Compósitos Portland-biopolímeros para cimentação de poços de petróleo

The oil production in mature areas can be improved by advanced recovery techniques. In special, steam injection reduces the viscosity of heavy oils, thus improving its flow to surrounding wells. On the other hand, the usually high temperatures and pressures involved in the process may lead to cement cracking, negatively affecting both the mechanical stability and zonal isolation provided by the cement sheath of the well. The addition of plastic materials to the cement is an alternative to prevent this scenario. Composite slurries consisting of Portland cement and a natural biopolymer were studied. Samples containing different contents of biopolymer dispersed in a Portland cement matrix were prepared and evaluated by mechanical and rheological tests in order to assess their behavior according to API (American Petroleum Institute) guidelines. FEM was also applied to map the stress distribution encountered by the cement at bottom bole. The slurries were prepared according to a factorial experiment plan by varying three parameters, i.e., cement age, contents of biopolymer and water-to-cement ratio. The results revealed that the addition of the biopolymer reduced the volume of free water and the setting time of the slurry. In addition, tensile strength, compressive strength and toughness improved by 30% comparing hardened composites to plain Portland slurries. FEM results suggested that the stresses developed at bottomhole may be 10 to 100 times higher than the strength of the cement as evaluated in the lab by unconfined mechanical testing. An alternative approach is proposed to adapt the testing methodology used to evaluate the mechanical behavior of oilwell cement slurries by simulating the confined conditions encountered at bottornhole

Avaliação do comportamento reológico de pastas de cimento para poços de petróleo com adição de plastificantes

The isolation of adjacent zones encountered during oilwell drilling is carried out by Portland-based cement slurries. The slurries are pumped into the annular positions between the well and the casing. Their rheological behavior is a very important component for the cementing process. Nowadays, several alternative materials are used in oilwell cementing, with goal the modification and the improvement of their properties, mainly the increase of the fluidity. And this can be reached by using plasticizers additives able to account for different oilwell conditions, yielding compatible cement slurries and allowing enough time for the complete cementing operation. If the rheological properties of the slurry are properly characterized, the load loss and flow regime can be correctly predicted. However, this experimental characterization is difficult. Rheological models capable of describing the cement slurry behavior must be capable of predicting the slurry cement deformation within reasonable accuracy. The aim of this study was to characterize rheologically the slurries prepared with a especial class of Portland cement, water and plasticizers based on lignosulfonate, melamine and polycarboxylate at temperatures varying from 27°C to 72°C. The tests were carried out according to the practical recommendations of the API RP 10B guidelines. The results revealed a great efficiency and the dispersive power of the polycarboxylate, for all temperatures tested. This additive promoted high fluidity of the slurries, with no sedimentation. High lignosulfonate and melamine concentrations did not reduce the rheological parameters (plastic viscosity and yield stress) of the slurries. It was verified that these additives were not compatible with the type of cement used. The evaluated rheological models were capable of describing the behavior of the slurries only within concentration and temperature ranges specific for each type of additive

Desenvolvimento de argamassa para restauração utilizando resíduo do polimento do porcelanato

