Obtenção de Mo2C com adição de Co por reação gás-sólido em reator de leito fixo

Sulfur compounds emissions have been, on the late years, subject to more severe environmental laws due to its impact on the environment (causing the acid rain phenomena) and on human health. It has also been object of much attention from the refiners worldwide due to its relationship with equipment’s life, which is decreased by corrosion, and also with products’ quality, as the later may have its color, smell and stability altered by the presence of such compounds. Sulfur removal can be carried out by hydrotreating (HDT) which is a catalytic process. Catalysts for HDS are traditionally based on Co(Ni)-Mo(W)/Al2O3. However, in face of the increased contaminants’ content on crude oil, and stricter legislation on emissions, the development of new, more active and efficient catalysts is pressing. Carbides of refractory material have been identified as potential materials for this use. The addition of a second metal to carbides may enhance catalytic activities by increasing the density of active sites. In the present thesis Mo2C with Co addition was produced in a fixed bed reactor via gas-solid reaction of CH4 (5%) and H2(95%) with a precursor made of a mix of ammonium heptamolybdate [(NH4)6[Mo7O24].4H2O] and cobalt nitrate[Co(NO3)2.6H2O] at stoichiometric amounts. Precursors’ where analyzed by XRF, XRD, SEM and TG/DTA. Carboreduction reactions were carried out at 700 and 750°C with two cobalt compositions (2,5 and 5%). Reaction’s products were characterized by XRF, XRD, SEM, TOC, BET and laser granulometry. It was possible to obtain Mo2C with 2,5 and 5% cobalt addition as a single phase at 750°C with nanoscale crystallite sizes. At 700°C, however, both MoO2 and Mo2C phases were found by XRD. No Co containing phases were found by XRD. XRF, however, confirmed the intended Co content added. SEM images confirmed XRD data. The increase on Co content promoted a more severe agglomeration of the produced powder. The same effect was noted when the reaction temperature was increased. The powder synthesized at 750°C with 2,5% Co addition TOC analysis indicated the complete conversion from oxide material to carbide, with a 8,9% free carbon production. The powder produced at this temperature with 5% Co addition was only partially converted (86%)

Desenvolvimento de material BaCexPr1-xO3 (0 ≤ X ≤ 1) com estrutura perovskita para oxidação catalítica do CO a CO2 em reator de leito fixo

Barium Cerate (BaCeO3) is perovskite type structure of ABO3, wherein A and B are metal cations. These materials, or doped, have been studied by having characteristics that make them promising for the application in fuel cells solid oxide, hydrogen and oxygen permeation, as catalysts, etc .. However, as the ceramic materials mixed conductivity have been produced by different synthesis methods, some conditions directly influence the final properties, one of the most important doping Site B, which may have direct influence on the crystallite size, which in turn directly influences their catalytic activity. In this study, perovskite-type (BaCexO3) had cerium gradually replaced by praseodymium to obtain ternary type materials BaCexPr1-xO3 and BaPrO3 binaries. These materials were synthesized by EDTA/Citrate complexing method and the material characterized via XRD, SEM and BET for the identification of their structure, morphology and surface area. Moreover were performed on all materials, catalytic test in a fixed bed reactor for the identification of that person responsible for complete conversion of CO to CO2 at low operating temperature, which step can be used as the subsequent production of synthesis gas (CO + H2) from methane oxidation. In the present work the crystalline phase having the orthorhombic structure was obtained for all compositions, with a morphology consisting of agglomerated particles being more pronounced with increasing praseodymium in the crystal structure. The average crystal size was between 100 nm and 142,2 nm. The surface areas were 2,62 m²g-1 for the BaCeO3 composition, 3,03 m²g-1 to BaCe0,5Pr0,5O3 composition and 2,37 m²g-1 to BaPrO3 composition. Regarding the catalytic tests, we can conclude that the optimal flow reactor operation was 50 ml / min and the composition regarding the maximum rate of conversion to the lowest temperature was BaCeO3 to 400° C. Meanwhile, there was found that the partially replaced by praseodymium, cerium, there was a decrease in the catalytic activity of the material.

