Oxidação úmida de fenóis com catalisadores de ferro suportado em argilominerais em reator de leito de lama (slurry)

The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ° C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved.

Analytical procedure based on slurry sampling for determining selenium in organic vegetable samples by graphite furnace atomic absorption spectrometry

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

GFAAS Determination of Zinc in Fish Feed and Feces Using Slurry Sampling

This paper presents a simple, fast, and sensitive method to determine zinc in samples of feces and fish feed by electrothermal atomic absorption spectrometry through the direct introduction of slurries of the samples into the spectrometer's graphite tube. The procedure is based on the injection of 10 mu L of an acidified aqueous solution containing 0.50% w/v of feces or feed and 0.50% v/v HNO(3) into graphite tube. The limits of detection and quantification calculated for 20 readings of the blank of the standard slurries (0.50% w/v of feces or feed devoid of zinc) were 0.04 and 0.13 mu g L(-1) for the standard feces slurries and 0.05 and 0.17 mu g L(-1) for the standard feed slurries. The proposed method was applied in studies of digestibility of zinc in different fish feeds, and their results proved compatible with that obtained from samples mineralized by acid digestion using microwave oven.

Simultaneous Determination of Cadmium and Lead in Medicinal Plants Using Graphite Furnace Atomic Absorption Spectrometry and Direct Slurry Sampling

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

Development and testing of anode-supported solid oxide fuel cells with slurry-coated electrolyte and cathode

A laboratory setup was designed and put into operation for the development of solid oxide fuel cells (SOFCs). The whole project consisted of the preparation of the component materials: anode, cathode and electrolyte, and the buildup of a hydrogen leaking-free sample chamber with platinum leads and current collectors for measuring the electrochemical properties of single SOFCs. Several anode-supported single SOFCs of the type (ZrO(2):Y(2)O(3)+NiO) thick anode/(ZrO(2):Y(2)O(3)) thin electrolyte/(La(0.65)Sr(0.35)MnO(3)+ZrO(2):Y(2)O(3)) thin cathode have been prepared and tested at 700 and 800 degrees C after in situ H(2) anode reduction. The main results show that the slurry-coating method resulted in single-cells with good reproducibility and reasonable performance, suggesting that this method can be considered for fabrication of SOFCs. (c) 2005 Elsevier B.V. All rights reserved.

Oxidation of p,p'-DDT and p,p'-DDE in highly and long-term contaminated soil using Fenton reaction in a slurry system

The degradation of DDT [1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane] and DDE [2,2-bis(4-chlorophenyl)-1,1-dichloroethylene] in highly and long-term contaminated soil using Fenton reaction in a slurry system is studied in this work. The influence of the amount of soluble iron added to the slurry versus the mineral iron originally present in the soil, and the influence of H2O2 concentration on the degradation process are evaluated. The main iron mineral species encountered in the soil, hematite (Fe2O3), did not show catalytic activity in the decomposition of H2O2, resulting in low degradation of DDT (24%) and DDE (4%) after 6 h. The addition of soluble iron (3.0 mmol L-1) improves the reaction reaching 53% degradation of DDT and 46% of DDE. The increase in iron concentration from 3.0 to 24 mmol L-1 improves slightly the degradation rate of the contaminants. However, similar degradation percentages were obtained after 24 h of reaction. It was observed that low concentrations of H2O2 were sufficient to degrade around 50% of the DDT and DDE present in the soil, while higher degradation percentages were achieved only with high amounts of this reagent (1.1 mol L-1). (c) 2006 Elsevier B.V. All rights reserved.

Joint (X)over-bar and R charts with two-stage samplings

When joint (X) over bar and R charts are in use, samples of fixed size are regularly taken from the process, and their means and ranges are plotted on the (X) over bar and R charts, respectively. In this article, joint (X) over bar and R charts have been used for monitoring continuous production processes. The sampling is performed, in two stages. During the first stage, one item of the sample is inspected and, depending on the result, the sampling is interrupted if the process is found to be in control; otherwise, it goes on to the second stage, where the remaining sample items are inspected. The two-stage sampling procedure speeds up the detection of process disturbances. The proposed joint (X) over bar and R charts are easier to administer and are more efficient than the joint (X) over bar and R charts with variable sample size where the quality characteristic of interest can be evaluated either by attribute or variable. Copyright (C) 2004 John Wiley Sons, Ltd.

