Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process

Síntese e caracterização de catalisadores nanométricos de LaSrNiO4 para aplicação em dessulfurização de tiofeno

The mixed metal oxides constitute an important class of catalytic materials widely investigated in different fields of applications. Studies of rare earth nickelates have been carried by several researchers in order to investigate the structural stability afforded by oxide formed and the existence of catalytic properties at room temperature. So, this study aims synthesize the nanosized catalyst of nickelate of lanthanum doped with strontium (La(1-x)SrxNiO4-d; x = 0,2 and 0,3), through the Pechini method and your characterization for subsequent application in the desulfurization of thiophene reaction. The precursor solutions were calcined at 300ºC/2h for pyrolysis of polyester and later calcinations occurred at temperatures of 500 - 1000°C. The resulting powders were characterized by thermogravimetric analysis (TG / DTG), surface area for adsorption of N2 by BET method, X-ray diffraction (XRD), scanning electron microscopy (HR_SEM) and spectrometry dispersive energy (EDS). The results of XRD had show that the perovskites obtained consist of two phases (LSN and NiO) and from 700ºC have crystalline structure. The results of SEM evidenced the obtainment of nanometric powders. The results of BET show that the powders have surface area within the range used in catalysis (5-50m2/g). The characterization of active sites was performed by reaction of desulfurization of thiophene at room temperature and 200ºC, the relation F/W equal to 0,7 mol h-1mcat -1. The products of the reaction were separated by gas chromatography and identified by the selective detection PFPD sulfur. All samples had presented conversion above 95%

Influência do método de síntese e caracterização de pós compósitos de NiO- Ce1-xEuxO2-δ para anodos catalíticos de células a combustível

Fuel cells are electrochemical devices that convert chemical energy into electricity. Due to the development of new materials, fuel cells are emerging as generating clean energy generator. Among the types of fuel cells, categorized according to the electrode type, the solid oxide fuel cells (SOFC) stand out due to be the only device entirely made of solid particles. Beyond that, their operation temperature is relatively high (between 500 and 1000 °C), allowing them to operate with high efficiency. Another aspect that promotes the use of SOFC over other cells is their ability to operate with different fuels. The CeO2 based materials doped with rare earth (TR+3) may be used as alternatives to traditional NiO-YSZ anodes as they have higher ionic conductivity and smaller ohmic losses compared to YSZ, and can operate at lower temperatures (500-800°C). In the composition of the anode, the concentration of NiO, acting as a catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, providing internal reform in the cell. In this work compounds of NiO - Ce1-xEuxO2-δ (x = 0.1, 0.2 and 0.3) were synthesized from polymeric precursor, Pechini, method of combustion and also by microwave-assisted hydrothermal method. The materials were characterized by the techniques of TG, TPR, XRD and FEG-SEM. The refinement of data obtained by X-ray diffraction showed that all powders of NiO - Cex-1EuxO2-δ crystallized in a cubic phase with fluorite structure, and also the presence of Ni. Through the characterizations can be proved that all routes of preparation used were effective for producing ceramics with characteristics suitable for application as SOFC anodes, but the microwave-assisted hydrothermal method showed a significant reduction in the average grain size and improved control of the compositions of the phases

Estudo das propriedades magnéticas e estruturais do composto (Sm1 - xMMx)2Fe17 e seus nitretos

Conselho Nacional de Desenvolvimento Científico e Tecnológico

Geologia, Geocronologia, Geoquímica e Petrogênese das Rochas Ígneas Cretácicas da Província Magmática do Cabo e suas Relações com as Unidades Sedimentares da Bacia de Pernambuco (NE do Brasil)