Síntese de ferritas de cobalto e níquel dopadas com zinco e caracterização de suas propriedades eletromagnéticas

This work shows that the synthesis by combustion is a prominent alternative to obtain ceramic powders of higher oxides, nanostructured and of high purity, as the ferrites of formulas Co(1-x)Zn(x)Fe2O4 e Ni(1-x)Zn(x)Fe2O4 with x ranging from 0.2 mols, in a range from 0.2 ≤ x ≥ 1.0 mol, that presents magnetic properties in coexistence of ferroelectric and ferrimagnetic states, which can be used in antennas of micro tapes and selective surfaces of low frequency in a range of miniaturized microwaves, without performance loss. The obtainment occurred through the combustion process, followed by appropriate physical processes and ordered to the utilization of the substrate sinterization process, it gave us a ceramic material, of high purity degree in a nanometric scale. The Vibrating Sample Magnetometer (VSM) analysis showed that those ferritic materials presents parameters, as materials hysteresis, that have own behavior of magnetic materials of good quality, in which the magnetization states can be suddenly changed with a relatively small variation of the field intensity, having large applications on the electronics field. The X-ray Diffraction (XRD) analysis of the ceramic powders synthesized at 900 °C, characterize its structural and geometrical properties, the crystallite size and the interplanar spacing. Other analysis were developed, as Scanning Electron Microscopy (SEM), X-ray Fluorescence (XRF), electric permittivity and the tangent loss, in high frequencies, through the equipment ZVB - 14 Vector Network Analyzer 10 MHz-14 GHz, of ROHDE & SCHWART.

Efeito da adição de WC e Co na sinterização e propriedades mecânicas da alumina

Composites based on alumina (Al2O3), tungsten carbide (WC) and cobalt (Co) exhibit specific properties such as low density, high oxidation resistance, high melting point and high chemical inertia. That composite shows to be a promising material for application in various fields of engineering. In this work, the mechanical properties of the composite (Al2O3 – WC – Co), particularly density and hardness, were evaluated according to the effects of the variables of powder processing parameters, green compact and sintered. Powder composites with the composition of 80 wt% Al2O3, 18 wt% WC and 2 wt% Co were processed by high energy ball milling in a planetary mill for 50 hours as well as mixed by manual mixing in a glass vessel with the same proportion. Samples were collected (2, 10, 20, 30, 40 and 50 hours) during the milling process. Then, the powders were compacted in a cylindrical die with 5 mm in diameter in a uniaxial press with pressures of 200 and 400 MPa. The sintering was in two stages: first, the solid phase sintering was performed at 1126 and 1300 °C for 1 hour with a heating rate of 10 °C/min in a resistive furnace under argon atmosphere for green samples compacted in 200 and 400 MPa; the second sintering was performed on dilatometer in solid phase at 1300 °C for green sample compacted in 200 MPa, another sintering also was performed on dilatometer, this time in liquid phase at 1550 °C for green samples compacted in 200 and 400 MPa, with the same parameters used in resistive furnace. The raw materials were characterized by X – ray diffraction (XRD), X – ray fluorescence (XRF), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and laser particlemeter. The sintered samples were subjected to microhardness testing. The results showed that high energy milling achieved to the objectives regarding the particle size and the dispersion of composite phases. However, the hardness did not achieve to significant results, this is an indication that the composite has low fracture toughness.

Efeito da adição de WC e Co na sinterização e propriedades mecânicas da alumina

Composites based on alumina (Al2O3), tungsten carbide (WC) and cobalt (Co) exhibit specific properties such as low density, high oxidation resistance, high melting point and high chemical inertia. That composite shows to be a promising material for application in various fields of engineering. In this work, the mechanical properties of the composite (Al2O3 – WC – Co), particularly density and hardness, were evaluated according to the effects of the variables of powder processing parameters, green compact and sintered. Powder composites with the composition of 80 wt% Al2O3, 18 wt% WC and 2 wt% Co were processed by high energy ball milling in a planetary mill for 50 hours as well as mixed by manual mixing in a glass vessel with the same proportion. Samples were collected (2, 10, 20, 30, 40 and 50 hours) during the milling process. Then, the powders were compacted in a cylindrical die with 5 mm in diameter in a uniaxial press with pressures of 200 and 400 MPa. The sintering was in two stages: first, the solid phase sintering was performed at 1126 and 1300 °C for 1 hour with a heating rate of 10 °C/min in a resistive furnace under argon atmosphere for green samples compacted in 200 and 400 MPa; the second sintering was performed on dilatometer in solid phase at 1300 °C for green sample compacted in 200 MPa, another sintering also was performed on dilatometer, this time in liquid phase at 1550 °C for green samples compacted in 200 and 400 MPa, with the same parameters used in resistive furnace. The raw materials were characterized by X – ray diffraction (XRD), X – ray fluorescence (XRF), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and laser particlemeter. The sintered samples were subjected to microhardness testing. The results showed that high energy milling achieved to the objectives regarding the particle size and the dispersion of composite phases. However, the hardness did not achieve to significant results, this is an indication that the composite has low fracture toughness.

