Effects of adding La and Ce to hydrotalcite-type Ni/Mg/Al catalyst precursors on ethanol steam reforming reactions

Catalyst precursors composed of Ni/Mg/Al oxides with added La and Ce were tested in ethanol steam reforming (ESR) reactions. La and Ce were added by anion-exchange. The oxides were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) analysis. The catalyst precursors consist of a mixture of oxides, with the nickel in the form of NiO strongly interacting with the support Mg/Al. The XPS analysis showed a lanthanum-support interaction, but no interaction of Ce species with the support. The reaction data obtained with the active catalysts showed that the addition of Ce and La resulted in better H(2) production at 550 degrees C. The CeNi catalyst provided the higher ethanol conversion, with lower acetaldehyde production, possibly clue to a favoring of water adsorption on the weakly interacting clusters of CeO(2) on the surface. (C) 2010 Elsevier B.V. All rights reserved.

Ni catalysts with Mo promoter for methane steam reforming

NiO/Al(2)O(3) catalyst precursors were prepared by simultaneous precipitation, in a Ni:Al molar ratio of 3:1, promoted with Mo oxide (0.05, 0.5, 1.0 and 2.0 wt%). The solids were characterized by adsorption of N(2), XRD, TPR, Raman spectroscopy and XPS, then activated by H(2) reduction and tested for the catalytic activity in methane steam reforming. The characterization results showed the presence of NiO and Ni(2)AlO(4) in the bulk and Ni(2)AlO(4) and/or Ni(2)O(3) and MoO(4)(-2) at the surface of the samples. In the catalytic tests, high stability was observed with a reaction feed of 4:1 steam/methane. However, at a steam/methane ratio of 2: 1, only the catalyst with 0.05% Mo remained stable throughout the 500 min of the test. The addition of Mo to Ni catalysts may have a synergistic effect, probably as a result of electron transfer from the molybdenum to the nickel, increasing the electron density of the catalytic site and hence the catalytic activity. (C) 2009 Elsevier Ltd. All rights reserved.

Estudos de Durabilidade Frente ao Ataque Ácido de Compósitos Portland-Polímero para Cimentação de Poços de Petróleo

Portland-polymers composites are promising candidates to be used as cementing material in Northeastern oil wells of Brazil containing heavy oils submitted to steam injection. In this way, it is necessary to evaluate its degradation in the commonly acidizind agents. In addition, to identify how aggressive are the different hostile environments it is an important contribution on the decision of the acidic systems to be used in. It was investigated the performance of the Portland-polymer composites using powdered polyurethane, aqueous polyurethane, rubber tire residues and a biopolymer, those were reinforced with polished carbon steel SAE 1045 to make the electrochemical measurements. HCl 15,0 %, HCl 6,0 % + HF 1,5 % (soft mud acid), HCl 12,0 % + HF 3,0 % (regular mud acid) and HAc 10 % + HF 1,5 % were used as degrading environment and electrolytes. The more aggressive acid solution to the plain Portland hardened cement paste was the regular mud acid, that showed loss of weight around 23.0 %, followed by the soft mud acid, the showed 11.0 %, 15.0 % HCl with 7,0 % and, at last the 10.0 % HAc plus HF 1.5 % with just 1.0 %. The powdered polyurethane-composite and the aqueous polyurethane one showed larger durability, with reduction around 87.0 % on the loss of weight in regular mud acid. The acid attack is superficial and it occurs as an action layer, where the degraded layer is responsible for the decrease on the kinetic of the degrading process. This behavior can be seen mainly on the Portland- aqueous polyurethane composite, because the degraded layer is impregnated with chemically modified polymer. The fact of the acid attack does not have influence on the compressive strength or fratography of the samples, in a general way, confirms that theory. The mechanism of the efficiency of the Portland-polymers composites subjected to acid attack is due to decreased porosity and permeability related with the plain Portland paste, minor quantity of Ca+2, element preferentially leached to the acidic solution, wave effect and to substitute part of the degrading bulk for the polymeric one. The electrolyte HAc 10 % + HF 1,5 % was the least aggressive one to the external corrosion of the casing, showing open circuit potentials around +250 mV compared to -130 mV to the simulated pore solution to the first 24 hours immersion. This behavior has been performed for two months at least. Similar corrosion rates were showed between both of the electrolytes, around 0.01 μA.cm-2. Total impedance values, insipient arcs and big polarization resistance capacitive arcs on the Nyquist plots, indicating passivity process, confirm its efficiency. In this way, Portlandpolymers composites are possible solutions to be succeed applied to oilwell cementing concomitant submitted to steam injection and acidizing operation and the HAc 10,0 % + HF 1,5 % is the less aggressive solution to the external corrosion of the casing