The coatings mortars are essential elements of building structures because they execute an important role in protecting walls and are particularly exposed to aggressive action responsible for its degradation over time. The importance of wall coverings has been the subject of discussion and analysis in the conservation and rehabilitation of old buildings. Are sometimes removed and replaced with inappropriate solutions of constructive point of view or architecture. The most commonly used coatings on walls of old buildings is based on traditional hydraulic lime mortars. The present study aims at the formulation of new lime- based mortars and aerial fine aggregate, in order to contribute to a better field of conservation and restoration mortar coating of old buildings. Residue was used for polishing porcelain as fine aggregate, replacing the aggregate (sand), in percentages 05-30% by mass. We conducted a thorough evaluation of the mortar properties in fresh and hardened state by comparing the performance of the same with a reference mortar. The residue used was characterized as the density, bulk density, and particle size laser, scanning electron microscopy, X-ray diffraction and X-ray fluorescence. Formulations were produced 7, 6 with residue and one commonly used formulation, which served as a reference. In the formulations of lime mortars air (hydrated lime powder CH-I) has been adopted a stroke volume (1:3) with constant binder, was varied and the water / binder and aggregate and waste. For evaluation of mortars fresh, proceeded to consistency analysis, specific gravity, water retention and air content embedded. In the hardened state assays were performed in specific gravity, water retention, modulus of elasticity, tensile strength in bending, compressive strength, water absorption by capillary action, adhesion, tensile strength, resistance to shrinkage and salts by of crystallization trials with resources chloride solution, nitrate and sulfate all sodium in prismatic at 90 days of age, in addition to the micro structural analysis of mortars. Based on the results we can see that the mortar formulated with 10% content of waste and the reference free retraction feature more stable closer to neutrality. The composition of 10% was obtained better performance against the action of the salt crystallization. The mortar with 15% residue obtained better density, lower air content embedded and high capacity for water retention developing good workability. The replacement of 20% of waste generates a satisfactory utilization of resistance to compression, flexion and traction grip the base. And, finally, it can be seen that the mortar with 10, 15 and 20% residual show, in principle, good suitability as coatings, thus enabling a final result consistent with durability, workability and aesthetics developing therefore a material with better performance to repair or replace existing mortars in old buildings

Avaliação da incorporação combinada dos resíduos de cascalho de perfuração de poço de petróleo e de polimento do porcelanato em cerâmica vermelha

Among the industries, those that produce ceramic porcelain for use in construction industry and oil, during the exploration and production period, play an important role in the production of waste. Much research has been carried out both by academia and the productive sector, sometimes reintroducing them in the same production line that generated them, sometimes in areas unrelated to their generation, as in the production of concrete and mortar for the construction, for example, but each one in an isolated way. In this research, the aim is to study the combined incorporation of the waste drill cuttings of oil well and the residue of the polishing of porcelain, generated in the final stage of finishing of this product in a clay matrix, for the production of red pottery, specifically bricks, ceramic blocks and tiles. The clay comes from the municipality of São Gonçalo, RN, the drilling waste is from the Natal basin, in Rio Grande do Norte, and the residue of the polishing proceeds from a ceramic porcelain of the State of Paraíba. For this purpose, we used a mixture of a plastic clay with a non-plastic, in a ratio of 50% each, settling formulations with the addition of these two residues in this clay matrix. In the formulations, both residues were incorporated with a minimum percentage of 2.5% and maximum of 12.5%, varying from 2.5% each, in each formulation, which the sum of the waste be no more than 15%. It should be noted that the residue of the polishing of ceramic porcelain is a IIa class (not inert). The materials were characterized by XRF, XRD, TG, DTA, laser granulometry and the plasticity index. The technological properties of water absorption, apparent porosity, linear shrinkage of burning, flexural tensile strength and bulk density were evaluated after the sintering of the pieces to 850 °C, 950 °C and 1050 °C, with a burning time of 3 hr, 3 hr and 30 minutes, and 3 hr and 50 minutes, respectively, with a heating rate of 10 °C/minute, for all formulations and landing of 30 minutes. To better understand the influence of each residue and temperature on the evaluated properties, we used the factorial planning and its surfaces of response for the interpretation of the results. It was found that the temperature has no statistical significance at a 95% of reliability level in flexural tensile strength and that it decreases the water absorption and the porosity, but increases the shrinkage and the bulk density. The results showed the feasibility of the desired incorporation, but adjusting the temperature to each product and formulation, and that the temperatures of 850 °C and 950 °C were the one that responded to the largest number of formulations

Aditivação de pastas geopoliméricas com tetraborato de sódio e látex não iônico para cimentação de Poços de Petróleo