(Table 1, Page 1046-1047) Chemical composition of iron-manganese concretions from the Indian Ocean recovered by the R/V Vityaz and the R/V Ob

The data given in this and previous communications is insufficient to assess the quantitative role of these supplementary sources in the Indian Ocean, but they do not rule out their local significance. Elucidation of this problem requires further data on the characteristics of the composition and structure of nodules in various different metallogenic regions of the ocean floor. A study of the distribution of ore elements in nodules both depthwise and over the area of the floor together with compilation of the first schematic maps based on the results of analyses of samples from 54 stations) enables us to give a more precise empirical relation between the Mn, Fe, Ni, Cu, and Co contents in Indian Ocean nodules, the manganese ratio and the values of the oxidation potential, which vary regularly with depth. This in turn also enables us to confirm that formation of nodules completes the prolonged process of deposition of ore components from ocean waters, and the complex physico-chemical transformations of sediments in the bottom layer. Microprobe investigation of ore rinds revealed the nonuniform distribution of a num¬ber of elements within them, owing to the capacity of particles of hydrated oxides of manganese and iron to adsorb various elements. High concentration of individual elements is correlated with local sectors of the ore rinds, in which the presence of todorokite, in particular, has been noted. The appearance of this mineral apparently requires elevated Ca, Mg, Na, and K concentrations, because the stable crystalline phase of this specific mineral form of the psilomelane group may be formed when these cations are incorporated into a lattice of the delta-MnO2 type.

Geochemical analysis of two sediment cores from the southern Mendeleev Ridge

We present results of an inorganic geochemical pore water and sediment study conducted on Quaternary sediments from the western Arctic Ocean. The sediment cores were recovered in 2008 from the southern Mendeleev Ridge during RV Polarstern Expedition ARK-XXIII/3. With respect to sediment sources and depositional processes, peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg indicate enhanced input of both ice-rafted (mainly dolomite) and biogenic carbonate during deglacial warming phases. Distinct and repetitive brown layers enriched in Mn (oxyhydr)oxides occur mostly in association with these carbonate-rich intervals. For the first time, we show that the brown layers are also consistently enriched in scavenged trace metals Co, Cu, Mo and Ni. The bioturbation patterns of the brown layers, specifically well-defined brown burrows into the underlying sediments, support formation close to the sediment-water interface. The Mn and trace metal enrichments were probably initiated under warmer climate conditions. Both river runoff and melting sea ice delivered trace metals to the Arctic Ocean, but also enhanced seasonal productivity and organic matter export to the sea floor. As Mn (oxyhydr)oxides and scavenged trace metals were deposited at the sea floor, a co-occurring organic matter "pulse" triggered intense diagenetic Mn cycling at the sediment-water interface. These processes resulted in the formation of Mn and trace metal enrichments, but almost complete organic matter degradation. As warmer conditions ceased, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, and greyish-yellowish sediments poor in Mn and trace metals were deposited. Oxygen depletion of Arctic bottom waters as potential cause for the lack of Mn enrichments during glacial intervals is highly improbable. While the original composition and texture of the brown layers resulted from specific climatic conditions (including transient Mn redox cycling at the sediment-water interface), pore water data show that early diagenetic Mn redistribution is still affecting the organic-poor sediments in several meters depth. Given persistent steady state diagenetic conditions, purely authigenic Mn-rich brown layers may form, while others may completely vanish. The degree of diagenetic Mn redistribution largely depends on the depositional environment within the Arctic Ocean, the availability of Mn and organic matter, and seems to be recorded by the Co/Mo ratios of single Mn-rich layers. We conclude that brown Arctic sediment layers are not necessarily synchronous features, and correlating them across different parts of the Arctic Ocean without additional age control is not recommended.