Adição de resíduo cerâmico em pastas geopoliméricas para cimentação de poços de petróleo

The development of activities the of oil and gas sector have promoted the search for suitable materials for cementing oil wells. In the state of the Rio Grande do Norte, the integrity of the cement sheath tends to be impaired during steam injection, a procedure necessary to increase oil recovery in reservoirs with low-viscosity oil. The geopolymer is a material that can be used as alternative cement, since it has been used in the production of fire-resistant components, building structures, and for the control of toxic or radioactive residues. Geopolymers result from condensation polymer alkali aluminosilicates and silicates resulting three-dimensional polymeric structures. They are produced in a manner different from that of Portland cement, which is made an activating solution that is mixed with geopolymer precursor. Among the few works studied allowed us to conclude that the pastes prepared with metakaolin as precursor showed better performance of its properties. Several studies show the addition of waste clay as a means of reducing cost and improving end of the folder properties. On this basis, the goal is to study the influence of the addition of ceramic waste in geopolymer paste. To develop the study of rheology tests were carried out, filtered, thickening time, compressive strength, free water, specific gravity and permeability, according to the American Pretoleum Institute (API). The results for all formulations studied show that the folders have high mechanical strength to a light paste; low filtrate volume, absence of free water, very low permeability, slurry, consistent with a light paste, and thickening time low that can be corrected with the use of a retardant handle. For morphological characterization, microstructural, physical, chemical and thermal tests were carried out by XRD, MEV, DTA, TG, FTIR. In the trial of XRD, it was found that geopolymer is an amorphous material, with a peak of crystalline kaolinite. In tests of TG / DTA, revealed the presence of a significant event, which represents the mass loss related to water, and also observed the reduction of weight loss by increasing the concentration of ceramic waste. In the trial of MEV, we found a uniform matrix without the presence of other phases. In the trial of FT-IR, we observed the presence of the band related to water. From all results it was determined that the optimum concentration range of use is between 2.5 and 5% of waste ceramic

Influência das tensões tectônicas na permeabilidade da formação Açu - Bacia Potiguar

The behavior of the fluid flux in oil fields is influenced by different factors and it has a big impact on the recovery of hydrocarbons. There is a need of evaluating and adapting the actual technology to the worldwide reservoirs reality, not only on the exploration (reservoir discovers) but also on the development of those that were already discovered, however not yet produced. The in situ combustion (ISC) is a suitable technique for these recovery of hydrocarbons, although it remains complex to be implemented. The main objective of this research was to study the application of the ISC as an advanced oil recovery technique through a parametric analysis of the process using vertical wells within a semi synthetic reservoir that had the characteristics from the brazilian northwest, in order to determine which of those parameters could influence the process, verifying the technical and economical viability of the method on the oil industry. For that analysis, a commercial reservoir simulation program for thermal processes was used, called steam thermal and advanced processes reservoir simulator (STARS) from the computer modeling group (CMG). This study aims, through the numerical analysis, find results that help improve mainly the interpretation and comprehension of the main problems related to the ISC method, which are not yet dominated. From the results obtained, it was proved that the mediation promoted by the thermal process ISC over the oil recovery is very important, with rates and cumulated production positively influenced by the method application. It was seen that the application of the method improves the oil mobility as a function of the heating when the combustion front forms inside the reservoir. Among all the analyzed parameters, the activation energy presented the bigger influence, it means, the lower the activation energy the bigger the fraction of recovered oil, as a function of the chemical reactions speed rise. It was also verified that the higher the enthalpy of the reaction, the bigger the fraction of recovered oil, due to a bigger amount of released energy inside the system, helping the ISC. The reservoir parameters: porosity and permeability showed to have lower influence on the ISC. Among the operational parameters that were analyzed, the injection rate was the one that showed a stronger influence on the ISC method, because, the higher the value of the injection rate, the higher was the result obtained, mainly due to maintaining the combustion front. In connection with the oxygen concentration, an increase of the percentage of this parameter translates into a higher fraction of recovered oil, because the quantity of fuel, helping the advance and the maintenance of the combustion front for a longer period of time. About the economic analysis, the ISC method showed to be economically feasible when evaluated through the net present value (NPV), considering the injection rates: the higher the injection rate, the higher the financial incomes of the final project