The development of activities in the oil and gas sector has been promoting the search for materials more adequate to oilwell cementing operation. In the state of Rio Grande do Norte, the cement sheath integrity tend to fail during steam injection operation which is necessary to increase oil recovery in reservoir with heavy oil. Geopolymer is a material that can be used as alternative cement. It has been used in manufacturing of fireproof compounds, construction of structures and for controlling of toxic or radioactive waste. Latex is widely used in Portland cement slurries and its characteristic is the increase of compressive strength of cement slurries. Sodium Tetraborate is used in dental cement as a retarder. The addition of this additive aim to improve the geopolymeric slurries properties for oilwell cementing operation. The slurries studied are constituted of metakaolinite, potassium silicate, potassium hydroxide, non-ionic latex and sodium tetraborate. The properties evaluated were: viscosity, compressive strength, thickening time, density, fluid loss control, at ambient temperature (27 ºC) and at cement specification temperature. The tests were carried out in accordance to the practical recommendations of the norm API RP 10B. The slurries with sodium tetraborate did not change either their rheological properties or their mechanical properties or their density in relation the slurry with no additive. The increase of the concentration of sodium tetraborate increased the water loss at both temperatures studied. The best result obtained with the addition of sodium tetraborate was thickening time, which was tripled. The addition of latex in the slurries studied diminished their rheological properties and their density, however, at ambient temperature, it increased their compressive strength and it functioned as an accelerator. The increase of latex concentration increased the presence of water and then diminished the density of the slurries and increased the water loss. From the results obtained, it was concluded that sodium tetraborate and non-ionic latex are promising additives for geopolymer slurries to be used in oilwell cementing operation

Adição de poliuretana em pastas de cimento para poços de petróleo como agente de correção do filtrado

Chemical admixtures, when properly selected and quantified, play an important role in obtaining adequate slurry systems for quality primary cementing operations. They assure the proper operation of a well and reduce costs attributed to corrective cementing jobs. Controlling the amount lost by filtering through the slurry to permeable areas is one of the most important requirements in an operation, commonly controlled by chemical admixtures, such as carboxymethylcellulose (CMC). However, problems related to temperature, salttolerance and the secundary retarding effect are commonly reported in the literature. According to the scenario described above, the use of an aqueous dispersion of non-ionic poliurethane was proposed to control the filter loss, given its low ionic interaction with the free ions present in the slurries in humid state. Therefore, this study aims at assessing the efficiency of poliurethane to reduce filter loss in different temperature and pressure conditions as well as the synergistic effect with other admixtures. The temperatures and pressures used in laboratory tests simulate the same conditions of oil wells with depths of 500 to 1200 m. The poliurethane showed resistance to thermal degradation and stability in the presence of salts. With the increase in the concentration of the polymer there was a considerable decrease in the volume lost by filtration, and this has been effective even with the increase in temperature

Selective hydrogenation by novel composite supported Pd egg-shell catalysts

Two organic–inorganic mixed phase supports were prepared, comprising an alumina filler and polymers of different chemical nature. Four low loaded Pd catalysts were prepared. Good activities and selectivities were obtained during the hydrogenations of styrene, 1-heptyne and 2,3-butanedione. The catalysts were found to have excellent mechanical properties and could be used in applications needing high attrition resistance and crushing strength. In this sense, processes for fine chemicals using slurry reactors or processes for commodities using long packed beds could advantageously use them.