Nanostructured copper oxides and phosphates from a new solid-state route

Nanostructured copper containing materials of CuO, Cu3(PO4)3 and Cu2P2O7 have been prepared by solid-state pyrolysis of molecular CuCl2·NC5H4OH (I), CuCl2·CNCH2C6H4OH (II), oligomeric [Cu(PPh3)Cl]4 (III), N3P3[OC6H4CH2CN·CuCl]6[PF6] (IV), N3P3[OC6H5]5[OC5H4N·Cu][PF6] (V), polymeric chitosan·(CuCl2)n (VI) and polystyrene-co-4-vinylpyridine PS-b-4-PVP·(CuCl2) (VII) precursors. The products strongly depend on the precursor used. The pyrolytic products from phosphorus-containing precursors (III), (IV) and (V) are Cu phosphates or pyrophosphates, while non-phosphorous-containing precursors (VI) and (VII), result in mainly CuO. The use of chitosan as a solid-state template/stabilizer induces the formation of CuO and Cu2O nanoparticles. Copper pyrophosphate (Cu2P2O7) deposited on Si using (IV) as the precursor exhibits single-crystal dots of average diameter 100 nm and heights equivalent to twice the unit cell b-axis (1.5–1.7 nm) and an areal density of 5.1–7.7 Gigadots/in.2. Cu2P2O7 deposited from precursor (VI) exhibits unique labyrinthine high surface area deposits. The morphology of CuO deposited on Si from pyrolysis of (VI) depends on the polymer/Cu meta ratio. Magnetic measurements performed using SQUID on CuO nanoparticle networks suggest superparamagnetic behavior. The results give insights into compositional, shape and morphological control of the as-formed nanostructures through the structure of the precursors.

Geochemical composition of sulfide and oxide minerals from ODP Sites 193-1188 and 193-1189, PACMANUS field

Ocean Drilling Program (ODP) Leg 193 recovered core from the active PACMANUS hydrothermal field (eastern Manus Basin, Papua New Guinea) that provided an excellent opportunity to study mineralization related to a seafloor hydrothermal system hosted by felsic volcanic rocks. The purpose of this work is to provide a data set of mineral chemistry of the sulfide-oxide mineralization and associated gold occurrence in samples drilled at Sites 1188 and 1189. PACMANUS consists of five active vent sites, namely Rogers Ruins, Roman Ruins, Satanic Mills, Tsukushi, and Snowcap. In this work two sites were studied: Snowcap and Roman Ruins. Snowcap is situated in a water depth of 1670 meters below sea level [mbsl], covers a knoll of dacite-rhyodacite lava, and is characterized by low-temperature diffuse venting. Roman Ruin lies in a water depth of 1693-1710 mbsl, is 150 m across, and contains numerous large, active and inactive, columnar chimneys. Sulfide mineralogy at the Roman Ruins site is dominated by pyrite with lesser amounts of chalcopyrite, sphalerite, pyrrhotite, marcasite, and galena. Sulfide minerals are relatively rare at Snow Cap. These are dominated by pyrite with minor chalcopyrite and sphalerite and traces of pyrrhotite. Native gold has been found in a single sample from Hole 1189B (Roman Ruins). Oxide minerals are represented by Ti magnetite, magnetite, ilmenite, hercynite (Fe spinel), and less abundant Al-Mg rich chromite (average = 10.6 wt% Al2O3 and 5.8 wt% MgO), Fe-Ti oxides, and a single occurrence of pyrophanite (Mn Ti O3). Oxide mineralization is more developed at Snowcap, whereas sulfide minerals are more extensive and show better development at Roman Ruins. The mineralogy was obtained mainly by a detailed optical microscopy study. Oxide mineral identifications were confirmed by X-ray diffraction, and mineral chemistry was determined by electron probe microanalyses.