The area studied forms a thin NNE-directed belt situated south of Recife town (Pernambuco state), northeastern Brazil. Geologically, it comprises the Pernambuco Basin (PB), which is limited by the Pernambuco Lineament to the north, the Maragogi high to the south and the Pernambuco Alagoas massif to the west, all of them with Precambrian age. This thesis reports the results obtained for the Cabo Magmatic Province (CMP), aiming the characterization of the geology, stratigraphy, geochronology, geochemistry and petrogenesis of the Cretaceous igneous rocks presented in the PB. The PB is composed of the Cabo Formation (rift phase) at the base (polymictic conglomerates, sandstones, shales), an intermediate unit, the Estiva Formation (marbles and argillites), and, at the top, the Algodoais Formation (monomictic conglomerates, sandstones, shales). The CMP is represented by trachytes, rhyolites, pyroclastics (ignimbrites), basalts / trachy-andesites, monzonites and alkali-feldspar granite, which occur as dykes, flows, sills, laccoliths and plugs. Field observations and well descriptions show that the majority of the magmatic rocks have intrusive contacts with the Cabo Formation, although some occurrences are also suggestive of synchronism between volcanism and siliciclastic sedimentation. 40Ar/39Ar and zircon fission tracks for the magmatic rocks indicate an average age of 102 r 1 Ma for the CMP. This age represents an expressive event in the province and is detected in all igneous dated materials. It is considered as a minimum age (Albian) for the magmatic episode and the peak of the rift phase in the PB. The 40Ar/39Ar dates are about 10-14 Ma younger than published palynologic ages for this basin. Geochemically, the CMP may be divided in two major groups; i) a transitional to alkaline suite, constituted by basalts to trachy-andesites (types with fine-grained textures and phenocrysts of sanidine and plagioclase), trachytes (porphyrytic texture, with phenocrysts of sanidine and plagioclase) and monzonites; ii) a alkaline suite, highly fractionated, acidic volcano-plutonic association, formed by four subtypes (pyroclastic flows ignimbrites, fine-to medium-grained rhyolites, a high level granite, and later rhyolites). These four types are distinguished essentially by field aspects and petrographic and textural features. Compatible versus incompatible trace element concentrations and geochemical modeling based on both major and trace elements suggest the evolution through low pressure fractional crystallization for trachytes and other acidic rocks, whereas basalts / trachy-andesites and monzonites evolved by partial melting from a mantle source. Sr and Nd isotopes reveal two distinct sources for the rocks of the CMP. Concerning the acidic ones, the high initial Sr ratios (ISr = 0.7064-1.2295) and the negative HNd (-0.43 to -3.67) indicate a crustal source with mesoproterozoic model ages (TDM from 0.92 to 1.04 Ga). On the other hand, the basic to intermediate rocks have low ISr (0.7031-0.7042) and positive HNd (+1.28 to +1.98), which requires the depleted mantle as the most probable source; their model ages are in the range 0.61-0.66 Ga. However, the light rare earth enrichment of these rocks and partial melting modeling point to an incompatible-enriched lherzolitic mantle with very low quantity of garnet (1-3%). This apparent difference between geochemical and Nd isotopes may be resolved by assuming that the metasomatizing agent did not obliterate the original isotopic characteristics of the magmas. A 2 to 5% partial melting of this mantle at approximately 14 kbar and 1269oC account very well the basalts and trachy-andesites studied. By using these pressure and temperatures estimates for the generation of the basaltic to trachy-andesitic magma, it is determined a lithospheric stretching (E) of 2.5. This E value is an appropriated estimate for the sub-crustal stretching (astenospheric or the base of the lithosphere?) region under the Pernambuco Basin, the crustal stretching probably being lower. The integration of all data obtained in this thesis permits to interpret the magmatic evolution of the PB as follows; 1st) the partial melting of a garnet-bearing lherzolite generates incompatible-enriched basaltic, trachy-andesitic and monzonitic magmas; 2nd) the underplating of these basaltic magmas at the base of the continental crust triggers the partial melting of this crust, and thus originating the acidic magmas; 3rd) concomitantly with the previous stage, trachytic magmas were produced by fractionation from a monzonitic to trachy-andesitic liquid; 4th) the emplacement of the several magmas in superficial (e.g. flows) or sub-superficial (e.g. dykes, sills, domes, laccoliths) depths was almost synchronically, at about 102 r 1 Ma, and usually crosscutting the sedimentary rocks of the Cabo Formation. The presence of garnet in the lherzolitic mantle does not agree with pressures of about 14 kbar for the generation of the basaltic magma, as calculated based on chemical parameters. This can be resolved by admitting the astenospheric uplifting under the rift, which would place deep and hot material (mantle plume?) at sub-crustal depths. The generation of the magmas and their subsequent emplacement would be coupled with the crustal rifting of the PB, the border (NNE-SSW directed) and transfer (NW-SE directed) faults serving as conduits for the magma emplacement. Based on the E parameter and the integration of 40Ar/39Ar and palynologic data it is interpreted a maximum duration of 10-14 Ma for the rift phase (Cabo Formation clastic sedimentation and basic to acidic magmatism) of the PB

