Reforma a vapor catalítica do metano: Otimização da produção e seletividade em hidrogênio por absorção in situ do CO2 produzido

Topics of research related to energy and environment have significantly grown in recent years, with the need of its own energy as hydrogen. More particularly, numerous researches have been focused on hydrogen as energy vector. The main portion of hydrogen is presently obtained by reforming of methane or light hydrocarbons (steam, oxy, dry or auto reforming). During the methane steam reforming process the formation of CO2 undesirable (the main contributor to the greenhouse effect) is observed. Thus, an oxide material (sorbent) can be used to capture the CO2 generated during the process and simultaneously shifting the equilibrium of water gas shift towards thermodynamically more favorable production of pure hydrogen. The aim of this study is to develop a material with dual function (catalyst/sorbent) in the reaction of steam reforming of methane. CaO is well known as CO2 sorbent due to its high efficiency in reactions of carbonation and easy regeneration through calcination. However the kinetic of carbonation decreases quickly with time and carbonation/calcination cycles. A calcium aluminate (Ca12Al14O33) should be used to avoid sintering and increase the stability of CaO sorbents for several cycles. Nickel, the industrial catalyst choice for steam reforming has been added to the support from different manners. These bi-functional materials (sorbent/catalyst) in different molar ratios CaO.Ca12Al14O33 (48:52, 65:35, 75:25, 90:10) were prepared by different synthesis methodologies, among them, especially the method of microwave assisted self-combustion. Synthesis, structure and catalytic performances of Ni- CaO.Ca12Al14O33 synthesized by the novel method (microwave assisted selfcombustion) proposed in this work has not being reported yet in literature. The results indicate that CO2 capture time depends both on the CaO excess and on operating conditions (eg., temperature and H2O/CH4 ratio). To be efficient for CO2 sorption, temperature of steam reforming needs to be lower than 700 °C. An optimized percentage corresponding to 75% of CaO and a ratio H2O/CH4 = 1 provides the most promising results since a smaller amount of water avoids competition between water and CO2 to form carbonate and hydroxide. If this competition is most effective (H2O/CH4 = 3) and would have a smaller amount of CaO available for absorption possibly due to the formation of Ca(OH)2. Therefore, the capture time was higher (16h) for the ratio H2O/CH4 = 1 than H2O/CH4 = 3 (7h) using as catalyst one prepared by impregnating the support obtained by microwave assisted self-combustion. Therefore, it was demonstrated that, with these catalysts, the CO2 sorption on CaO modifies the balance of the water gas-shift reaction. Consequently, steam reforming of CH4 is optimized, producing pure H2, complete conversion of methane and negligible concentration of CO2 and CO during the time of capture even at low temperature (650 °C). This validates the concept of the sorption of CO2 together with methane steam reforming

Avaliação da influência do nacl em pastas de cimento portland para cimentação de poços de petróleo em zonas evaporíticas

One of the major current challenges for oilwell companies is the extraction of oil from evaporitic zones, also known as pre-salt basins. Deep reservoirs are found under thick salt layers formed from the evaporation of sea water. Salt layers seal the flow of oil from underneath rock formations, which store hydrocarbons and increase the probability of success in oil and gas exploration. Oilwells are cemented using Portland-based slurries to promote mechanical stability and zonal isolation. For pre-salt oilwells, NaCl must be added to saturate the cement slurries, however, the presence of salt in the composition of slurries affects their overall behavior. Therefore, the objective of the present study was to evaluate the effect of the addition of 5 to 25% NaCl on selected properties of Portland-based slurries. A series of tests were carried out to assess the rheological behavior, thickening time, free water and ultrassonic compressive strength. In addition, the slurries were also characterized by thermal analysis, X ray diffraction and scanning electron microscopy. The results showed that the addition of NaCl affected the thickening time of the slurries. NaCl contents up to 10% shortened the thickening time of the slurries. On the other hand, concentrations in excess of 20% not only extended the thickening time, but also reduced the strength of hardened slurries. The addition of NaCl resulted in the formation of a different crystalline phase called Friedel´s salt, where free chlorine is bonded to tricalcium aluminate

Influência da adição de cálcio nas propriedades de pastas geopoliméricas destinadas a cimentação de poços de petróleo

