Pigmentos de pinturas rupestres pré-históricas do sítio Letreiro do Quinto, Pedro II, Piauí, Brasil

The Letreiro do Quinto rock shelter is located in the rural area of the city of Pedro II, Piauí, Brazil. The sandstone walls of the shelter are covered with prehistoric rupestrian paintings, painted in patterns of yellow and light and dark red hues. The chemical-mineralogical characterization of the prehistoric pigments was made with energy dispersive spectroscopy, scanning electron microscopy, energy dispersive X-ray fluorescence and 57Fe transmission Mössbauer spectroscopy at 110 K. Results confirm the occurrence of hematite- and goethite-rich ochres and also that the pigment layers are indeed made of a mixture of clay minerals mixed with iron oxides.

Diesel/biodiesel soot oxidation with ceo2 and ceo2-zro2-modified cordierites: a facile way of accounting for their catalytic ability in fuel combustion processes

CeO2 and mixed CeO2-ZrO2 nanopowders were synthesized and efficiently deposited onto cordierite substrates, with the evaluation of their morphologic and structural properties through XRD, SEM, and FTIR. The modified substrates were employed as outer heterogeneous catalysts for reducing the soot originated from the diesel and diesel/biodiesel blends incomplete combustion. Their activity was evaluated in a diesel stationary motor, and a comparative analysis of the soot emission was carried out through diffuse reflectance spectroscopy. The analyses have shown that the catalyst-impregnated cordierite samples are very efficient for soot oxidation, being capable of reducing the soot emission in more than 60%.

Interaction between cationic and conventional nonionic surfactants in the mixed micelle and monolayer formed in aqueous medium

Mixed micellization and surface properties of cationic and nonionic surfactants dimethyl decyl-, tetradecyl- and hexadecyl phosphineoxide mixtures are studied using conductivity and surface tension measurements. The models of Rubingh, Rosen, and Clint, are used to obtain the interaction parameter, minimum area per molecule, mixed micelle composition, free energies of mixing and activity coefficients. The micellar mole fractions were always higher than ideal values indicating high contributions of cationics in mixed micelles. Activity coefficients were less than unity indicating synergism in micelles. The negative free energies of mixing showed the stability of the surfactants in the mixed micelles.

Methanol steam reforming over Cu/CeO2 catalysts: influence of zinc addition

Methanol steam reforming reaction was studied over Cu(5 wt.%)/CeO2 with and without the presence of Zn. The Zn addition decreased the Cu+2 reducibility and increased the oxygen mobility of ceria. The main products were CO2 and H2 with small amount of CO. Selectivity to CO decreased with the Zn addition and it was lower at lower reaction temperatures and lower space velocities. At 230 ºC and W/F MeOH = 648 g min mol-1 selectivities to H2 and to CO2 were 100% on Zn/Cu/Ce. The catalytic results indicated that CO was mainly a secondary product formed from reverse water gas shift reaction.

Análise e discriminação de quimiotipos de Lippia graveolens H.B.K. da Guatemala por microextração em fase sólida, CG-EM e análise multivariada

SPME-GC-MS, PCA and HCA multivariate techniques were used in order to evaluate their applicability to discriminate the three chemotypes (thymol, carvacrol and mixed) described for L. graveolens of Guatemala. The leaves of L. graveolens are used for treatment of colds, bronchitis, and as seasoning for food preparations, yielding essential oil up to 4.34 %. Leaves of 35 individuals from eight populations, and eight composite samples were analyzed using a DVB/Carboxen/PDMS fiber and GC-MS. PCA and HCA were carried out using eight markers (p-cymene, cis-sabinene hydrate, linalool, terpinen-4-ol, thymol, carvacrol, (E)-caryophyllene and caryophyllene oxide). The three chemotypes of L. graveolens were satisfactorily discriminated.

Synthesis of indium tin oxide nanoparticles by a nonhydrolytic sol-gel method

Indium tin oxide nanoparticles were synthesized in two different sizes by a nonhydrolytic sol-gel method. These powders were then transformed into ITO via an intermediate metastable state at between 300 and 600 ºC. The presence of characteristic O-In-O and O-Sn-O bands at 480 and 670 cm-1 confirmed the formation of ITO. The X-ray diffraction patterns indicated the preferential formation of metastable hexagonal phase ITO (corundum type) as opposed to cubic phase ITO when the reflux time was less than 3 h and the heat treatment temperature was below 600 ºC. Particle morphology and crystal size were examined by scanning electron microscopy.

Kinetics of oxidation of biodiesel from soybean oil mixed with TBHQ: determination of storage time

Synthetic antioxidants are an alternative to prevent or retard the degradation of biofuels made from vegetable oils. In this study, it was evaluated the oxidative stability of B100 soybean oil biodiesel, in the presence of tercbutylhydroquinone (TBHQ). The results showed that the induction period, that precedes the seeding process, was delayed in the presence of the antioxidant. Moreover, the obtained results suggest that the B100 biodiesel containing TBHQ can present a storage time at 25 ºC, three times longer than the estimated time for the pure B100.

Modification of the performance of WO3-ZrO2 catalysts by metal addition in hydrocarbon reactions

A study of the different hydrocarbon reactions over Ni doped WO3-ZrO2 catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane) increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition.