Petrologia do magmatismo tardi-brasiliano no Maciço São José de Campestre(RN/PB), com ênfase no Plúton Alcalino Caxexa

The area studied is located on the north-easternmost portion of the Borborema Province, on the so-called São José de Campestre Massif, States of RN and PB, Northeast Brazil. Field relations and petrographic, geochemical and isotope data permitted the separation of five suites of plutonic rocks: alkali-feldspar granite (Caxexa Pluton), which constitutes the main subject of this dissertation, amphibole-biotite granite (Cabeçudo Pluton), biotite microgranite, gabbronorite to monzonite (Basic to Intermediate Suite) and aluminous granitoid. The Caxexa Pluton is laterally associated to the Remígio Pocinhos Shear Zone, with its emplacement along the mylonitic contact between the gneissic basement and the micashists. This pluton corresponds to a syntectonic intrusion elongated in the N-S direction, with about 50 km2 of outcropping surface. It is composed exclusively of alkali-feldspar granites, having clinopyroxene (aegirine-augite and hedenbergite), andradite-rich garnet, sphene and magnetite. It is classified geochemically as high silica rocks (>70 % wt), metaluminous to slightly peraluminous (normative corindon < 1%), with high total alkalis (>10% wt), Sr, iron number (#Fe=90-98) and agpaitic index (0.86-1.00), and positive europium anomaly. The Cabeçudo Pluton is composed of porphyritic rocks, commonly containing basic to intermediate magmatic enclaves often with mingling and mixing textures. Petrographically, it presents k-feldspar and plagioclase phenocrysts as the essential minerals, besides the accessories amphibole, biotite, sphene and magnetite. It is metaluminous and shows characteristics transitional between the calc-alkaline and alkaline series (or monzonitic subalkaline). Its REE content is greater than those ones of the Caxexa Pluton and biotite microgranite, and all spectra have negative europium anomalies. The biotite microgranites occur mainly on the central and eastern portion of the mapped area, as dykes and sheets with decimetric thickness, hosted principally in orthogneisses and micashists. Their field relationships as regards the Caxexa and Cabeçudo plutons suggested that they are late-tectonic intrusions. They are typically biotite granites, having also sphene, amphibole, allanite, opaques and zircon in the accessory assemblage. Geochemically they can be distinguished from the porphyritic types because the biotite microgranites are more evolved, peraluminous, and have more fractionated REE spectra. The Basic to Intermediate rocks form a volumetrically expressive elliptical, kilometric scale body on the Southeast, as well as sheets in micashists. They are classified as gabbronorites to monzonites, with the two pyroxenes and biotite, besides subordinated amounts of amphibole, sphene, ilmenite and allanite. These rocks do not show a well-defined geochemical trend, however they may possibly represent a monzonitic (shoshonitic) series. Their REE spectra have negative europium anomalies and REE contents greater than the other suites. The aluminous granitoids are volumetrically restricted, and have been observed in close association with migmatised micashists bordering the gabbronorite pluton. They are composed of almandine-rich garnet, andalusite, biotite and muscovite, and are akin to the peraluminous suites. Rb-Sr (whole rock) and Sm-Nd (whole-rock and mineral) isotopes furnished a minimum estimate of the crystallization (578±14 Ma) and the final resetting age of the Rb-Sr system (536±4 Ma) in the Caxexa Pluton. The aluminous granitoid has a Sm-Nd garnet age similar to that one of the Caxexa Pluton, that is 574±67 Ma. The strong interaction of shear bands and pegmatite dykes favoured the opening of the Rb-Sr system for the Caxexa Pluton and biotite microgranite. The amphibole-plagioclase geothermometer and the Al-in amphibole geobarometer indicate minimum conditions of 560°C and 7 kbar for the Cabeçudo Pluton, 730°C and 6 kbar for the microgranite and 743°C and 5 kbar for the basic to intermediate suite. The Zr saturation geothermometer reveals temperatures of respectively 855°C, 812°C and 957°C for those suites, whereas the Caxexa Pluton shows temperatures of around 757°C. The Caxexa, Cabeçudo and microgranites suites crystallized under high fO2 (presence of magnetite). On the other hand, the occurrence of ilmenite suggests less oxidant conditions in the basic to intermediate suite. Field relations demonstrate the intrusive character of the granitoids into a tectonically relatively stable continental crust. This is corroborated by petrographic and geochemical data, which suggest a late- or post-collisional tectonic context. It follows that the generation and emplacement of those granitoid suites is related to the latest events of the Brasiliano orogeny. Finally, the relationships between eNd (600 Ma), TDM (Nd) and initial Sr isotope ratio (ISr) do not permit to define the precise sources of the granitoids. Nevertheless, trace element modelling and isotopic comparisons suggest the participation of the metasomatised mantle in the generation of these suites, probably modified by different degrees of crustal contamination. In this way, a metasomatised mantle would not be a particular characteristic of the Neoproterozoic lithosphere, but a remarkable feature of this portion of the Borborema Province since Archaean and Paleoproterozoic times.