Estudo paramétrico da segregação gravitacional na injeção contínua de vapor

Steam injection is the most used method of additional recovery for the extraction of heavy oil. In this type procedure is common to happen gravitational segregation and this phenomenon can affect the production of oil and therefore, it shoulds be considered in the projects of continuous steam injection. For many years, the gravitational segregation was not adequately considered in the calculation procedures in Reservoir Engineering. The effect of the gravity causes the segregation of fluids inside the porous media according to their densities. The results of simulation arising from reservoirs could provide the ability to deal with the gravity, and it became apparent that the effects of the gravity could significantly affect the performance of the reservoir. It know that the gravitational segregation can happen in almost every case where there is injection of light fluid, specially the steam, and occurs with greater intensity for viscous oil reservoirs. This work discusses the influence of some parameters of the rock-reservoir in segregation as viscosity, permeability, thickness, cover gas, porosity. From a model that shows the phenomenon with greater intensity, optimized some operational parameters as the rate flow rate steam, distance between the wells injector-producer, and interval of completion which contributed to the reduction in gravity override, thus increasing the oil recovery. It was shown a greater technical-economic viability for the model of distance between the wells 100 m. The analysis was performed using the simulator of CMG (Computer Modeling Group-Stars 2007.11, in which was observed by iterating between studied variables in heavy oil reservoirs with similar characteristics to Brazilian Northeast

Estudo paramétrico da injeção de vapor em reservatórios delgados

Exploration of heavy oil reservoirs is increasing every year in worldwide, because the discovery of light oil reservoirs is becoming increasingly rare. This fact has stimulated the research with the purpose of becoming viable, technically and economically, the exploration of such oil reserves. In Brazil, in special in the Northeast region, there is a large amount of heavy oil reservoir, where the recovery by the so called secondary methods Water injection or gas injection is inefficient or even impracticable in some reservoirs with high viscosity oils (heavy oils). In this scenario, steam injection appears as an interesting alternative for recover of these kinds of oil reservoirs. Its main mechanism consists of oil viscosity reduction through steam injection, increasing reservoir temperature. This work presents a parametric simulation study of some operational and reservoir variables that had influence on oil recovery in thin reservoirs typically found in Brazilian Northeast Basins, that use the steam injection as improved oil recovery method. To carry out simulations, it was used the commercial software STARS (Steam, Thermal, and Advanced Processes Reservoir Simulator) from CMG (Computer Modeling Group) version 2007.11. Reservoirs variables studied were horizontal permeability, vertical and horizontal permeability ratio, water zone and pay zone thickness ratio, pay zone thickness and thermal conductivity of the rock. Whereas, operational parameters studied were distance between wells and steam injection rate. Results showed that reservoir variables that had more influence on oil recovery were horizontal permeability and water zone and pay zone thickness ratio. In relation to operational variables, results showed that short distances between wells and low steam injection rates improved oil recovery

Estudo da segregação gravitacional do processo de injeção de vapor em reservátórios heterogêneos

Due to reservoirs complexity and significantly large reserves, heavy oil recovery has become one of the major oil industry challenges. Thus, thermal methods have been widely used as a strategic method to improve heavy oil recovery. These methods improve oil displacement through viscosity reduction, enabling oil production in fields which are not considered commercial by conventional recovery methods. Among the thermal processes, steam flooding is the most used today. One consequence in this process is gravity segregation, given by difference between reservoir and injected fluids density. This phenomenon may be influenced by the presence of reservoir heterogeneities. Since most of the studies are carried out in homogeneous reservoirs, more detailed studies of heterogeneities effects in the reservoirs during steam flooding are necessary, since most oil reservoirs are heterogeneous. This paper presents a study of reservoir heterogeneities and their influence in gravity segregation during steam flooding process. In this study some heterogeneous reservoirs with physical characteristics similar those found in the Brazilian Northeast Basin were analyzed. To carry out the simulations, it was used the commercial simulator STARS by CMG (Computer Modeling Group) - version 2007.11. Heterogeneities were modeled with lower permeability layers. Results showed that the presence of low permeability barriers can improve the oil recovery, and reduce the effects of gravity segregation, depending on the location of heterogeneities. The presence of these barriers have also increased the recovered fraction even with the reduction of injected steam rate

Estudo paramétrico da recuperação de petróleo pesado por aquecimento eletromagnético resistivo

Electrical resistive heating (ERH) is a thermal method used to improve oil recovery. It can increase oil rate and oil recovery due to temperature increase caused by electrical current passage through oil zone. ERH has some advantage compared with well-known thermal methods such as continuous steam flood, presenting low-water production. This method can be applied to reservoirs with different characteristics and initial reservoir conditions. Commercial software was used to test several cases using a semi-synthetic homogeneous reservoir with some characteristics as found in northeast Brazilian basins. It was realized a sensitivity analysis of some reservoir parameters, such as: oil zone, aquifer presence, gas cap presence and oil saturation on oil recovery and energy consumption. Then it was tested several cases studying the electrical variables considered more important in the process, such as: voltage, electrical configurations and electrodes positions. Energy optimization by electrodes voltage levels changes and electrical settings modify the intensity and the electrical current distribution in oil zone and, consequently, their influences in reservoir temperature reached at some regions. Results show which reservoir parameters were significant in order to improve oil recovery and energy requirement in for each reservoir. Most significant parameters on oil recovery and electrical energy delivered were oil thickness, presence of aquifer, presence of gas cap, voltage, electrical configuration and electrodes positions. Factors such as: connate water, water salinity and relative permeability to water at irreducible oil saturation had low influence on oil recovery but had some influence in energy requirements. It was possible to optimize energy consumption and oil recovery by electrical variables. Energy requirements can decrease by changing electrodes voltages during the process. This application can be extended to heavy oil reservoirs of high depth, such as offshore fields, where nowadays it is not applicable any conventional thermal process such as steam flooding

