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

Pirólise de borras oleosas de petroleo utilizando nanomateriais

The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery

Análise de desempenho de um fogão solar construído a partir de sucatas de antena de tv

Given the growing environmental crisis caused by degradation, mainly due to the use of polluting energy sources, increasing the growing use of renewable energies worldwide, with emphasis on solar energy, an abundant supply and available to everyone, which can be harnessed in several ways: electricity generation; dehydration of food; heating, disinfection and distillation and cooking. The latter has as its primary feature the viability of clean, renewable energy for society, combating ecological damage caused by large-scale use of firewood for cooking foods, use in tropical countries with high solar radiation, and has funding NGOs throughout the world with the goal of achieving low-income population. The proposed project consists of a solar cooker for concentration, working from the reflection of sunlight by a hub that they converge to a focal point at the bottom of the pot, getting lots of heat. The solar cooker under study consists of two elliptical reflecting parabolas made from the recycling of scrap TV antenna, having 0.29 m² of surface area for each antenna, which were covered by multiple mirrors of 2 mm thick and mounted on a metal structure, with correction for the mobility of the apparent movement of the sun. This structure was built with the recycling of scrap metal, possessing a relatively low cost compared with other solar cookers, around US$ 50.00. This cost becomes negligible, since that will involve a great benefit to not have fuel costs for each meal, unlike the use of gas or firewood for cooking food. The tests show that the cooker has reached the maximum temperature of 740 ° C, for boiling water in an average time of 28 minutes, cooking various types of foods such as potatoes, rice and pasta in an average time of 45 minutes and still going as a solar oven, making pizza baking and meat. These cooking times do not differ much from the cooking times on a gas stove, it becomes the solar cooker as a good consumer acceptance, and furthermore not to deliver the same gases that can poison the food as with the wood stove. Proves the viability of using the stove to cook or bake in two daily meals for a family, still presenting a position to improve his performance with the addition of new materials, equipment and techniques

Projeto e Operação em Escala Semi-Industrial de um Equipamento para Tratamento de Águas Produzidas na Indústria do Petróleo Utilizando Nova Tecnologia: misturador-decantador à inversão de fases - MDIF

The aim of this work is to use a new technology in the treatment of produced wastewaters from oil industry. An unit for treat produced waters called UTMDIF, was designed, installed and operated in an industrial plant for treatment of effluents from oil industry. This unit operates by means of the method of separation of phase inversion and can become a promising alternative to solve the problem of oil/water separation. This method constitutes the basis of the working of a new design of mixersettler of vertical configuration which occupies small surface area. The last characteristic becomes specially important when there is limitation on the lay-out of the plant, for example, over maritime platforms to explore oil. This equipment in a semi-industrial scale treats produced wastewaters contaminated with oil at low concentrations (ranging from 30 to 150 mg/L) and throughputs of 320 m3/d (47,4 m3 m-2 h-1). Good results were obtained in oil/water separation which leads to the necessary specification to discharge those wastewaters. Besides, the non dependence of the efficiency of separation in spite of the salinity of the medium becomes the equipment an attractive new technology to treat wastewaters containing oil at low concentrations

Remoção biológica de nitrato em água de abastecimento humano utilizando o endocarpo de coco como fonte de carbono

The groundwater quality has been compromised as a result of the intensification of human activities over the years. Groundwater contamination by nitrate is one of the effects of this degradation, a socio-environmental problem that affects many regions of the world and particular the city of Natal (RN). Developing techniques for nitrate removal in water is intended to eliminate or reduce the concentration of this compound, and those that involve biological processes have produced economic and environmental advantages. This study proposes a technology for biological removal of nitrate in water supply for humans, using the endocarp s coconut as a carbon source and bacteria support. The experiments were performed in pilot scale anoxic, testing different areas of the substrate surface. Results showed high rates nitrate removal during the monitoring period, noting the occurrence of denitrification after the beginning of system operation. The best performance was achieved in the treatment system containing substrate surface area increased, indicating that the decrease in the endocarp size contributed to increased bacterial activity, improving the ability to remove nitrate. About the quality analyzed aspects of water, it was found that the proposed technology has the potential water use for human consumption

Síntese, caracterização e aplicação do MCM-41 e A1-MCM-41 na pirólise do resíduo atmosférico de petróleo