The non-central chi-square chart with two-stage samplings

In this paper, we consider the non-central chi-square chart with two stage samplings. During the first stage, one item of the sample is inspected and, depending on the result, the sampling is either interrupted, or it goes on to the second stage, where the remaining sample items are inspected and the non-central chi-square statistic is computed. The proposed chart is not only more sensitive than the joint (X) over bar and R charts, but operationally simpler too, particularly when appropriate devices, such as go-no-go gauges, can be used to decide if the sampling should go on to the second stage or not. (c) 2004 Elsevier B.V. All rights reserved.

Sand-water slurry erosion of API 5L X65 pipe steel as quenched from intercritical temperature

The objective of this study was to analyze the erosion of API 5L X65 pipe steel whose microstructure consisted of ferrite and martensite obtained by quenching from intercritical temperature (770 °C). Jet impingement tests with sand-water slurry were used. The changes in mechanical properties, caused by heat treatment carried out, did not induce changes in either the mechanism or erosion resistance. The erosion rate increased with angle of attack until 30° and later decreased until 90°. The microtexture of the eroded surfaces, at angles of attack of 30° and 90°, were similar for both conditions and were composed of craters and platelets at several stages of evolution. The erosion mechanism was by extrusion with the forming and forging of platelets.

Mitigation of N2O emissions from grassland by nitrification inhibitor and actilith F2 applied with fertilizer and cattle slurry

Nitrous oxide (N2O) is involved in both ozone destruction and global warming. In agricultural soils it is produced by nitrification and denitrification mainly after fertilization. Nitrification inhibitors have been proposed as one of the management tools for the reduction of the potential hazards of fertilizer-derived N2O. Addition of nitrification inhibitors to fertilizers maintains soil N in ammonium form, thereby gaseous N losses by nitrification and denitrification are less likely to occur and there is increased N utilization by the sward. We present a study aimed to evaluate the effectiveness of the nitrification inhibitor dicyandiamide (DCD) and of the slurry additive Actilith F2 on N2O emissions following application of calcium ammonium nitrate or cattle slurry to a mixed clover/ryegrass sward in the Basque Country. The results indicate that large differences in N2O emission occur depending on fertilizer type and the presence or absence of a nitrification inhibitor. There is considerable scope for immediate reduction of emissions by applying DCD with calcium ammonium nitrate or cattle slurry. DCD, applied at 25 kg ha-1, reduced the amount of N lost as N2O by 60% and 42% when applied with cattle slurry and calcium ammonium nitrate, respectively. Actilith F2 did not reduce N2O emissions and it produced a long lasting mineralization of previously immobilized added N.

Flow evolution of a metallic slurry during thixoextrusion of an automotive valve

The aim of this work is to characterize a metallic slurry (Al-4.5%Cu) flow during thixoforming of an automotive valve. The necessary globular structure was obtained by first inoculating the alloy with TIBAL (5%Ti, 1%B, Al - rest) at 750.0°C, and then reheating to a state between liquidus and solidus prior to thixoforming. Two metallic slurries, with a solid phase of approximately 86.1 and 78.2 percent, were used to generate different experimental flow patterns during the thixoforming process. The flow of the material into the die was observed for total, and partial displacement (2.7, 5.4, 7.5mm) of the punch. The first displacement shows formation of the valve rod. The patterns at each step of displacement of the punch were preserved by quenching in water, thus revealing the profile of the die fill and microstructural evolution. Degeneration of the globular phase was observed along the piece thixoextruded. Thixoextrusion forces versus time curves were generated for partial and full displacement of the punch. Porosity was visible along the billet prior to thixoforming. However, some areas show that the porosity gradually decreased to zero as the thixoextrusion pressure increased. Turbulent, transient and laminar flow are analyzed in this work.