Petrologia do plúton Serra da Macambira, neoproterozóico da faixa seridó, província Borborema (NE do Brasil)

The final stage of Brasiliano/Pan-African orogeny in the Borborema Province is marked by widespread plutonic magmatism. The Serra da Macambira Pluton is an example of such plutonism in Seridó Belt, northeastern Borborema Province, and it is here subject of geological, petrographic, textural, geochemical and petrogenetic studies. The pluton is located in the State of Rio Grande do Norte, intrusive into Paleoproterozoic orthogneisses of the Caicó Complex and Neoproterozoic metassupracrustal rocks of the Seridó Group. Based upon intrusion/inclusion field relationships, mineralogy and texture, the rocks are classified as follows: intermediate enclaves (quartz-bearing monzonite and biotite-bearing tonalite), porphyritic monzogranite, equigranular syenogranite to monzogranite, and late granite and pegmatite dykes. Porphyritic granites and quartz-bearing monzonites represent mingling formed by the injection of an intermediate magma into a granitic one, which had already started crystallization. Both rocks are slightly older than the equigranular granites. Quartz-bearing monzonite has K-feldspar, plagioclase, biotite, hornblende and few quartz, meanwhile biotite-bearing tonalite are rich in quartz, poor in K-feldspar and hornblende is absent. Porphyritic and equigranular granites display mainly biotite and rare hornblende, myrmekite and pertitic textures, and zoned plagioclase pointing out to the relevance of fractional crystallization during magma evolution. Such granites have Rare Earth Elements (REE) pattern with negative Eu anomaly and light REE enrichment when compared to heavy REE. They are slight metaluminous to slight peraluminous, following a high-K calc-alkaline path. Petrogenesis started with 27,5% partial melting of Paleoproterozoic continental crust, generating an acid hydrous liquid, leaving a granulitic residue with orthopyroxene, plagioclase (An40-50), K-feldspar, quartz, epidote, magnetite, ilmenite, apatite and zircon. The liquid evolved mainly by fractional crystallization (10-25%) of plagioclase (An20), biotite and hornblende during the first stages of magmatic evolution. Granitic dykes are hololeucocratic with granophyric texture, indicating hypabissal crystallization and REE patterns similar to A-Type granites. Preserved igneous textures, absence or weak imprint of ductile tectonics, association with mafic to intermediate enclaves and alignment of samples according to monzonitic (high-K calcalkaline) series all indicate post-collisional to post-orogenic complexes as described in the literature. Such interpretation is supported by trace element discrimination diagrams that place the Serra da Macambira pluton as late-orogenic, probably reflecting the vanishing stages of the exhumation and collapse of the Brasiliano/Pan-African orogen.

