PPO Reaction Scale-up

O óxido de polifenileno com a marca comercial PPO® é uma das resinas principais produzidas na SABIC IP e o ingrediente principal do plástico de engenharia com a marca registada, Noryl®. A equipa de tecnologia de processo de PPO® desenvolve uma série de novos produtos em reactores de pequena escala, tanto em Selkirk como em Bergen op Zoom. Para se efectuar uma transição rápida da escala laboratorial para a fábrica, é necessário um conhecimento completo do reactor. O objectivo deste projecto consiste em esboçar linhas gerais para o scale-up de novos produtos de PPO1, do laboratório para a escala industrial, baseado no estudo de um tipo de PPO, PPO 803. Este estudo pode ser dividido em duas fases. Numa primeira fase, as receitas e os perfis da reacção são comparados, de onde se retiram as primeiras conclusões. Posteriormente, com base nestas conclusões, é realizado um planeamento experimental. O estudo inicial sugeriu que a receita, a temperatura inicial do reactor e a velocidade do agitador poderiam influenciar o tempo da reacção bem como a queda da velocidade intrínseca do polímero (IV drop). As reacções experimentais mostraram que a receita é o principal factor que influencia, tanto o tempo de reacção, como a queda de viscosidade intrínseca. O tempo de reacção será tanto maior quanto menor a agitação devido à má dispersão do oxigénio na mistura. O uso de temperaturas iniciais elevadas conduz a uma queda maior da viscosidade intrínseca devido à desactivação do catalisador. O método experimental utilizado no laboratório de Bergen op Zoom é um bom exemplo, simulador, do procedimento utilizado na fábrica.

Square-wave adsorptive-stripping voltammetric detection in the quality control of fluoxetine

Electroanalytical methods based on square-wave adsorptive-stripping voltammetry (SWAdSV) and flow-injection analysis with square-wave adsorptive-stripping voltammetric detection (FIA-SWAdSV) were developed for the determination of fluoxetine (FXT). The methods were based on the reduction of FXT at a mercury drop electrode at -1.2 V versus Ag/AgCl, in a phosphate buffer of pH 12.0, and on the possibility of accumulating the compound at the electrode surface. The SWAdSV method was successfully applied in the quantification of FXT in pharmaceutical products, human serum samples, and in drug dissolution studies. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was possible to quantify FXT in several pharmaceutical products using FIA-SWAdSV. This method enables analysis of up to 120 samples per hour at reduced costs.

Nova metodologia de execução do ensaio SCPTu com avaliação da influência da fonte sísmica quanto à sua dimensão e afastamento

O objectivo deste trabalho consiste na determinação das Ondas de Corte, onda S, através de uma nova metodologia de ensaio do piezocone sísmico, SCPTu. A nova metodologia adoptada de aquisição de dados, consiste na aquisição da onde de corte no movimento ascendente de remoção de varas, após execução do já conhecido ensaio CPTu, ao invés da tradicional aquisição, no movimento descendente, previamente ao acréscimo de nova vara. Além da introdução de uma nova metodologia de aquisição sísmica, tentou-se avaliar a influência da dimensão da fonte geradora da onda de corte e a influência do afastamento das mesmas ao ponto de cravação, do ensaio de penetração estática mencionado. Na avaliação das influências foram usadas três fontes de madeira de secção rectangular, com uma chapa de ferro a topo e diferenciadas entre si pelas dimensões de 1m, 2m e 3m e afastamentos até 4m.

Optimização do corte de chapas

O presente trabalho visa denotar a importância de ferramentas e técnicas utilizadas como apoio à tomada de decisão. Foi proposto um problema de corte cujo objectivo primordial procura minimizar o desperdício gerado resultante do processo de obtenção de um produto, utilizando um caso representativo de um produto em chapa, fabricado por uma empresa que conta três décadas de laboração contínua, proposeram-se e realizaram-se estudos no sentido de solucionar recursos causadores de desperdício. Neste trabalho aplicou-se um problema de corte bi-dimensional a uma indústria que recorre ao fabrico de produtos em chapa, por forma a minimizar o desperdício relativo ao processo utilizado. Propôs-se quatro alternativas à solução actual realizada na empresa, que passa pela disposição e combinação de vários tipos de cortes-padrão que podem ser executados nas diferentes dimensões de matéria-prima disponibilizada. Estas alternativas têm como vantagem apresentar reduções que se traduzam significativas para os custos implícitos à realização do processo produtivo. Os estudos computacionais praticados mostraram que as soluções propostas como alternativa obtiveram melhores resultados que os obtidos pela empresa, excepto num caso.