Influência da areia argilosa na recuperação de petróleo por injeção de vapor

Continuous steam injection is one of heavy oil thermal recovery methods used in the Brazilian Northeast because of high occurrence of heavy oil reservoir. In this process, the oil into the reservoir is heated while reduces, substantially, its viscosity and improves the production. This work analyzed how the shaly sand layers influenced in the recovery. The studied models were synthetics, but the used reservoir data can be extrapolated to real situations of Potiguar Basin. The modeling was executed using the STARS - Steam Thermal and Advanced Process Reservoir Simulator - whose version was 2007.10. STARS is a tool of CMG Computer Modeling Group. The study was conducted in two stages, the first we analyzed the influence of reservoir parameters in the thermal process, so some of these were studied, including: horizontal permeability of the reservoir and the layer of shaly sand, ratio of horizontal permeability to vertical permeability, the influence of capillary pressure layer of shaly sand and as the location and dimensions of this heterogeneity can affect the productivity of oil. Among the parameters studied the horizontal permeability of the reservoir showed the most significant influence on the process followed by diversity. In the second stage three models were selected and studied some operational parameters such as injection rate, distance between wells, production time and completion intervals. Among the operating parameters studied the low rate and intermediate distances between wells showed the best recoveries

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

Análise da trajetória de poços horizontais em reservatório de óleo pesado

The application of thermal methods, to increase the recovery of heavy oil in mature fields through drainage with multilateral and horizontal wells, has been thoroughly studied, theorically, experimentally, testing new tools and methods. The continuous injection of steam, through a steam injector well and a horizontal producer well in order to improve horizontal sweep of the fluid reservoir, it is an efficient method. Starting from an heterogeneous model, geologically characterized, modeling geostatistics, set history and identification of the best path of permeability, with seismic 3D, has been dubbed a studying model. It was studied horizontal wells in various directions in relation to the steam and the channel of higher permeability, in eight different depths. Into in the same area were studied, the sensitivity of the trajectories of horizontal wells, according to the depth of navigation. With the purpose of obtaining the highest output of oil to a particular flow, quality, temperature and time for the injection of steam. The wells studied showed a significant improvement in the cumulative oil recovery in one of the paths by promoting an alternative to application in mature fields or under development fields with heavy oil

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

Isolation of nanocellulose from pineapple leaf fibres by steam explosion

Steam explosion process is employed for the successful extraction of cellulose nanofibrils from pineapple leaf fibres for the first time. Steam coupled acid treatment on the pineapple leaf fibres is found to be effective in the depolymerization and defibrillation of the fibre to produce nanofibrils of these fibres. The chemical constituents of the different stages of pineapple fibres undergoing treatment were analyzed according to the ASTM standards. The crystallinity of the fibres is examined from the XRD analysis. Characterization of the fibres by SEM. AFM and TEM supports the evidence for the successful isolation of nanofibrils from pineapple leaf. The developed nanocellulose promises to be a very versatile material having the wide range of biomedical applications and biotechnological applications, such as tissue engineering, drug delivery, wound dressings and medical implants. (C) 2010 Elsevier Ltd. All rights reserved.

Structure, morphology and thermal characteristics of banana nano fibers obtained by steam explosion

In this work, cellulose nanofibers were extracted from banana fibers via a steam explosion technique. The chemical composition, morphology and thermal properties of the nanofibers were characterized to investigate their suitability for use in bio-based composite material applications. Chemical characterization of the banana fibers confirmed that the cellulose content was increased from 64% to 95% due to the application of alkali and acid treatments. Assessment of fiber chemical composition before and after chemical treatment showed evidence for the removal of non-cellulosic constituents such as hemicelluloses and lignin that occurred during steam explosion, bleaching and acid treatments. Surface morphological studies using SEM and AFM revealed that there was a reduction in fiber diameter during steam explosion followed by acid treatments. Percentage yield and aspect ratio of the nanofiber obtained by this technique is found to be very high in comparison with other conventional methods. TGA and DSC results showed that the developed nanofibers exhibit enhanced thermal properties over the untreated fibers. (C) 2010 Elsevier Ltd. All rights reserved.