In present work, mesoporous materials of the M41S family were synthesized, which were discovered in the early 90s by researchers from Mobil Oil Corporation, thus allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal array of mesopores with pore diameters ranging from 2 to 10 nm and a high surface area, enabling it to become very promising for the use as a catalyst in the refining of oil in the catalytic cracking process, since the mesopores facilitate the access of large hydrocarbon molecules, thereby increasing the production of light products, that are in high demand in the market. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more beneficial for application in the petrochemical industry. The mesoporous materials MCM-41 and Al-MCM-41 (ratio Si / Al = 50) were synthesized through the hydrothermal method, starting with silica gel, NaOH and distilled water. CTMABr was used as template, for structural guiding. In Al-MCM-41 the same reactants were used, with the adding of pseudoboehmite (as a source of aluminum) in the synthesis gel. The syntheses were carried out over a period of four days with a daily adjustment of pH. The optimum conditions of calcination for the removal of the organic template (CTMABr) were discovered through TG / DTG and also through analysis by XRD, FTIR and Nitrogen Adsorption. It was found that both the method of hydrothermal synthesis and calcination conditions of the studies based on TG were promising for the production of mesoporous materials with a high degree of hexagonal array. The acidic properties of the materials were determined by desorption of n-butylamine via thermogravimetry. One proved that the addition of aluminum in the structure of MCM-41 promoted an increase in the acidity of the catalyst. To check the catalytic activity of these materials, a sample of Atmospheric Residue (RAT) that is derived from atmospheric distillation of oil from the Pole of Guamaré- RN was used. This sample was previously characterized by various techniques such as Thermogravimetry, FTIR and XRF, where through thermal analysis of a comparative study between the thermal degradation of the RAT, the RAT pyrolysis + MCM-41 and RAT + Al- MCM-41. It was found that the Al-MCM-41 was most satisfactory in the promotion of a catalytic effect on the pyrolysis of the RAT, as the cracking of heavy products in the waste occurred at temperatures lower than those observed for the pyrolysis with MCM-41, and thereby also decreasing the energy of activation for the process and increasing the rates of conversion of residue into lighter products

efeito da aplicação de uma solução salina no crescimento e na composição química da atriplex nummularia

This study aimed to analyze the effect of a saline solution on growth and chemical composition of Atriplex nummularia, shrubby plant, absorbing salts used in the diet of animals and the management of water and saline soils. These plant seedlings were planted and grown in a reserved area at the Federal University of Rio Grande do Norte. The plantation was divided into two blocks, in which one of them was irrigated with saline solution with a concentration of 2840 mgL-1 of NaCl and the second group was irrigated with drinking water. After six months, the plants were collected, harvested and divided into three parts: leaf, thin and thick stem. Monthly, dimension measurements were carried out for cataloging the growth of Atriplex. Ion Chromatography (IC) and Optical Emission Spectroscopy Inductively Coupled Plasma (ICP-OES) were used to analyze the chemical composition of the partition plant parts. The results of these analyses revealed that an absorption process of anions and cations by Atriplex nummularia plant during its growth was achieved, in particular by a higher concentration of sodium and chloride ions. Scanning electron microscopy images showed and confirmed the presence of small crystals on the leaf surface. Electrical conductivity and pH measurements of the aerial parts of the plant were carried out and these results showed that the leaf is the plant part where there is a largest concentration of ions. In addition, measurements of specific surface were obtained from irrigated plants with saline solution, achieving higher surface area, in all cases. Plant dimensions obtained monthly showed that the plants irrigated with water grew 5% more than those plants irrigated with saline solution. Based on results obtained, Atriplex plant showed a higher potential to survive and adapt to environments (aquatic or geological) with high levels of salinity and this property can be used as a tool for removing salts/metals from industrial contaminated soils and effluents.

Craqueamento termocatalítico de óleo de girassol na presença da peneira molecular SAPO-5

The catalytic cracking of triglycerides presents itself as a possible alternative to the production of biofuels with low emission of pollutants. In this work were synthesized the SAPO-5, the catalysts for the cracking reaction of soybean oil is presented. The solids were powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG) and infrared spectroscopy (FTIR). The analyses indicated that the synthesis method has employed to obtain materials with high surface area and high acid. The soybean oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ºC in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. The products obtained in the cracking of soybean oil were analyzed by distillation, acid number, infra-red spectroscopy, density, viscosity, carbon residue, cetane number determination and characterization. The analysis of the products obtained in the presence and in the absence of the SAPO-5 permitted to conclude that all the solids tested presented catalytic activity in the deoxygenation of final products only at the second step of the cracking process

