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.

Dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous separation/preconcentration of nickel, cobalt and copper prior to determination by electrothermal atomic absorption spectrometry

A dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous extraction of trace amounts of nickel, cobalt and copper followed by their determination with electrothermal atomic absorption spectrometry was developed. 300 µL of acetone and 1-undecanol was injected into an aqueous sample containing diethyldithiocarbamate complexes of metal ions. For a sample volume of 10 mL, enrichment factors of 277, 270 and 300 and detection limits of 1.2, 1.1 and 1 ng L-1 for nickel, cobalt and copper were obtained, respectively. The method was applied to the extraction and determination of these metals in different water samples.

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.

Kinetical study about the cobalt electrodeposition onto polycrystalline platinum

An electrochemical study of Co electrodeposition onto polycrystalline Pt from an aqueous solution containing 10-2 M CoCl2 + 1 M NH4CI (pH = 9.3) was conducted at overpotential conditions. The current density transients showed two maxima that corresponded to two nucleation and growth processes. The entire transient behavior was adequately predicted considering the contribution to the total current of four different processes: a Langmuir-type adsorption process, a diffusion-controlled two-dimensional instantaneous nucleation, and two three-dimensional nucleation and growth processes.

Catálise assimétrica no Brasil: desenvolvimento e potencialidades para o avanço da indústria química brasileira

The preparation of enantiomerically pure or enriched substances is of fundamental importance to pharmaceutical, food, agrochemical, and cosmetics industries and involves a growing market of hundreds of billions of dollars. However, most chemical processes used for their production are not environmentally friendly because in most cases, stoichiometric amounts of chiral inductors are used and substantial waste is produced. In this context, asymmetric catalysis has emerged as an efficient tool for the synthesis of enantiomerically enriched compounds using chiral catalysts. More specifically, considering the current scenario in the Brazilian chemical industry, especially that of pharmaceuticals, the immediate prospect for the use of synthetic routes developed in Brazil in an enantioselective fashion or even the discovery of new drugs is practically null. Currently, the industrial production of drugs in Brazil is primarily focused on the production of generic drugs and is basically supported by imports of intermediates from China and India. In order to change this panorama and move forward toward the gradual incorporation of genuinely Brazilian synthetic routes, strong incentive policies, especially those related to continuous funding, will be needed. These incentives could be a breakthrough once we establish several research groups working in the area of organic synthesis and on the development and application of chiral organocatalysts and ligands in asymmetric catalysis, thus contributing to boost the development of the Brazilian chemical industry. Considering these circumstances, Brazil can benefit from this opportunity because we have a wide biodiversity and a large pool of natural resources that can be used as starting materials for the production of new chiral catalysts and are creating competence in asymmetric catalysis and related areas. This may decisively contribute to the growth of chemistry in our country.

Advances in ethanol reforming for the production of hydrogen

Catalytic steam reforming of ethanol (SRE) is a promising route for the production of renewable hydrogen (H2). This article reviews the influence of doping supported-catalysts used in SRE on the conversion of ethanol, selectivity for H2, and stability during long reaction periods. In addition, promising new technologies such as membrane reactors and electrochemical reforming for performing SRE are presented.

Estudo de catalisadores de níquel suportados em cinza de casca de arroz na reforma de metano com dióxido de carbono visando a produção de hidrogênio e gás de síntese

Rice husk ash (RHA) is used as a silica source for several purposes, among them to obtain metal catalysts, as was done in this work. The catalysts were characterized by chemisorption, physisorption, thermal analyses (TG, DSC), X-ray diffraction, X-ray fluorescence, temperature-programmed reduction and scanning electron microscopy. The catalysts synthesized with different Ni loadings supported on RHA were applied to the reaction of dry reforming of methane. The reaction was tested at three temperatures of catalytic reduction (500, 600 and 700 ºC). All synthesized catalysts were active for the studied reaction, with different H2/CO ratios achieved according to degree of metallic dispersion.

SYNGAS PRODUCTION FROM CO2-REFORMING OF CH4 OVER SOL-GEL SYNTHESIZED Ni-Co/Al2O3-MgO-ZrO2 NANOCATALYST: EFFECT OF ZrO2 PRECURSOR ON CATALYST PROPERTIES AND PERFORMANCE

Ni-Co/Al2O3-MgO-ZrO2 nanocatalyst with utilization of two different zirconia precursors, namely, zirconyl nitrate hydrate (ZNH) and zirconyl nitrate solution (ZNS), was synthesized via the sol-gel method. The physiochemical properties of nanocatalysts were characterized by XRD, FESEM, EDX, BET and FTIR analyses and employed for syngas production from CO2-reforming of CH4. XRD patterns, exhibiting proper crystalline structure and homogeneous dispersion of active phase for the nanocatalyst ZNS precursor employed (NCAMZ-ZNS). FESEM and BET results of NCAMZ-ZNS presented more uniform morphology and smaller particle size and consequently higher surface areas. In addition, average particle size of NCAMZ-ZNS was 15.7 nm, which is close to the critical size for Ni-Co catalysts to avoid carbon formation. Moreover, FESEM analysis indicated both prepared samples were nanoscale. EDX analysis confirmed the existence of various elements used and also supported the statements made in the XRD and FESEM analyses regarding dispersion. Based on the excellent physiochemical properties, NCAMZ-ZNS exhibited the best reactant conversion across all of the evaluated temperatures, e.g. CH4 and CO2 conversions were 97.2 and 99% at 850 ºC, respectively. Furthermore, NCAMZ-ZNS demonstrated a stable yield with H2/CO close to unit value during the 1440 min stability test.