Nowadays, the search for new technologies that are able to follow the upcoming challenges in oil industry is a constant. Always trying properties improvements of the used materials, looking for the best performance and greater life time. Besides the search for technologies that show an improvement of performance, the search for materials environmentally correct along the whole production process. In Oil well cementing, this search for new technologies passes through the development of slurry systems that support these requests and that are also environmentally friendly. In this context, the use of geopolymer slurries is a great alternative route to cementing oil wells. Besides having good properties, comparable to Portland cement slurries, this alternative material releases much less CO2 gas in the production of their root materials when compared the production of Portland cement, which releases tons of CO2. In order to improve the properties of geopolymer slurries has been added Calcium Oxide, as observed in other studies that slurries where the Calcium is present the values of compressive strength is greater. The addition has been realized based in the CaO/SiO2 molar ratio of 0.05, 0.10 and 0.15. Have been performed compressive strength tests, thickening time, rheology and fliud loss control test of the slurries, following NBR 9831, as well as the physical chemical characterization of XRD, SEM and TG. Has been observed in most of the tests the slurries follow a tendency until the ratio of 0.10, which inverses in the ratio 0.15. This behavior can be explained by two phenomena that occur simultaneously, the first one is the break of the polymer chains and a consequent increase in molucules mobility, which prevails until the ratio of 0.1, and the second is possible approach of the chains due to the capacity of the calcium ions stabilize the charges of two different aluminum. There is only one linearity in the mechanical behavior that can be attributed to the appereance of the C-S-H phase. Based on this, it is concluded that the phenomenon of breaking the polymer chains predominates until the ratio of 0.1, causing an increase of the filtrate volume, lower rheological parameters and increasing thickening time. From the ratio of 0.15 the approach of the chains predominates, and the behavior is reversed

Influência da adição de gres porcelanato no comportamento mecânico e microestrutural em pastas de cimento portland para cimentação de poços de petróleo

Cementation operation consists in an extremely important work for the phases of perforation and completion of oil wells, causing a great impact on the well productivity. Several problems can occur with the cement during the primary cementation, as well as throughout the productive period. The corrective operations are frequent, but they are expensive and demands production time. Besides the direct cost, prejudices from the interruption of oil and gas production till the implementation of a corrective operation must be also taken into account. The purpose of this work is the development of an alternative cement paste constituted of Portland cement and porcelainized stoneware residue produced by ceramic industry in order to achieve characteristics as low permeability, high tenacity, and high mechanical resistance, capable of supporting various operations as production or oil wells recuperation. Four different concentration measures of hydrated paste were evaluated: a reference paste, and three additional ones with ceramic residue in concentrations of the order of 10%, 20% and 30% in relation to cement dough. High resistance and low permeability were found in high concentration of residues, as well as it was proved the pozolanic reactivity of the residue in relation to Portland cement, which was characterized through x-ray and thermogravimetry assays. It was evident the decrease of calcium hydroxide content, once it was substituted by formation of new hydrated products as it was added ceramic residue

Pastas compósitas cimento/sílica/polímero para cimentação de poços de baixa profundidade sujeitas à injeção de vapor

The production of heavy oil fields, typical in the Northeastern region, is commonly stimulated by steam injection. High bottom hole temperatures are responsible not only for the development of deleterious stresses of the cement sheath but also for cement strength retrogression. To overcome this unfavorable scenario, polymeric admixtures can be added to cement slurries to improve its fracture energy and silica flour to prevent strength retrogression. Therefore, the objective of the present study was to investigate the effect of the addition of different concentrations of polyurethane (5-25%) to cement slurries containing 40% BWOC silica flour. The resulting slurries were characterized using standard API (American Petroleum Institute) laboratory tests. In addition to them, the mechanical properties of the slurries, including elastic modulus and microhardness were also evaluated. The results revealed that density, free water and stability of the composite cement/silica/polyurethane slurries were within acceptable limits. The rheological behavior of the slurries, including plastic viscosity, yield strength and gel strength increased with the addition of 10% BWOC polyurethane. The presence of polyurethane reduced the fluid loss of the slurries as well as their elastic modulus. Composite slurries also depicted longer setting times due to the presence of the polymer. As expected, both the mechanical strength and microhardness of the slurries decreased with the addition of polyurethane. However, at high bottom hole temperatures, the strength of the slurries containing silica and polyurethane was far superior than that of plain cement slurries. In summary, the use of polyurethane combined with silica is an interesting solution to better adequate the mechanical behavior of cement slurries to heavy oil fields subjected to steam injection

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

Avaliação de compatibilidade entre pasta de cimento e fluido de perfuração não-aquoso utilizados em poços petrolíferos