Granulometry, mineralogy and geochemistry of ODP Holes 184-1147A and 184-1148A, South China Sea

Green clay layers are reported from the Pliocene-Holocene intervals in five of the six sites drilled in the South China Sea (SCS) during Leg 184. Centimeter-scale discrete, discontinuous, and bioturbated layers, constituted by stiff and porous green clays, were observed, sometimes associated with iron sulfides and pyrite. Detailed mineralogical and geochemical analyses indicate that they differentiate from the host sediments in their higher content of iron, smectite, and mixed-layered clays and lower amounts of calcite, authigenic phosphorus, quartz, and organic matter. Although no glauconite was observed, the mineralogy and geochemistry of green clay layers, along with their geometrical relation to background sediments, suggest that they most likely represent the result of the first steps of glauconitization. Correlation between green layers and volcanic ash layers was suggested for green laminae observed elsewhere in Pacific sediments but was not confirmed at SCS sites. Statistical analysis of the temporal distribution of green layers in the records of the last million years suggests that green clay layers have become more frequent since 600 ka. Only at Site 1148 does the green layer record show a statistically significant cyclicity which may be related to orbital eccentricity. A possible influence of sea level variations, related both to climatic changes and tectonism, is postulated.

Net-surplus as a useful tool to analyse financial information in co-op societies

This paper aims to analyse a sample of Galician co-ops to verify whether or not it is possible to deduce different financial behaviours among co-op partners from the amount of net-surplus. To this end, our study adds net-surplus to the variation registered in some account entries so that other residual incomes yielded by the co-op may be considered. The distribution of these revenues shows that partners do not usually choose to fully anticipate residual incomes. This reveals that some firms follow a positive net-surplus strategy, which is actually different from the null net-surplus strategy asserted by the classical financial theory. Furthermore, results show that differences between both strategies are statistically significant. This opens a path to future research on determinants explaining why co-op partners voluntarily renounce to anticipating these residual incomes. Such behaviour only arises when yearly accounts render a positive result, thereby making the accounting net-surplus a useful tool to analyse financial information in co-op societies.

Fabrication of Sr- and Co-doped lanthanum chromite interconnectors for SOFC

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Produção de biogás a partir da co-digestão de resíduos da geração de energia

Aplicações de microalgas tem tornado esses micro-organismos importantes em pesquisas com fins tanto comerciais como energéticos. A biofixação de CO2 por microalgas é vista como uma forma economicamente viável e ambientalmente sustentável para mitigar as emissões de CO2 e geração de biomassa para obtenção de bioprodutos de alto valor agregado como os biocombustíveis. Na digestão anaeróbia da biomassa de microalgas a adição de um cosubstrato rico em carbono pode facilitar o processo de produção de biogás. O glicerol possui alta concentração de carbono orgânico e é solúvel em água. Neste sentido, a combinação de ambos os substratos pode solucionar um dos principais problemas para o processo de digestão, que reside no equilíbrio da razão (C/N). Co-digestão anaeróbia consiste na digestão anaeróbia de uma mistura de dois ou mais substratos com composições complementares. O objetivo do estudo foi avaliar a geração de biogás através da co-digestão anaeróbia de biomassa de Spirulina sp. LEB 18 e glicerol bruto. Para a realização do estudo foram construídos e operados sete biorreatores com volume útil de 1,5 L, alimentados com 5, 6, 10, 15 e 20 g.L -1 da mistura de biomassa de Spirulina e glicerol. A adição de diferentes quantidades de glicerol (5 e 10 g.L -1 ) foi utilizada como um suplemento na digestão anaeróbia em sistema de batelada. A razão C/N variou de 3,3×103 a 23,7. Os ensaios foram realizados a 35 °C, em reatores equipados com sistema de coleta de gás, alimentação e retirada do efluente líquido, operados em batelada sequencial. O efluente líquido dos reatores foi analisado quanto ao pH, nitrogênio amoniacal e alcalinidade. O volume de biogás produzido diariamente foi medido em gasômetro de frasco invertido. Em todos os ensaios, os valores médios de pH variaram de 7,0 a 7,3 e nitrogênio amoniacal de 62,02 a 1100,99 mg.L-1 . A alcalinidade do efluente variou entre 1133,37 e 3578,98 mg.L-1 CaCO3. Em todos os ensaios com adição de glicerol houve incremento na produção específica de biogás (0,16 – 0,24 d -1 ) quando comparado ao ensaio em que somente biomassa microalgal era alimentada no processo (0,03 L.d-1 ), demonstrando ser esta uma alternativa interessante para a produção de biocombustível e concomitante agregação de valor ao glicerol residual da produção de biodiesel.