Caracterização petrográfica e litogeoquímica de granitoides ediacaranos no extremo NE da Província da Borborema (NE do Brasil) com ênfase nos plútons Gameleira, Pitombeira e Taipu

The studied area is situated in the northeastern extremity of the Rio Grande do Norte State, between the municipalities of Taipu and Poço Branco, and is geologically inserted into the São José do Campestre Crystalline Terrain within the Borborema Province, where the analysis of field relationships, petrographic and geochemical data allowed the distinction of three plutons named: Gameleira, Taipu and Pitombeira. The Gamaleira Pluton is composed of granodioritic rocks characterized by zoned plagioclase phenocrysts, with amphibole and biotite as the main mafic phases. Geochemically, these are metaluminous rocks of calc-alkaline nature and magnesian character. The Pitombeira Pluton encompasses two facies: (a) a coarse-grained to porphyritic monzo- to syenogranitic facies marked by K-feldspar phenocrysts; and (b) a quartz dioritic to tonalitic facies with partially zoned plagioclase laths showing chilled rims. Geochemically, rocks of the monzo- to syenogranitic facies are transitional between metaluminous and peraluminous, display a subalkaline nature (high K calc-alkaline) and a ferroan character, whereas rocks of the quartz dioritic to tonalitic facies are metaluminous, with shoshonitic affinity and ferroan character. Lastly, the Taipu Pluton is made of monzoto syenogranitic rocks with biotite as the chief mafic mineral. They are peraluminous rocks of subalkaline nature (high-K calc-alkaline) and ferroan character. Regarding the rare-earth elements (REE), it is possible to conclude that the three studied plutons display negative Eu anomalies and a relative enrichment of LREE over HREE, with LaN/YbN ratios between 9.39 to 16.20 (Gameleira Pluton), 17.99 to 31.39 (granitic facies of the Pitombeira Pluton), 14.15 to 21.81 (dioritic facies of the Pitombeira Pluton) and 15.17 to 175.41 (Taipu Pluton). Based on the combined investigation of geochemical data and discrimination tectonic diagrams, a late- to post-collisional tectonic environment is suggested for the plutons here studied

Petrologia e geoquímica do magmatismo ediacarano Serra do Caramuru, Rio Grande do Norte, NE do Brasil