Obtenção de biodiesel através da transesterificação do óleo de farelo de arroz utilizando KI/Al2O3

This study proposes to find a biodiesel through transesterification of rice bran oil with KI/Al2O3 checking the influence of two types of alumina (Amorphous and Crystalline) for conversion into methyl esters. The catalyst was synthesized by the wet impregnation method. Adding 30 mL of 35% KI(aq.) in 10 g of alumina, under stirring at 80 °C for 3 hours. The reaction conditions used in this study were optimized, with a molar ratio methanol:oil of 15:1, 8 h of reaction time and reflux temperature. The catalyst amount was varied in the range of 1 to 5 % wt. The solid catalysts materials were analyzed by: x-ray diffraction (XRD), thermogravimetry (TG), N2 adsorption/desorption, scanning electron microscopy (SEM) and basicity, for the identification of its structure and composition, verifying the presence of basic sites. The results showed that Al2O3(A) presents an amorphous structure, high surface area and a better catalytic activity, in relation to the catalyst synthesized with Al2O3(C) support that proved to have a more crystalline structure, having as well, a lesser surface area, enabling difficulties for the incorporation of active sites. The obtained biodiesel with 5% wt. KI/Al2O3(A) presented physicochemical properties within the standards specified by the Resolution No 7/2008 ANP and obtained the best reaction yield with 95.2%, according to quantitative measurement from the TG, which showed 96.2% conversion into methyl esters. It was furthermore found that with the increasing amount of the quantity of the catalyst in the reaction, there was also an increase in the ester content obtained. The specific mass and the kinematic viscosity were reduced with the increase of the amount of quantity of the catalyst, indicating an increase in the conversion of triglycerides

Adsorção de Mn (II) e Zn (II) em soluções aquosas usando perlita expandida revestida com quitosana

In this work, chitosan was used as a coating of pure perlite in order to increase the accessibility of the groups OH- e NH2+the adsorptionof ions Mn2+ e Zn2+.The characterization results of the expanded perlite classified as microporous and whose surface area 3,176 m2 g-1after the change resulted in 4,664 m2g-1.From the thermogravimetry(TG) it was found that the percentage of coating was34,3%.The infrared analysis can prove the presence of groups Si-OH, Si-O e Al-O-Siresulting from the perlite and C=O, NH2and OH characterization of chitosan. The experiments on experiments on the adsorption of Mn and Zn were performed in the concentration range of10 a 50 mgL-1and the adsorption capacity inpH 5,8 e 5,2 was 19,49 and 23,09 mgg-1to 25 oC,respectively.The adsorption data were best fitted to Langmuir adsorption model to Langmuir adsorption model for both metalionsisindicative of monolayer adsorption. The kinetics of adsorption were calculated from the equation of Lagergren fitting the model pseudo-second-order for all initial concentrations, suggesting that adsorption of ions Mn2+ and Zn2+ follows the kinetics of pseudo-second-order and whose constant Speedk2(g/mg.min) are 0,105 e 3,98 and capacity and maximum removal qe 4,326 e 3,348,respectively.In this study we used a square wave voltammetry cathodic stripping voltammetry to quantify the adsorbed ions, and the working electrode glassy carbon, reference electrode silver / silver chloride and a platinum auxiliary electrode. The attainment of the peaks corresponding to ions Mn2+ and Zn2+ was evaluated in and electrochemical cell with a capacity of 30 mL using a buffer system (Na2HPO4/NaH2PO4)at pH 4 and was adjusted with solutionsH3PO4 0,1molL-1and NaOH 0,1 molL-1and addition of the analyte has been a cathodic peak in- 0,873 Vand detection limit of2,55x10-6molL-1para Zn.The dough used for obtaining the adsorption isotherm was 150 mg and reached in 120 min time of equilibrium for both metal ions.The maximum adsorption for 120 min with Mn concentration 20 mgL-1 and Zn 10 mgL-1,was91, 09 e 94, 34%, respectively

Aplicação da parafina e do óleo de linhaça como hidrofobizantes da vermiculita, para remoção de derivados de óleo diesel resentes em água produzida sintética