Compatibility testing between a drilling fluid and a cement slurry is one of the steps before an operation of cementing oil wells. This test allows us to evaluate the main effects that contamination of these two fluids may cause the technological properties of a cement paste. The interactions between cement paste and drilling fluid, because its different chemical compositions, may affect the cement hydration reactions, damaging the cementing operation. Thus, we carried out the study of the compatibility of non-aqueous drilling fluid and a cement slurry additives. The preparation procedures of the non-aqueous drilling fluid, the cement paste and completion of compatibility testing were performed as set out by the oil industry standards. In the compatibility test is evaluated rheological properties, thickening time, stability and compressive strength of cement pastes. We also conducted analyzes of scanning electron microscopy and X-ray diffraction of the mixture obtained by the compatibility test to determine the microstructural changes in cement pastes. The compatibility test showed no visual changes in the properties of the cement paste, as phase separation. However, after the addition of nonaqueous drilling fluid to cement slurry there was an increased amount of plastic viscosity, the yield point and gel strength. Among the major causative factors can include: chemical reaction of the components present in the non-aqueous drilling fluid as the primary emulsifier, wetting agent and paraffin oil, with the chemical constituents of the cement. There was a reduction in the compressive strength of the cement paste after mixing with this drilling fluid. Thickening test showed that the oil wetting agent and high salinity of the non-aqueous fluid have accelerating action of the handle of the cement paste time. The stability of the cement paste is impaired to the extent that there is increased contamination of the cement slurry with the nonaqueous fluid. The X-ray diffraction identified the formation of portlandite and calcium silicate in contaminated samples. The scanning electron microscopy confirmed the development of the identified structures in the X-ray diffraction and also found the presence of wells in the cured cement paste. The latter, formed by the emulsion stability of the drilling fluid in the cement paste, corroborate the reduction of mechanical strength. The oil wetting agent component of the non-aqueous drilling fluid, the modified cement hydration processes, mainly affecting the setting time.

Avaliação da influência do nacl em pastas de cimento portland para cimentação de poços de petróleo em zonas evaporíticas

One of the major current challenges for oilwell companies is the extraction of oil from evaporitic zones, also known as pre-salt basins. Deep reservoirs are found under thick salt layers formed from the evaporation of sea water. Salt layers seal the flow of oil from underneath rock formations, which store hydrocarbons and increase the probability of success in oil and gas exploration. Oilwells are cemented using Portland-based slurries to promote mechanical stability and zonal isolation. For pre-salt oilwells, NaCl must be added to saturate the cement slurries, however, the presence of salt in the composition of slurries affects their overall behavior. Therefore, the objective of the present study was to evaluate the effect of the addition of 5 to 25% NaCl on selected properties of Portland-based slurries. A series of tests were carried out to assess the rheological behavior, thickening time, free water and ultrassonic compressive strength. In addition, the slurries were also characterized by thermal analysis, X ray diffraction and scanning electron microscopy. The results showed that the addition of NaCl affected the thickening time of the slurries. NaCl contents up to 10% shortened the thickening time of the slurries. On the other hand, concentrations in excess of 20% not only extended the thickening time, but also reduced the strength of hardened slurries. The addition of NaCl resulted in the formation of a different crystalline phase called Friedel´s salt, where free chlorine is bonded to tricalcium aluminate

Influência da adição de cálcio nas propriedades de pastas geopoliméricas destinadas a cimentação de poços de petróleo

Nowadays, the search for new technologies that are able to follow the upcoming challenges in oil industry is a constant. Always trying properties improvements of the used materials, looking for the best performance and greater life time. Besides the search for technologies that show an improvement of performance, the search for materials environmentally correct along the whole production process. In Oil well cementing, this search for new technologies passes through the development of slurry systems that support these requests and that are also environmentally friendly. In this context, the use of geopolymer slurries is a great alternative route to cementing oil wells. Besides having good properties, comparable to Portland cement slurries, this alternative material releases much less CO2 gas in the production of their root materials when compared the production of Portland cement, which releases tons of CO2. In order to improve the properties of geopolymer slurries has been added Calcium Oxide, as observed in other studies that slurries where the Calcium is present the values of compressive strength is greater. The addition has been realized based in the CaO/SiO2 molar ratio of 0.05, 0.10 and 0.15. Have been performed compressive strength tests, thickening time, rheology and fliud loss control test of the slurries, following NBR 9831, as well as the physical chemical characterization of XRD, SEM and TG. Has been observed in most of the tests the slurries follow a tendency until the ratio of 0.10, which inverses in the ratio 0.15. This behavior can be explained by two phenomena that occur simultaneously, the first one is the break of the polymer chains and a consequent increase in molucules mobility, which prevails until the ratio of 0.1, and the second is possible approach of the chains due to the capacity of the calcium ions stabilize the charges of two different aluminum. There is only one linearity in the mechanical behavior that can be attributed to the appereance of the C-S-H phase. Based on this, it is concluded that the phenomenon of breaking the polymer chains predominates until the ratio of 0.1, causing an increase of the filtrate volume, lower rheological parameters and increasing thickening time. From the ratio of 0.15 the approach of the chains predominates, and the behavior is reversed