The Serra do Caramuru and Tapuio stocks, located in the extreme NE of Rio Piranhas-Seridó Domain (RN), are representative of the Ediacaran-Cambrian magmatism, an important magmatic feature of the Brasilian / Panafrican orogeny of the Borborema Province. These bodies are lithologically similar, intrusive in paleoproterozoic gneiss embasement, being separated by a thin belt of mylonitic orthogneiss. The field relations show a magmatic stratigraphy initiated by dioritic facies that coexists with the porphyritic granitic and equigranular granitic I facies, and less frequently with equigranular granitic II facies. These rocks are crosscut by late granitic dykes and sheets with NE-SW / NNE-SSW orientation. The dioritic facies (diorite, quartz diorite, quartz monzodiorites, tonalite and granodiorite) is leucocratic to melanocratic, rich in biotite and hornblende. The granitic facies are hololeucocratic to leucocratic, and have biotite ± hornblende. Petrographic and geochemical (whole rock) data, especially from Serra do Caramuru pluton, suggest fractionation of zircon, apatite, clinopyroxene (in diorites), opaque minerals, titanite, biotite, hornblende, allanite, plagioclase, microcline and garnet (in dykes). The behavior of trace elements such as Zr, La and Yb indicates that the dioritic magma does not constitute the parental magma for the granitic facies. On the other hand, the granitic facies seems to be cogenetic to each other, displaying differentiation trends and very similar rare earth elements (REE) spectra [12.3≤(La/Yb)N≤190.8; Eu/Eu*=0.30-0.68]. Field relationships and REE patterns [6.96≤(La/Yb)N≤277.8; Eu/Eu*=0.18-0.58] demonstrate that the granitic dykes and sheets are not cogenetically related to the Serra do Caramuru magmatism. The dioritic facies is metaluminous (A/CNK = 0.88-0.74) and shoshonitic, whereas the granitic ones are metaluminous to peraluminous (A/CNK = 1.08-0.93) and high potassium calc-alkaline. Dykes and sheets are strictly peraluminous (A/CNK = 1.01-1.04). Binary diagrams relating compatible and incompatible trace elements and microtextures indicate the fractional crystallization as the dominant mechanism of magmatic evolution of the various facies. The Serra do Caramuru and Tapuio stocks have well preserved magmatic fabric, do not show metamorphic minerals and are structurally isotropic, showing crosscutting contact with the ductile fabric of the basement. These observations lead to interpretate a stage of relative tectonic stability, consistent with the orogenic relaxation period of the Brasiliano / Pan-African orogeny. Chemical plots involving oxides and trace elements indicate late to post-collisional emplacement. In this context, the assumed better mechanism to describe the stocks emplacement within an extensional T Riedel joint, with ENE-WSW extensional vector. The U-Pb zircon age of 553 ± 10 Ma allows correlating the Serra do Caramuru magmatism to the group of post-collisional bodies, equigranular high potassium calc-alkaline granites of the NE of Rio Piranhas-Seridó Domain.

Petrologia e geoquímica do magmatismo ediacarano Serra do Caramuru, Rio Grande do Norte, NE do Brasil

The Serra do Caramuru and Tapuio stocks, located in the extreme NE of Rio Piranhas-Seridó Domain (RN), are representative of the Ediacaran-Cambrian magmatism, an important magmatic feature of the Brasilian / Panafrican orogeny of the Borborema Province. These bodies are lithologically similar, intrusive in paleoproterozoic gneiss embasement, being separated by a thin belt of mylonitic orthogneiss. The field relations show a magmatic stratigraphy initiated by dioritic facies that coexists with the porphyritic granitic and equigranular granitic I facies, and less frequently with equigranular granitic II facies. These rocks are crosscut by late granitic dykes and sheets with NE-SW / NNE-SSW orientation. The dioritic facies (diorite, quartz diorite, quartz monzodiorites, tonalite and granodiorite) is leucocratic to melanocratic, rich in biotite and hornblende. The granitic facies are hololeucocratic to leucocratic, and have biotite ± hornblende. Petrographic and geochemical (whole rock) data, especially from Serra do Caramuru pluton, suggest fractionation of zircon, apatite, clinopyroxene (in diorites), opaque minerals, titanite, biotite, hornblende, allanite, plagioclase, microcline and garnet (in dykes). The behavior of trace elements such as Zr, La and Yb indicates that the dioritic magma does not constitute the parental magma for the granitic facies. On the other hand, the granitic facies seems to be cogenetic to each other, displaying differentiation trends and very similar rare earth elements (REE) spectra [12.3≤(La/Yb)N≤190.8; Eu/Eu*=0.30-0.68]. Field relationships and REE patterns [6.96≤(La/Yb)N≤277.8; Eu/Eu*=0.18-0.58] demonstrate that the granitic dykes and sheets are not cogenetically related to the Serra do Caramuru magmatism. The dioritic facies is metaluminous (A/CNK = 0.88-0.74) and shoshonitic, whereas the granitic ones are metaluminous to peraluminous (A/CNK = 1.08-0.93) and high potassium calc-alkaline. Dykes and sheets are strictly peraluminous (A/CNK = 1.01-1.04). Binary diagrams relating compatible and incompatible trace elements and microtextures indicate the fractional crystallization as the dominant mechanism of magmatic evolution of the various facies. The Serra do Caramuru and Tapuio stocks have well preserved magmatic fabric, do not show metamorphic minerals and are structurally isotropic, showing crosscutting contact with the ductile fabric of the basement. These observations lead to interpretate a stage of relative tectonic stability, consistent with the orogenic relaxation period of the Brasiliano / Pan-African orogeny. Chemical plots involving oxides and trace elements indicate late to post-collisional emplacement. In this context, the assumed better mechanism to describe the stocks emplacement within an extensional T Riedel joint, with ENE-WSW extensional vector. The U-Pb zircon age of 553 ± 10 Ma allows correlating the Serra do Caramuru magmatism to the group of post-collisional bodies, equigranular high potassium calc-alkaline granites of the NE of Rio Piranhas-Seridó Domain.

Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process

Síntese e caracterização de catalisadores nanométricos de LaSrNiO4 para aplicação em dessulfurização de tiofeno

The mixed metal oxides constitute an important class of catalytic materials widely investigated in different fields of applications. Studies of rare earth nickelates have been carried by several researchers in order to investigate the structural stability afforded by oxide formed and the existence of catalytic properties at room temperature. So, this study aims synthesize the nanosized catalyst of nickelate of lanthanum doped with strontium (La(1-x)SrxNiO4-d; x = 0,2 and 0,3), through the Pechini method and your characterization for subsequent application in the desulfurization of thiophene reaction. The precursor solutions were calcined at 300ºC/2h for pyrolysis of polyester and later calcinations occurred at temperatures of 500 - 1000°C. The resulting powders were characterized by thermogravimetric analysis (TG / DTG), surface area for adsorption of N2 by BET method, X-ray diffraction (XRD), scanning electron microscopy (HR_SEM) and spectrometry dispersive energy (EDS). The results of XRD had show that the perovskites obtained consist of two phases (LSN and NiO) and from 700ºC have crystalline structure. The results of SEM evidenced the obtainment of nanometric powders. The results of BET show that the powders have surface area within the range used in catalysis (5-50m2/g). The characterization of active sites was performed by reaction of desulfurization of thiophene at room temperature and 200ºC, the relation F/W equal to 0,7 mol h-1mcat -1. The products of the reaction were separated by gas chromatography and identified by the selective detection PFPD sulfur. All samples had presented conversion above 95%

Influência do método de síntese e caracterização de pós compósitos de NiO- Ce1-xEuxO2-δ para anodos catalíticos de células a combustível

Fuel cells are electrochemical devices that convert chemical energy into electricity. Due to the development of new materials, fuel cells are emerging as generating clean energy generator. Among the types of fuel cells, categorized according to the electrode type, the solid oxide fuel cells (SOFC) stand out due to be the only device entirely made of solid particles. Beyond that, their operation temperature is relatively high (between 500 and 1000 °C), allowing them to operate with high efficiency. Another aspect that promotes the use of SOFC over other cells is their ability to operate with different fuels. The CeO2 based materials doped with rare earth (TR+3) may be used as alternatives to traditional NiO-YSZ anodes as they have higher ionic conductivity and smaller ohmic losses compared to YSZ, and can operate at lower temperatures (500-800°C). In the composition of the anode, the concentration of NiO, acting as a catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, providing internal reform in the cell. In this work compounds of NiO - Ce1-xEuxO2-δ (x = 0.1, 0.2 and 0.3) were synthesized from polymeric precursor, Pechini, method of combustion and also by microwave-assisted hydrothermal method. The materials were characterized by the techniques of TG, TPR, XRD and FEG-SEM. The refinement of data obtained by X-ray diffraction showed that all powders of NiO - Cex-1EuxO2-δ crystallized in a cubic phase with fluorite structure, and also the presence of Ni. Through the characterizations can be proved that all routes of preparation used were effective for producing ceramics with characteristics suitable for application as SOFC anodes, but the microwave-assisted hydrothermal method showed a significant reduction in the average grain size and improved control of the compositions of the phases

Estudo de adsorvente obtido de terras diatomáceas para remoção de metais pesados em águas produzidas: processamento, caracterização e dinâmica em leito fixo