Voltammetric oxidation of drugs of abuse III. Heroin and metabolites

The oxidative behavior of heroin in aqueous solution is reported. In order to identify its oxidation peaks, several metabolites, 6-monoacetylmorphine, 3-monoacetylmorphine and norheroin, were synthesized and their electrochemical behavior studied using differential pulse voltammetry. The anodic waves observed for heroin correspond to the oxidation of the tertiary amine group and its follow-up product (secondary amine), and to the oxidation of the phenolic group obtained from hydrolysis, at alkaline pHs, of the 3-acetyl group. The results enabled a new oxidative mechanism for heroin to be proposed in which a secondary amine, norheroin, and an aldehyde are obtained. The voltammetric behavior of 6-monoacetylmorphine and morphine was found to be similar demonstrating that the presence of an acetyl substituent on the 6-hydroxy group does not have a relevant influence on the peak potential of the wave resulting from oxidation of the 3-phenolic group.

Square-wave voltametric method for determination of molinate concentration in a biological process using a hanging mercury drop electrode

A square-wave voltammetric (SWV) method using a hanging mercury drop electrode (HMDE) has been developed for determination of the herbicide molinate in a biodegradation process. The method is based on controlled adsorptive accumulation of molinate for 10 s at a potential of -0.8 V versus AgCl/Ag. An anodic peak, due to oxidation of the adsorbed pesticide, was observed in the cyclic voltammogram at ca. -0.320 V versus AgCl/Ag; a very small cathodic peak was also detected. The SWV calibration plot was established to be linear in the range 5.0x10-6 to 9.0x10-6 mol L-1; this corresponded to a detection limit of 3.5x10-8 mol L-1. This electroanalytical method was used to monitor the decrease of molinate concentration in river waters along a biodegradation process using a bacterial mixed culture. The results achieved with this voltammetric method were compared with those obtained by use of a chromatographic method (HPLC–UV) and no significant statistical differences were observed.

Electroanalytical study of fluvoxamine

Fluvoxamine (FVX) can be reduced at a mercury- drop electrode, with a maximum peak current intensity being obtained at a potential of -0.7 V vs. Ag/ AgCl, in an aqueous electrolyte solution of pH 2. The compound was determined in a pharmaceutical product and in spiked human serum by square-wave adsorptivestripping voltammetry (SWAdSV) after accumulation at the electrode surface, under batch conditions. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was also possible to determine FVX in the pharmaceutical product by use of a flow-injection analysis (FIA) system with SWAdSV detection. The methods developed were validated and successfully applied to the quantification of FVX in a pharmaceutical product. Recoveries between 76 and 89% were obtained in serum analysis. The FIA– SWAdSV method enabled analysis of up to 120 samples per hour at reduced cost, implying the possibility of competing with the chromatographic methods usually used for this analysis.

Electroanalytical determination of paroxetine in pharmaceuticals

Electroanalytical methods based on square-wave adsorptive-stripping voltammetry (SWAdSV) and flow-injection analysis with SWAdSV detection (FIA-SWAdSV) were developed for the determination of paroxetine (PRX). The methods were based on the reduction of PRX at a mercury drop electrode at −1.55V versus Ag/AgCl, in a borate buffer of pH 8.8, and the possibility of accumulating the compound at the electrode surface. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was also possible to determine PRX using FIASWAdSV. This method enables analysis of up to 120 samples per hour at reduced costs. Both methods developed were validated and successfully applied to the quantification of PRX in pharmaceutical products.

Soil remediation time to achieve clean-up goals I: influence of soil water content

The current models are not simple enough to allow a quick estimation of the remediation time. This work reports the development of an easy and relatively rapid procedure for the forecasting of the remediation time using vapour extraction. Sandy soils contaminated with cyclohexane and prepared with different water contents were studied. The remediation times estimated through the mathematical fitting of experimental results were compared with those of real soils. The main objectives were: (i) to predict, through a simple mathematical fitting, the remediation time of soils with water contents different from those used in the experiments; (ii) to analyse the influence of soil water content on the: (ii1) remediation time; (ii2) remediation efficiency; and (ii3) distribution of contaminants in the different phases present into the soil matrix after the remediation process. For sandy soils with negligible contents of clay and natural organic matter, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) if the soil water content belonged to the range considered in the experiments with the prepared soils, then the remediation time of real soils of similar characteristics could be successfully predicted, with relative differences not higher than 10%, through a simple mathematical fitting of experimental results; (ii) increasing soil water content from 0% to 6% had the following consequences: (ii1) increased remediation time (1.8–4.9 h, respectively); (ii2) decreased remediation efficiency (99–97%, respectively); and (ii3) decreased the amount of contaminant adsorbed onto the soil and in the non-aqueous liquid phase, thus increasing the amount of contaminant in the aqueous and gaseous phases.

