC collection (deficient or not for DNA repair enzymes), showed that the flavonoids are able to increase the frequency of mutations, mainly in strains mutated in repair enzymes (MutM, MutY-glicosylases and double mutant), suggesting that these agents are responsible for the enhancement in the mutation rate. In order to determine the mutation spectrum caused by the flavonoids of the Brazilian pepper tree stem bark, plasmidial DNA previously treated with the flavonoids were transformed in bacterial strains deficient and proficient in the DNA repair enzymes, followed by a blue-white selection with X-gal, DNA amplification by PCR and sequencing the positive mutant clones. Analysis of the mutants obtained from strains CC104, CC104mutM, CC104mutY, CC104mutMmutY, BW9101, BW9109 indicated a predominance of some mutations like G:C to C:G that can be correlated with the origin of 8-oxoG, due to oxidative lesions caused by the flavonoids. So it can concluded that the flavonoid isolated or in fractions enriched on them are genotoxic and mutagenic, and their mutations are predominantly oxidative, mediated by ROS, and the lesions are recognized by the BER system. In this way it is proposed that the flavonoids can act in two different ways to generate the DNA lesion: 1. in a Fenton-like reaction, when the flavonoid are in the presence of metal ions and that together with the water generate ROS that promotes the DNA lesions; 2. in another way the lesions can be generated by the formation of ROS due to the internal chemical structure of the flavonoid molecule due to the quantity and location of hydroxyl groups, and so producing the DNA lesions, those lesions can be directly (suggested by the in vitro experiments) or indirectly done (supported by the experiments using the CC bacterial strains)