Thermoanalytical study of the complexes of 4-dimetilaminocinnamylidenepiruvate with manganese (II), cobalt (II), nickel (II), cupper (II), zinc (II) and lead (II), in the solid state

Solid state compounds M-4-DMCP, where 4-DMCP is 4-dimethylaminocinnamylidenepyruvate and M represents Mn (II), Co (II), Ni (II), Cu (II), Zn (II) and Pb (II) were prepared. These compounds were studied by thermoanalitycal techniques: thermogravimetry (TG), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), X-ray diffraction powder patterns and complexometric titration with EDTA. From the results obtained by the complexometric titration with EDTA, TG, DTG and DSC curves, was possible to establish the hydration degree, stoichiometry and thermal stability of the prepared compounds.

Use of experimental design in the optimisation of a solid phase preconcentration system for Cobalt determination by GFAAS

In this work is proposed a solid phase preconcentration system of Co2+ ions and its posterior determination by GFAAS in which fractional factorial design and response surface methodology (RSM) were used for optimization of the variables associated with preconcentration system performance. The method is based on cobalt extraction as a complex Co2+-PAN (1:2) in a mini-column of polyurethane foam (PUF) impregnated with 1-(2-pyridylazo)-naphthol (PAN) followed by elution with HCl solution and its determination by GFAAS. The chemical and flow variables studied were pH, buffer concentration, eluent concentration and preconcentration and elution flow rates. Results obtained from fractional factorial design 2(5-1) showed that only the variables pH, buffer concentration and interaction (pH X buffer concentration) based on analysis of variance (ANOVA) were statistically significant at 95% confidence level. Under optimised conditions, the method provided an enrichment factor of 11.6 fold with limit of detection and quantification of 38 and 130 ng L-1, respectively, and linear range varying from 0.13 to 10 µg L-1. The precision (n = 9) assessed by relative standard deviation (RSD) was respectively 5.18 and 2.87% for 0.3 and 3.0 µg L-1 cobalt concentrations.

Numerical study of wedge supported oblique shock wave-oblique detonation wave transitions

The results of a numerical study of premixed Hydrogen-air flows ignition by an oblique shock wave (OSW) stabilized by a wedge are presented, in situations when initial and boundary conditions are such that transition between the initial OSW and an oblique detonation wave (ODW) is observed. More precisely, the objectives of the paper are: (i) to identify the different possible structures of the transition region that exist between the initial OSW and the resulting ODW and (ii) to evidence the effect on the ODW of an abrupt decrease of the wedge angle in such a way that the final part of the wedge surface becomes parallel to the initial flow. For such a geometrical configuration and for the initial and boundary conditions considered, the overdriven detonation supported by the initial wedge angle is found to relax towards a Chapman-Jouguet detonation in the region where the wedge surface is parallel to the initial flow. Computations are performed using an adaptive, unstructured grid, finite volume computer code previously developed for the sake of the computations of high speed, compressible flows of reactive gas mixtures. Physico-chemical properties are functions of the local mixture composition, temperature and pressure, and they are computed using the CHEMKIN-II subroutines.

Measurement of epidermal thickness in a patient with psoriasis by computer-supported image analysis

The aim of the present study was to measure full epidermal thickness, stratum corneum thickness, rete length, dermal papilla widening and suprapapillary epidermal thickness in psoriasis patients using a light microscope and computer-supported image analysis. The data obtained were analyzed in terms of patient age, type of psoriasis, total body surface area involvement, scalp and nail involvement, duration of psoriasis, and family history of the disease. The study was conducted on 64 patients and 57 controls whose skin biopsies were examined by light microscopy. The acquired microscopic images were transferred to a computer and measurements were made using image analysis. The skin biopsies, taken from different body areas, were examined for different parameters such as epidermal, corneal and suprapapillary epidermal thickness. The most prominent increase in thickness was detected in the palmar region. Corneal thickness was more pronounced in patients with scalp involvement than in patients without scalp involvement (t = -2.651, P = 0.008). The most prominent increase in rete length was observed in the knees (median: 491 µm, t = 10.117, P = 0.000). The difference in rete length between patients with a positive and a negative family history was significant (t = -3.334, P = 0.03), being 27% greater in psoriasis patients without a family history. The differences in dermal papilla distances among patients were very small. We conclude that microscope-supported thickness measurements provide objective results.