Incorporação de resíduo cerâmico para prevenção da retrogressão da resistência de cimentos de poços de petróleo submetidos à injeção de vapor

Steam injection is the most used thermal recovery method of oil nowadays because of the high degree of development of the technique that allows high recovery factors. However, injection of superheated steam into the reservoir affects the entire structure of the well, including the cemented layer that presents a retrogression of compressive strength and increases the permeability due to formation of more crystalline and denser phases at temperatures above 110 °C. These changes result in failures in the cement that favor the entrance of formation fluids into the annulus space resulting in unsafe operations and restrictions in the economic life of the well. But the strength retrogression can be prevented by partial replacement of cement by silica-based materials that reduce the CaO/SiO2 ratio of cement slurries changing the trajectory of the reactions, converting those deleterious phases in phases with satisfactory mechanical strength and permeability. The aim of this study was to evaluate the behavior of a ceramic waste material rich in silica in partial and total substitution of a mineral additive used to fight the strength retrogression of cement slurries subjected to high temperatures. The evaluation was made by compression, X-ray diffraction (XRD) and thermogravimetry (TG/DTG). The samples were submitted to a cycle of low temperature (38 °C) for 28 days and a cycle of low temperature followed by exposure to 280 ºC and 1000 psi by 3 days. The results showed that slurries with additions of up to 30% of the waste material are not enough to prevent the strength retrogression, while slurries with additions of the waste material combined with silica flour in various proportions produced hydrated products of low Ca/Si ratios that maintained the compressive strength at satisfactory levels

Desenvolvimento de pastas cimentantes utilizando cimentos portland compostos para cimentação de poços petrolíferos

The Compound Portland cements are commonly used in construction, among them stand out the CPII-Z, CPII-F and CPIV. These types of cement have limited application on oil well cementing, having its compositional characteristics focused specifically to construction, as cement for use in oil wells has greater complexity and properties covering the specific needs for each well to be coated. For operations of oil wells cementing are used Portland cements designed specifically for this purpose. The American Petroleum Institute (API) classifies cements into classes designated by letters A to J. In the petroleum industry, often it is used Class G cement, which is cement that meets all requirements needed for cement from classes A to E. According to the scenario described above, this paper aims to present a credible alternative to apply the compound cements in the oil industry due to the large availability of this cement in relation to oil well cements. The cements were micro structurally characterized by XRF, XRD and SEM tests, both in its anhydrous and hydrated state. Later technological tests were conducted to determine the limits set by the NBR 9831. Among the compound cements studied, the CPII-Z showed satisfactory properties for use in primary and secondary operations of oil wells up to 1200 meters cementing

Influência da adição de cinza do bagaço de cana calcinada em sistemas de pastas para cimentação de poços petrolíferos

Cementing operation is one of the most important stages in the oil well drilling processes and has main function to form hydraulic seal between the various permeable zones traversed by the well. However, several problems may occur with the cement sheath, either during primary cementing or during the well production period. Cements low resistance can cause fissures in the cement sheath and compromise the mechanical integrity of the annular, resulting in contamination of groundwater and producing zones. Several researches show that biomass ash, in particular, those generated by the sugarcane industry have pozzolanic activity and can be added in the composition of the cementing slurries in diverse applications, providing improvements in mechanical properties, revenue and cement durability. Due to the importance of a low cost additive that increases the mechanical properties in a well cementing operations, this study aimed to potentiate the use of sugarcane bagasse ash as pozzolanic material, evaluate the mechanisms of action of this one on cement pastes properties and apply this material in systems slurries aimed to cementing a well with 800 m depth and geothermal gradient of 1.7 °F/100 ft, as much primary cementing operations as squeeze. To do this, the ash beneficiation methods were realized through the processes of grinding, sifting and reburning (calcination) and then characterization by X-ray fluorescence, XRD, TG / DTG, specific surface area, particle size distribution by laser diffraction and mass specific. Moreover, the ash pozzolanic activity added to the cement at concentrations of 0%, 20% and 40% BWOC was evaluated by pozzolanic activity index with lime and with Portland cement. The evaluation of the pozzolanic activity by XRD, TG / DTG and compressive strength confirmed the ash reactivity and indicated that the addition of 20% in the composition of cement slurries produces improvement 34% in the mechanical properties of the slurry cured. Cement slurries properties evaluated by rheological measurements, fluid loss, free fluid, slurry sedimentation, thickening time and sonic strength (UCA) were satisfactory and showed the viability of using the sugarcane ash in cement slurries composition for well cementing