The acceleration of industrial growth in recent decades on all continents aroused the interest of the companies to counter the impacts produced on the environment, spurred primarily by major disasters in the petroleum industry. In this context, the water produced is responsible for the largest volume of effluent from the production and extraction of oil and natural gas. This effluent has in its composition some critical components such as inorganic salts, heavy metals (Fe, Cu, Zn, Pb, Cd, ), presence of oil and chemicals added in the various production processes. In response to impact, have been triggered by research alternative adsorbent materials for water treatment and water produced, in order to removing oils and acids and heavy metals. Many surveys of diatomaceous earth (diatomite) in Brazil involve studies on the physico-chemical, mineral deposits, extraction, processing and applications. The official estimated Jazi are around 2.5 million tonnes, the main located in the states of Bahia (44%) and Rio Grande do Norte (37,4%). Moreover, these two states appear as large offshore producers, earning a prominent role in research of adsorbents such as diatomite for treatment of water produced. Its main applications are as an agent of filtration, adsorption of oils and greases, industrial load and thermal insulator. The objective of this work was the processing and characterization of diatomite diatomaceous earth obtained from the municipality of Macaíba-RN (known locally as tabatinga) as a low cost regenerative adsorbent for removal of heavy metals in the application of water produced treatment. In this work we adopted a methodology for batch processing, practiced by small businesses located in producing regions of Brazil. The characterization was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area (BET). Research conducted showed that the improvement process used was effective for small volume production of diatomite concentrated. The diatomite obtained was treated by calcination at temperature of 900 oC for 2 hours, with and without fluxing Na2CO3 (4%), according to optimal results in the literature. Column adsorption experiments were conducted to percolation of the in nature, calcined and calcined fluxing diatomites. Effluent was used as a saline solution containing ions of Cu, Zn, Na, Ca and Mg simulating the composition of produced waters in the state of Rio Grande do Norte, Brazil. The breakthrough curves for simultaneous removal of copper ions and zinc as a result, 84.3% for calcined diatomite and diatomite with 97.3 % for fluxing. The calcined fluxing diatomite was more efficient permeability through the bed and removal of copper and zinc ions. The fresh diatomite had trouble with the permeability through the bed under the conditions tested, compared with the other obtained diatomite. The results are presented as promising for application in the petroleum industry

Síntese pelo método pechini e caracterização da zircônia dopada com cério e neodímio

In this study five compositions were synthesized zirconia doped with cerium and neodymium ions in the system Ce10-xNdx Zr90O2 with 0,5 ≤ x ≤ 4,0 using the Pechini method. The powders were characterized by thermogravimetric analysis, differential thermal analysis, infrared spectroscopy and X-ray diffraction, with application of Rietveld refinement of the calcination temperatures of 350ºC/3h and 30 minutes at 900ºC/3h. All compositions stabilized with a mixture of cubic and tetragonal phase zirconia. The samples were pressed into bars and sintered at 1500°C/3h and 1500°C/6h, being characterized by Xray diffraction, with application of the Rietveld refinement, density and porosity using Archimedes method, scanning electron microscopy and resistance the three point bending. It has been observed the increase in strength with increasing sintering temperature for the compositions x = 2,0 and x = 4,0. For x = 2,0 the main phase was the cubic with 92,56% with crystallite size of 0,56 μm, density and porosity of 96,82% from 1,36%. For x = 4,0 was a mixture of cubic and tetragonal phase with 21% and 37,98%, respectively. The crystallite size was 54,21 nm and 49,64 nm with a density porosity of 97,45% and 1,32% respectively. In the analysis of the fracture surface was observed a greater amount of grain fracture intragranular type, which contribute to increase the mechanical strength of the ceramic. Increased addition of the neodymium ion in the crystal lattice of the zirconium showed a nearly linear behavior with increasing mechanical strength of the zirconia ceramic. Was obtained a bending resistance of 537 ± 38 MPa for the composition x = 2,0 predominantly attributed to cubic phase with 92,56%