Produced water has lately aroused interest due to their high degree of salinity, suspended oil particles, chemicals added in various manufacturing processes, heavy metals and radioactivity sometimes. Along with oil and due to its high volume production, water production is one of the pollutants of most concern in the process of oil extraction. PAHs due to their ubiquity and their characteristics carcinogenic or mutagenic and teratogenic even have attracted the attention of every scientific society. Formed from the incomplete combustion of organic matter may be natural or anthropogenic. Some materials have been researched with the goal of cleaning up environmental matrices that may be contaminated by hydrocarbons. Among these materials researched various clays have been employed, of which highlights the vermiculite. The family of phyllosilicates, vermiculite for its potential and its high hydrophobic surface area has been a tool widely used in the decontamination of water in processes of oil spills. However, when it loses its capacity expanded hydrophobic having the necessity of using a hidrofobizante to make it organophilic. Among the numerous hidrofobizantes researched and used the linseed oil was the pioneer. In this study sought to evaluate the capacity of removal of PAHs using the vermiculite hydrofobized with linseed oil and wax also, for it was made use of the 24 full factorial design as the main tool for the experiments. We also evaluated the clay grain size (-20 +48 and -48 +80 #), the percentage of hidrofobizante applied (5 and 10%) and salinity of the water produced synthesized in our laboratory (35,000 and 55,000 ppm). The molecular fluorescence spectroscopy due to its sensitivity and speed was used to verify the adsorption capacity of clay, as well as gas chromatography served as an auxiliary technique to identify and quantify the PAHs in solution. In order to characterize the vermiculite was made use of X-ray fluorescence and X-ray diffraction. The infrared and thermogravimetry were essential to note hydrophobization and the amount of coating of clay. According to the fluorescence analysis showed that the test 12 was the best result in about 98% adsorption of fluorescent compounds, however the high salinity, the smallest particle size, the highest percentage of hidrofobizante and the use of linseed oil showed greater efficiency in the removal capacity of these hydrocarbons, in accordance with the trend followed by the analysis of the major factors of the factorial design. To verify the adsorption capacity of clay using a fixed volume of water produced synthetically, used as the test base 12, at their respective levels and factors. Thus, it was observed that after adding about 1 ½ liters of water solution produced synthetically, about 300 times its volume in mass, the vermiculite was able to adsorb 80% of fluorescent species present in solution

Estudo de titanatos nanoestruturados obtidos por tratamento hidrotérmico de óxido de titânio em meio alcalino

TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800ºC), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7·nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200ºC, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400ºC. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150ºC, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase

Síntese e caracterização de membranas zeolíticas tipo mfi e aplicação em separação de aromáticos

The synthesis of MFI-type zeolite membranes was carried by the process in situ or hydrothermal crystallization. We studied the homogenization time of the room temperature and gel filtration just before the crystallization step performed out in an oven, thus obtaining a more uniform zeolite film. The powder synthesized zeolite (structure type MFI, Silicalite) was characterized by several complementary techniques such as Xray diffraction (XRD), scanning electron microscopy (SEM), thermal analysis, temperature programmed desorption (TPD), Fourier Transform infrared spectroscopy (FTIR) and textural analysis by nitrogen adsorption (specific surface area). For the purpose of evaluating the quality of the layer supported on the ceramic support, N2 permeation tests were carried starting from room temperature to 600 °C, where values were observed values more appropriate permeation from 200 °C. With the data obtained, it was made into a graph of temperature versus permeation function, the curve of surface diffusion was found. For scanning electron microscopy, we observed the formation of homogeneous crystals and the zeolite film showed no fissures or cracks, indicating that the process of synthesis and subsequent treatments not damaged the zeolite layer on the support. Carried permeation studies were found values ranging from 3.64x10-6 to 3.78x10-6, 4.71x10-6 to 5.02x10-6, to pressures 20 and 25 psi, respectively. And the mixture xylenes/N2 values were between 5.39x10-6 to 5.67x10-6 and 8.13x10-6 to 8.36x10-6, also for pressures of 20 and 25 psi. The values found for the separation factor were 15.22 at 400 °C in the first experiment and 1.64 for the second experiment at a temperature of 150 °C. It is concluded that the Silicalite membrane was successfully synthesized and that it is effective in the separation of binary mixtures of xylenes

Obtenção de diesel verde por craqueamento termocatalítico de óleo de buriti (Mauritia flexuosa L.) sobre materiais nanoestruturados do tipo LaSBA-15