Metodologia para avaliação de cinemática de partículas gasosas em fluidos de viscosidade variável com o tempo e sua aplicação na construção de poços de petróleo

Many challenges have been presented in petroleum industry. One of them is the preventing of fluids influx during drilling and cementing. Gas migration can occur as result of pressure imbalance inside the well when well pressure becomes lower than gas zone pressure and in cementing operation this occurs during cement slurry transition period (solid to fluid). In this work it was developed a methodology to evaluate gas migration during drilling and cementing operations. It was considered gel strength concept and through experimental tests determined gas migration initial time. A mechanistic model was developed to obtain equation that evaluates bubble displacement through the fluid while it gels. Being a time-dependant behavior, dynamic rheological measurements were made to evaluate viscosity along the time. For drilling fluids analyzed it was verified that it is desirable fast and non-progressive gelation in order to reduce gas migration without affect operational window (difference between pore and fracture pressure). For cement slurries analyzed, the most appropriate is that remains fluid for more time below critical gel strength, maintaining hydrostatic pressure above gas zone pressure, and after that gels quickly, reducing gas migration. The model developed simulates previously operational conditions and allow changes in operational and fluids design to obtain a safer condition for well construction

Avaliação da ecotoxicidade de percolados em áreas de disposição de resíduos na região metropolitana de Natal/RN

Leachates are effluent produced by decomposition of solid waste, they have complex composition and can be highly toxic. Therefore such percolated liquid should be collected and treated properly to avoid environmental contamination of soil and of water bodies. The objective of this study was to evaluate the toxicity through ecotoxicological tests with Ceriodaphnia dubia (Cladocera - Crustacea) of percolated liquids generated in two different systems of municipal solid waste (MSW) disposal in the city of Natal/ RN: A Sanitary Landfill in the Metropolitan Region of Natal/ RN, and in a dump off area. Furthermore, it was evaluated the possible contamination of the underground water of the dump off area. Two monthly samples were taken at four points between the months of May/2009 and January/2010. The Point "A" corresponds to the end of the pond leachate treatment in ASRMN; The Point "B" corresponds to a containment pond at the dump. The Point "C" is an area near one of the cells of the dump off area where the leachate outcrops; The Point "D" stands for an underground water well at the area. The last point, called "E" was sampled only once and corresponds to the slurry produced by temporary accumulation of solid waste in the open area of the dump. The ecotoxicological tests, acute and chronic, followed the ABNT 13373/2005 rules, with some modifications. The samples were characterized by measuring the pH number, the dissolved oxygen (DO), the salinity, BOD5, COD, Cd, Cu, Pb, Cr, Fe, Mg, Ni, and Zn. At Point A, the average number of EC50-48h ranged between 1.0% and 2.77% (v/v), showing a high toxicity of the leachate to C.dubia in all months. To this point, positive correlations were found between the EC50- 48 with precipitation. Negative correlations were found between the EC50- 48h with salinity. At point B there was no response of the acute exposure of organisms to the test samples. At point C the EC50-48h ranged from 17.68% to 35.36% in just two months of the five ones analyzed, not correlated meaning. Point D, the EC50-48h level ranged between 12.31% and 71.27%, showed a negative correlation with, only, precipitation. Although it was observed toxicity of underground water in the Landfill Area, there was no evidence of water contamination by leachate, however, due to the toxic character of this water, additional tests should be conducted to confirm the quality of water that is used for human supply. At point E there was no acute toxicity. These results support the dangers of inappropriate disposal of MSW to water bodies due to the high toxicity of the leachate produced highlighting the necessity of places of safe confinement and a treatment system more effective to it

Pré-concentração de cádmio com Saccharomyces cerevisiae e determinação em águas fluviais usando espectrometria de emissão óptica com plasma indutivamente acoplado

A preconcentration method based on the use of Saccharomyces cerevisiae as sorbent material is proposed for the determination of Cd(II) in river water. The solid phase extraction was performed in batch mode and the determination of the analyte in the solid phase was easily carried out by introducing a slurry of the yeast (0.0625 g / 2.5 mL) directly into the ICP OES. A limit of detection of 0.11 µg L-1 and a sample throughput in the range of 4 - 54 sample h-1 were obtained. Determinations of cadmium in a certified sample and in real river water samples were in excellent agreement with the expected values.