Influência da adição de gres porcelanato no comportamento mecânico e microestrutural em pastas de cimento portland para cimentação de poços de petróleo

Cementation operation consists in an extremely important work for the phases of perforation and completion of oil wells, causing a great impact on the well productivity. Several problems can occur with the cement during the primary cementation, as well as throughout the productive period. The corrective operations are frequent, but they are expensive and demands production time. Besides the direct cost, prejudices from the interruption of oil and gas production till the implementation of a corrective operation must be also taken into account. The purpose of this work is the development of an alternative cement paste constituted of Portland cement and porcelainized stoneware residue produced by ceramic industry in order to achieve characteristics as low permeability, high tenacity, and high mechanical resistance, capable of supporting various operations as production or oil wells recuperation. Four different concentration measures of hydrated paste were evaluated: a reference paste, and three additional ones with ceramic residue in concentrations of the order of 10%, 20% and 30% in relation to cement dough. High resistance and low permeability were found in high concentration of residues, as well as it was proved the pozolanic reactivity of the residue in relation to Portland cement, which was characterized through x-ray and thermogravimetry assays. It was evident the decrease of calcium hydroxide content, once it was substituted by formation of new hydrated products as it was added ceramic residue

Pastas compósitas cimento/sílica/polímero para cimentação de poços de baixa profundidade sujeitas à injeção de vapor

The production of heavy oil fields, typical in the Northeastern region, is commonly stimulated by steam injection. High bottom hole temperatures are responsible not only for the development of deleterious stresses of the cement sheath but also for cement strength retrogression. To overcome this unfavorable scenario, polymeric admixtures can be added to cement slurries to improve its fracture energy and silica flour to prevent strength retrogression. Therefore, the objective of the present study was to investigate the effect of the addition of different concentrations of polyurethane (5-25%) to cement slurries containing 40% BWOC silica flour. The resulting slurries were characterized using standard API (American Petroleum Institute) laboratory tests. In addition to them, the mechanical properties of the slurries, including elastic modulus and microhardness were also evaluated. The results revealed that density, free water and stability of the composite cement/silica/polyurethane slurries were within acceptable limits. The rheological behavior of the slurries, including plastic viscosity, yield strength and gel strength increased with the addition of 10% BWOC polyurethane. The presence of polyurethane reduced the fluid loss of the slurries as well as their elastic modulus. Composite slurries also depicted longer setting times due to the presence of the polymer. As expected, both the mechanical strength and microhardness of the slurries decreased with the addition of polyurethane. However, at high bottom hole temperatures, the strength of the slurries containing silica and polyurethane was far superior than that of plain cement slurries. In summary, the use of polyurethane combined with silica is an interesting solution to better adequate the mechanical behavior of cement slurries to heavy oil fields subjected to steam injection

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

Polissacarídeos sulfatados da Alga Marrom Dictyopteris justii como agentes antioxidantes e inibidores da formação de cristais de oxalato de cálcio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

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

Análise do comportamento reológico de pastas de cimento contendo resíduos de pneu para poços de petróleo

The low tenacity presented by the Portland cement pastes used in the oil wells cementation has been motivating several researches with attention focused on alternative materials. Additives have been developed to generate flexible pastes with mechanical resistance capable to support the expansions and retractions of the metallic covering of the wells that submit to the steam injection, technique very used to increase the recovery factor in oil reservoirs with high viscosity. A fresh paste with inadequate rheological behavior may commit the cementation process seriously, involving flaws that affect the performance of the paste substantially in the hardened state. This work proposes the elaboration and the rheological analysis of Portland cement pastes with addition of residues of rubber tire in several proportions, with the aim of minimizing the damages provoked in the hem cementing of these wells. By thermogravimetric analysis, the particles of eraser that go by the sieve of 0,5mm (35 mesh) opening and treated superficially with NaOH solution of 1 mol/L presented appropriate thermal resistance for wells that submit to thermal cyclic. The evaluation of the study based on the results of the rheological analysis of the pastes, complemented by the mechanical analysis, thickening, stability, tenor of free water and filtrate loss, being used as parameter a paste reference, without rubber addition. The results showed satisfactory rheology, passive of few corrections; considerable loss of mechanical resistance (traction and compression), compensated by earnings of tenacity, however with established limits for its application in oil wells; satisfactory stability, free water and thickening time