Soil remediation time to achieve clean-up goals II: influence of natural organic matter and water contents

This work reports a relatively rapid procedure for the forecasting of the remediation time (RT) of sandy soils contaminated with cyclohexane using vapour extraction. The RT estimated through the mathematical fitting of experimental results was compared with that of real soils. The main objectives were: (i) to predict the RT of soils with natural organic matter (NOM) and water contents different from those used in experiments; and (ii) to analyse the time and efficiency of remediation, and the distribution of contaminants into the soil matrix after the remediation process, according to the soil contents of: (ii1) NOM; and (ii2) water. For sandy soils with negligible clay contents, artificially contaminated with cyclohexane before vapour extraction, it was concluded that: (i) if the NOM and water contents belonged to the range of the prepared soils, the RT of real soils could be predicted with relative differences not higher than 12%; (ii1) the increase of NOM content from 0% to 7.5% increased the RT (1.8–13 h) and decreased the remediation efficiency (RE) (99–90%) and (ii2) the increase of soil water content from 0% to 6% increased the RT (1.8–4.9 h) and decreased the RE (99–97%). NOM increases the monolayer capacity leading to a higher sorption into the solid phase. Increasing of soil water content reduces the mass transfer coefficient between phases. Concluding, NOM and water contents influence negatively the remediation process, turning it less efficient and more time consuming, and consequently more expensive.

Screening of grapes and wine for azoxystrobin, kresoxim-methyl and trifloxystrobin fungicides by HPLC with diode array detection

The Quinone outside Inhibitors (QoI) are one of the most important and recent fungicide groups used in viticulture and also allowed by Integrated Pest Management. Azoxystrobin, kresoxim-methyl and trifloxystrobin are the main active ingredients for treating downy and powdery mildews that can be present in grapes and wines. In this paper, a method is reported for the analysis of these three QoI-fungicides in grapes and wine. After liquid–liquid extraction and a clean-up on commercial silica cartridges, analysis was by isocratic HPLC with diode array detection (DAD) with a run time of 13 min. Confirmation was by solid-phase micro-extraction (SPME), followed by GC/MS determination. The main validation parameters for the three compounds in grapes and wine were a limit of detection up to 0.073mg kg-1, a precision not exceeding 10.0% and an average recovery of 93% ±38.

Biocomplementation of SVE to achieve clean-up goals in soils contaminated with toluene and xylene

Soil vapor extraction (SVE) and bioremediation (BR) are two of the most common soil remediation technologies. Their application is widespread; however, both present limitations, namely related to the efficiencies of SVE on organic soils and to the remediation times of some BR processes. This work aimed to study the combination of these two technologies in order to verify the achievement of the legal clean-up goals in soil remediation projects involving seven different simulated soils separately contaminated with toluene and xylene. The remediations consisted of the application of SVE followed by biostimulation. The results show that the combination of these two technologies is effective and manages to achieve the clean-up goals imposed by the Spanish Legislation. Under the experimental conditions used in this work, SVE is sufficient for the remediation of soils, contaminated separately with toluene and xylene, with organic matter contents (OMC) below 4 %. In soils with higher OMC, the use of BR, as a complementary technology, and when the concentration of contaminant in the gas phase of the soil reaches values near 1 mg/L, allows the achievement of the clean-up goals. The OMC was a key parameter because it hindered SVE due to adsorption phenomena but enhanced the BR process because it acted as a microorganism and nutrient source.

Local fractional variational iteration and decomposition methods for wave equation on cantor sets within local fractional operators

We perform a comparison between the fractional iteration and decomposition methods applied to the wave equation on Cantor set. The operators are taken in the local sense. The results illustrate the significant features of the two methods which are both very effective and straightforward for solving the differential equations with local fractional derivative.

Run-time monitoring in real-time operating systems

Embedded systems are increasingly complex and dynamic, imposing progressively higher developing time and costs. Tuning a particular system for deployment is thus becoming more demanding. Furthermore when considering systems which have to adapt themselves to evolving requirements and changing service requests. In this perspective, run-time monitoring of the system behaviour becomes an important requirement, allowing to dynamically capturing the actual scheduling progress and resource utilization. For this to succeed, operating systems need to expose their internal behaviour and state, making it available to external applications, and a runtime monitoring mechanism must be available. However, such mechanism can impose a burden in the system itself if not wisely used. In this paper we explore this problem and propose a framework, which is intended to provide this run-time mechanism whilst achieving code separation, run-time efficiency and flexibility for the final developer.