Palladium-supported catalysts in methane combustion: comparison of alumina and zirconia supports

Palladium catalysts supported on alumina and zirconia were prepared by the impregnation method and calcined at 600 and 1000 ºC. Catalysts were characterized by BET measurements, XRD, XPS, O2-TPD and tested in methane combustion through temperature programmed surface reaction. Alumina supported catalysts were slightly more active than zirconia supported catalysts, but after initial heat treatment at 1000 ºC, zirconia supported palladium catalyst showed better performance above 500 ºC A pattern between temperature interval stability of PdOx species and activity was observed, where better PdOx stability was associated with more active catalysts.

Alkaline earth layered benzoates as reusable heterogeneous catalysts for the methyl esterification of benzoic acid

This paper describes the synthesis and characterization of layered barium, calcium and strontium benzoates and evaluates the potential of these materials as catalysts in the synthesis of methyl benzoate. The methyl esterification of benzoic acid was investigated, where the effects of temperature, alcohol:acid molar ratio and amount of catalyst were evaluated. Ester conversions of 65 to 70% were achieved for all the catalysts under the best reaction conditions. The possibility of recycling these metallic benzoates was also demonstrated, evidenced by unaltered catalytic activity for three consecutive reaction cycles.

Basic properties of potassium oxide supported on zeolite y studied by pyrrole-tpd and catalytic conversion of methylbutynol

ABSTRACT We report on the basic properties of zeolite NaY and potassium supported on NaY (K/NaY) assessed by pyrrole-TPD and MBOH transformation. Pyrrole-TPD revealed that impregnation of zeolite NaY with potassium promoted additional adsorption sites for pyrrole compared to parent zeolite. For zeolite with various potassium loadings, pyrrole adsorbed on K/NaY decreased with increased potassium loading. Reduction in pyrrole adsorption could be due to potassium hindering intrinsic basic sites (lattice oxygen), to oxide of potassium occluding in zeolite cavities restricting access for pyrrole, or to K2O reacting with pyrrole to form nondesorbed pyrrolate anions. On MBOH transformation, potassium almost completely suppressed NaY acid sites while K/NaY basicity increased with potassium loading.

Nitrous oxide emissions from an intermittent aeration activated sludge system of an urban wastewater treatment plant

This study investigated the emission of N2O during the sequential aerated (60-min) and non-aerated (30-min) stages of an intermittent aeration cycle in an activated sludge wastewater treatment plant (WWTP). N2O emission occurred during both stages; however, emission was much higher during aeration. Air stripping is the major factor controlling transfer of N2O from the sewage to the atmosphere. The N2O emissions exclusively from the aeration tank represented 0.10% of the influent total nitrogen load and the per capita emission factor was almost 3 times higher than that suggested by the IPCC for inventories of N2O emission from WWTPs.

Development and validation of a dissolution test for primaquine/polyethylene oxide matrix tablets

A simple, precise, specific, repeatable and discriminating dissolution test for primaquine (PQ) matrix tablets was developed and validated according to ICH and FDA guidelines. Two UV assaying methods were validated for determination of PQ released in 0.1 M hydrochloric acid and water media. Both methods were linear (R²>0.999), precise (R.S.D.<1.87%) and accurate (97.65-99.97%). Dissolution efficiency (69-88%) and equivalence of formulations (f2) was assessed in different media and apparatuses (basket/100 rpm and paddle/50 rpm) tested. Discriminating condition was 900 mL aqueous medium, basket at 100 rpm and sampling times at 1, 4 and 8 h. Repeatability (R.S.D.<2.71%) and intermediate precision (R.S.D.<2.06%) of dissolution method were satisfactory.

Processing of spent NiW/Al2O3 catalysts

Spent oxidized (500 ºC, 5 h) commercial NiW/Al2O3 catalysts were processed using two different routes: a) fusion with NaOH (650 ºC, 1 h), the roasted mass was leached in water; b) leaching with HCl or H2SO4 (70 ºC, 1-3 h). HCl was the best leachant. In both routes, soluble tungsten was extracted at pH 1 with Alamine 336 (10 vol.% in kerosene) and stripped with 2 mol L-1 NH4OH (25 ºC, one stage, aqueous/organic ratio = 1 v/v). Tungsten was isolated as ammonium paratungstate at very high yield (> 97.5%). The elements were better separated using the acidic route.

Isomerization-cracking of n-octane on catalysts based on heteropolyacid H3Pw12O40 and heteropolyacid supported on zirconia and promoted with Pt and Cs

Isomerization - cracking of n-octane was studied using H3PW12O40 (HPA) and HPA supported on zirconia and promoted with Pt and Cs. The addition of Pt and Cs to the supported HPA did not modify the Keggin structure. The Pt addition to the supported HPA did not substantially modify the total acidity; however, the Brönsted acidity increased significantly. Cs increased the total acidity and Brönsted acidity. A linear relation was observed between the n-C8 total conversion and Brönsted acidity. The most adequate catalysts for performing isomerization and cracking to yield high research octane number (RON) are those with higher values of Brönsted acidity.