Dynamics and diversity of Escherichia coli in animals and system management of the manure on a commercial farrow-to-finish pig farm

The objective of this study was to determine the dynamics and diversity of Escherichia coli populations in animal and environmental lines of a commercial farrow-to-finish pig farm in Spain along a full production cycle (July 2008 to July 2009), with special attention to antimicrobial resistance and the presence of integrons. In the animal line, a total of 256 isolates were collected from pregnant sows (10 samples and 20 isolates), 1-week-old piglets (20 samples and 40 isolates), unweaned piglets (20 samples and 38 isolates), growers (20 samples and 40 isolates), and the finishers' floor pen (6 samples and 118 isolates); from the underfloor pits and farm slurry tank environmental lines, 100 and 119 isolates, respectively, were collected. Our results showed that E. coli populations in the pig fecal microbiota and in the farm environment are highly dynamic and show high levels of diversity. These issues have been proven through DNA-based typing data (repetitive extragenic palindromic PCR [REP-PCR]) and phenotypic typing data (antimicrobial resistance profile comprising 19 antimicrobials). Clustering of the sampling groups based on their REP-PCR typing results showed that the spatial features (the line) had a stronger weight than the temporal features (sampling week) for the clustering of E. coli populations; this weight was less significant when clustering was performed based on resistotypes. Among animals, finishers harbored an E. coli population different from those of the remaining animal populations studied, considering REP-PCR fingerprints and resistotypes. This population, the most important from a public health perspective, demonstrated the lowest levels of antimicrobial resistance and integron presence.

Biomethane production from macroalgae

Irish brown seaweeds have been identified as a potential bio-resource with potentially high specific methane yields. Anaerobic digestion is deemed the most feasible technology due to its commercial viability for handling such wet feedstock. However, the biomethane potential of seaweed is highly dependent on its chemical composition which can vary by species type, cultivation method, and time of harvest. This study aims to investigate and optimize the process for the production of biomethane from Irish brown seaweeds focusing on the key technology bottlenecks including for seaweed characterization, biomethane potential assessment, optimization of long-term anaerobic digestion and suitable pre-treatment technologies to enhance potential gas yields. Laminaria digitata and Ascophyllum nodosum were tested for seasonal variation. From the characterization and batch digestion of L. digitata, August was found to be the optimal month for harvest due to high organic matter content, low level of ash and ultimately highest biomethane yield. The specific methane yield of 53 m3 CH4 t-1 wwt in August was 4.5 times higher than the yield in December (12 m3 CH4 t-1 wwt), with ash content the key factor in seasonal variation. For A. nodosum, the optimal harvest month was October with polyphenol content found to be a more influential factor than ash. The gross energy yields from both species were evaluated in the range of 116-200 GJ ha-1 yr-1. Continuous digestion trials were subsequently designed for S. latissima and L. digitata to optimize the key digestion parameters. Results from mono-digestion and co-digestion with dairy slurry revealed that both seaweeds could be digested at maximum biomethane efficiency to a loading rate of 4 kg VS m-3 d-1. Accumulation of salt in the digesters was a concern for long term digestion and it was reasoned that suitable pretreatment may be required prior to digestion. Various pre-treatments were subsequently tested on L. digitata to enhance the gas yield. It was found that maceration after hot water washing yielded 25% more specific methane and up to 54% salt removal as compared to untreated L. digitata. The experiments undertaken aim to assist in providing a basic guideline for feasible design and operation of seaweed digesters in Ireland.