In order to obtain a biofuel similar to mineral diesel, lanthanum-incorporated SBA- 15 nanostructured materials, LaSBA-15(pH), with different Si/La molar ratios (75, 50, 25), were synthesized in a two-steps hydrothermal procedure, with pH-adjusting of the synthesis gel at 6, and were used like catalytic solids in the buriti oil thermal catalytic cracking. These solids were characterized by X-ray fluorescence (XRF), powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), infrared spectroscopy (FTIR), nitrogen porosimetry and ethanol dehydration, aiming to active sites identify. Taken together, the analyses indicated that the synthesis method has employed to obtain materials highly ordered mesostructures with large average pore sizes and high surface area, besides suggested that the lanthanum was incorporated in the SBA-15 both into the framework as well as within the mesopores. Catalytic dehydration of ethanol over the LaSBA-15(pH) products has shown that they have weak Lewis acid and basic functionalities, indicative of the presence of lanthanum oxide in these samples, especially on the La75SBA-15(pH) sample, which has presented the highest selectivity to ethylene. The buriti oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ºC in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. One the other hand, OL coming from second ones, called green diesel (GD), have presented low acid index, particularly that one obtained from the thermal catalytic process realized over LaSBA-15(pH) samples. The acid sites presence in these samples, associated to their large average pore sizes and high surface areas, have allowed them, especially the La75SBA-15(pH), to present deoxygenating activity in the buriti oil thermal catalytic cracking, providing an oxygenates content reduction, particularly carboxylic acids, in the GD. Furthermore, the GD comes from the second liquid fraction obtained in the buriti oil thermal catalytic cracking over this latest solid sample has shown hydrocarbons composition and physic-chemical properties similar to that mineral diesel, beyond sulfur content low

Estudo do desempenho de catalisadores tipo Ni/CexM1-xO2 (M = Zr ou Mn) na reação de oxidação parcial do metano

One of the main applications of methane is in the production of syngas, a mixture of hydrogen and carbon monoxide. Procedures used in this process are steam reforming, CO2 reforming, partial oxidation and autothermal reforming. The present study evaluated and compared the behavior of nickel catalysts supported on mixed oxides of cerium and manganese in the partial oxidation of methane with that of nickel catalysts supported on mixed oxides of cerium and zirconium. Mixed oxides of cerium and zirconium or cerium and manganese were synthesized using two different preparation methods, the polymeric precursor based on Pechini method and combustion reaction using a microwave. This was followed by impregnation with nickel content of 15 %. Samples were calcined at 300, 800 and 900 °C and characterized by specific surface area (SSA), X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed reduction (TPR) and the reaction of partial oxidation of methane. The specific areas of samples decrease with the rise in calcination temperature and after nickel impregnation. Metal-cerium solid solution was formed and the presence of other manganese species outside the solid solution structure was confirmed in the compound with the highest amounts of manganese oxides showed. With regard to scanning electron microscopy, supports based on cerium and zirconium prepared by Pechini method exhibited agglomerated particles without uniform geometry or visible pores on the surface. However, compounds containing manganese presented empty spaces in its structure. Through synthesis by combustion reaction, morphology acquired independently of the proposed composition demonstrated greater porosity in relation to Pechini synthesis. Although catalysts were prepared using different synthesis methods, the insertion of nickel showed very similar reduction profiles (TPR). In relation to nickel catalysts supported on mixed oxide of cerium and zirconium, there is an initial reduction of NiO species that present certain interaction with the support. This is followed by the reduction of Ce4+ in Ce3+ surface, with subsequent bulk reduction. For catalysts containing manganese, a reduction of nickel oxide species occurs, followed by two stages of reduction for species Mn2O3 in Mn3O4 and Mn3O4 in MnO, with subsequent reduction of bulk. With respect to partial oxidation reactions, the nickel catalyst supported on mixed oxide of cerium and zirconium, prepared using the Pechini method, exhibited CH4 conversion of approximately 80 %, with conversion of 81 % when prepared by combustion. This behavior continued for 10 hours of reaction. Manganese content was also found to directly influence catalytic activity of materials; the greater the manganese oxide content, the faster deactivation and destabilization occurred in the catalyst. In both synthesis methods, the nickel catalyst supported on mixed oxide of cerium and zirconium maintained an H2/CO ratio very close to 2 during the 10 hours of partial oxidation reaction. Samples containing manganese displayed smaller H2/CO ratios and lower performance in partial oxidation.