The no-central chi-square chart with two-stage samplings

Throughout this article, it is assumed that the no-central chi-square chart with two stage samplings (TSS Chisquare chart) is employed to monitor a process where the observations from the quality characteristic of interest X are independent and identically normally distributed with mean μ and variance σ2. The process is considered to start with the mean and the variance on target (μ = μ0; σ2 = σ0 2), but at some random time in the future an assignable cause shifts the mean from μ0 to μ1 = μ0 ± δσ0, δ >0 and/or increases the variance from σ0 2 to σ1 2 = γ2σ0 2, γ > 1. Before the assignable cause occurrence, the process is considered to be in a state of statistical control (defined by the in-control state). Similar to the Shewhart charts, samples of size n 0+ 1 are taken from the process at regular time intervals. The samplings are performed in two stages. At the first stage, the first item of the i-th sample is inspected. If its X value, say Xil, is close to the target value (|Xil-μ0|< w0σ 0, w0>0), then the sampling is interrupted. Otherwise, at the second stage, the remaining n0 items are inspected and the following statistic is computed. Wt = Σj=2n 0+1(Xij - μ0 + ξiσ 0)2 i = 1,2 Let d be a positive constant then ξ, =d if Xil > 0 ; otherwise ξi =-d. A signal is given at sample i if |Xil-μ0| > w0σ 0 and W1 > knia:tl, where kChi is the factor used in determining the upper control limit for the non-central chi-square chart. If devices such as go and no-go gauges can be considered, then measurements are not required except when the sampling goes to the second stage. Let P be the probability of deciding that the process is in control and P 1, i=1,2, be the probability of deciding that the process is in control at stage / of the sampling procedure. Thus P = P1 + P 2 - P1P2, P1 = Pr[μ0 - w0σ0 ≤ X ≤ μ0+ w 0σ0] P2=Pr[W ≤ kChi σ0 2], (3) During the in-control period, W / σ0 2 is distributed as a non-central chi-square distribution with n0 degrees of freedom and a non-centrality parameter λ0 = n0d2, i.e. W / σ0 2 - xn0 22 (λ0) During the out-of-control period, W / σ1 2 is distributed as a non-central chi-square distribution with n0 degrees of freedom and a non-centrality parameter λ1 = n0(δ + ξ)2 / γ2 The effectiveness of a control chart in detecting a process change can be measured by the average run length (ARL), which is the speed with which a control chart detects process shifts. The ARL for the proposed chart is easily determined because in this case, the number of samples before a signal is a geometrically distributed random variable with parameter 1-P, that is, ARL = I /(1-P). It is shown that the performance of the proposed chart is better than the joint X̄ and R charts, Furthermore, if the TSS Chi-square chart is used for monitoring diameters, volumes, weights, etc., then appropriate devices, such as go-no-go gauges can be used to decide if the sampling should go to the second stage or not. When the process is stable, and the joint X̄ and R charts are in use, the monitoring becomes monotonous because rarely an X̄ or R value fall outside the control limits. The natural consequence is the user to pay less and less attention to the steps required to obtain the X̄ and R value. In some cases, this lack of attention can result in serious mistakes. The TSS Chi-square chart has the advantage that most of the samplings are interrupted, consequently, most of the time the user will be working with attributes. Our experience shows that the inspection of one item by attribute is much less monotonous than measuring four or five items at each sampling.

Slurry sample injection for determination of ferrite nanocolloids chemical composition by ICP spectrometry

This work proposes a new method to determine the chemical composition of magnetic ferrite nanoparticles by the slurry injection technique using the inductively coupled plasma optical emission spectroscopy. In this way, experimental conditions such as aerosol gas flow rate and colloidal stability were optimized in order to use aqueous calibration curves in the slurry nebulization and to determine the chemical composition of a series of sols containing chemically synthesized size-tailored NiFe 2O 4 nanograms. Then, the results of direct sampling and those of conventional aqueous introduction analysis are compared, showing the efficiency of the proposed method.

Sequential Determination of Cd, Cu and Pb in Tea Leaves by Slurry Introduction to Thermospray Flame Furnace Atomic Absorption Spectrometry

A simple procedure for the sequential determination of Cd, Cu and Pb in tea leaves by slurry introduction to thermospray flame furnace atomic absorption spectrometry was developed. Detection limits were 0.05 mg kg-1 for Cd, 2.1 mg kg-1 for Cu and 0.68 mg kg-1 for Pb using 0.67 % (m/v) slurries (100 mg/15 mL). © 2013 Springer Science+Business Media New York.

Simultaneous determination of chromium and nickel in medicinal plants by slurry sampling graphite furnace atomic absorption spectrometry

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