Treatment of Aqueous Effluents Containing Phenol by the O(3), O(3)-UV, and O(3)-H(2)O(2) Processes: Experimental Study and Neural Network Modeling

In this work, the oxidation of the model pollutant phenol has been studied by means of the O(3), O(3)-UV, and O(3)-H(2)O(2) processes. Experiments were carried out in a fed-batch system to investigate the effects of initial dissolved organic carbon concentration, initial, ozone concentration in the gas phase, the presence or absence of UVC radiation, and initial hydrogen peroxide concentration. Experimental results were used in the modeling of the degradation processes by neural networks in order to simulate DOC-time profiles and evaluate the relative importance of process variables.

A dynamic model with on-line identification for rotary sugar drying processes

A dynamic modelling methodology, which combines on-line variable estimation and parameter identification with physical laws to form an adaptive model for rotary sugar drying processes, is developed in this paper. In contrast to the conventional rate-based models using empirical transfer coefficients, the heat and mass transfer rates are estimated by using on-line measurements in the new model. Furthermore, a set of improved sectional solid transport equations with localized parameters is developed in this work to reidentified on-line using measurement data, the model is able to closely track the dynamic behaviour of rotary drying processes within a broad range of operational conditions. This adaptive model is validated against experimental data obtained from a pilot-scale rotary sugar dryer. The proposed modelling methodology can be easily incorporated into nonlinear model based control schemes to form a unified modelling and control framework.place the global correlation for the computation of solid retention time. Since a number of key model variables and parameters are identified on-line using measurement data, the model is able to closely track the dynamic behaviour of rotary drying processes within a broad range of operational conditions. This adaptive model is validated against experimental data obtained from a pilot-scale rotary sugar dryer. The proposed modelling methodology can be easily incorporated into nonlinear model based control schemes to form a unified modelling and control framework.

One-pot enzymatic resolution/separation of enantiomers using green solvents

Dissertação para obtenção do Grau de Mestre em Biotecnologia

Using relational algebra on the specification of real world ETL processes

Modeling Extract-Transform-Load (ETL) processes of a Data Warehousing System has always been a challenge. The heterogeneity of the sources, the quality of the data obtained and the conciliation process are some of the issues that must be addressed in the design phase of this critical component. Commercial ETL tools often provide proprietary diagrammatic components and modeling languages that are not standard, thus not providing the ideal separation between a modeling platform and an execution platform. This separation in conjunction with the use of standard notations and languages is critical in a system that tends to evolve through time and which cannot be undermined by a normally expensive tool that becomes an unsatisfactory component. In this paper we demonstrate the application of Relational Algebra as a modeling language of an ETL system as an effort to standardize operations and provide a basis for uncommon ETL execution platforms.

Nonsolvent induced phase separation preparation of poly(vinylidene fluoride-co-chlorotrifluoroethylene) membranes with tailored morphology, piezoelectric phase content and mechanical properties

Poly(vinylidene fluoride-co-chlorotrifluoroethylene) – P(VDF-CTFE) membranes are increasingly interesting for a wide range of applications, including battery separators, filtration membranes and biomedical applications. This work reports on the morphology, hydrophobicity, thermal and mechanical properties variation of P(VDF-CTFE) membranes processed by nonsolvent induced phase separation technique (NIPS) as a function of the main processing parameters. All membranes show a porous structure composed of large spherulites, (interconnected) micropores and/or microvoids depending on the processing conditions used that in turn affect their hydrophobicity and mechanical properties. The degree of crystallinity of the membranes remains approximately constant with a value of about 15 %, except for the membranes immediately immersed in ethanol, which is of about 23 %. In turn, the crystalline phases present in the copolymer is mainly affected by the temperature and nonsolvent characteristics of the coagulation bath, the β-phase content ranging from 33 to 100 %, depending on those processing parameters. It was show that the temperature of water-based coagulation bath plays an important role in order to produce structurally uniform and homogeneous porous membranes, which is particularly important from the point of view of technological applications.

Protein recovery, separation and purification: selection of optimal techniques using an expert system

The paper discusses the utilization of new techniques ot select processes for protein recovery, separation and purification. It describesa rational approach that uses fundamental databases of proteins molecules to simplify the complex problem of choosing high resolution separation methods for multi component mixtures. It examines the role of modern computer techniques to help solving these questions.

Separation of ammonia and carbon dioxide by adsorption

Tässä työssä on tutkittu ammoniakin ja hiilidioksidin erottamista adsorptio prosessilla ja suunniteltiin paineen muunteluun perustuvan adsorptioprosessin (PSA) käyttöä. Työn tarkoituksena oli laskea adsorptioon perustuvan prosessin kannattavuus melamiinitehtaan poistokaasujen erotuksessa. Tätä varten työssä suunniteltiin tehdasmitta-kaavainen prosessi ja arvioitiin sen kannattavuus. Työssä mitattiin adsorptiotasapainot, joiden perusteella sovitettiin sopiva kokeellinen adsorptioisotermi. Adsorptioisotermi lisättiin simulointiohjelmaan, jonka avulla suunniteltiin kaksi vaihtoehtoista pilot laitteistoa kaasujen erottamiseksi. Toisella pilot laitteistolla saadaan mitattua vain läpäisykäyrät, mutta paremmalla versiolla saadaan myös tietoa erotettujen komponenttien puhtaudesta. Suunnittelun tärkeimpiä lähtökohtia on molempien komponenttien mahdollisimman korkea puhtaus ja talteenottoaste. Täysimittakaavainen tehdas suunniteltiin simulointiohjelmiston avulla kahdelle eri kapasiteetille ja arvioitiin niiden kustannukset ja kannattavuus. Adsorptioprosessit osoittautuivat kannattaviksi kaasuseoksen erottamisessa kummassakin tapauksessa

Source separation techniques applied to linear prediction

The prediction filters are well known models for signal estimation, in communications, control and many others areas. The classical method for deriving linear prediction coding (LPC) filters is often based on the minimization of a mean square error (MSE). Consequently, second order statistics are only required, but the estimation is only optimal if the residue is independent and identically distributed (iid) Gaussian. In this paper, we derive the ML estimate of the prediction filter. Relationships with robust estimation of auto-regressive (AR) processes, with blind deconvolution and with source separation based on mutual information minimization are then detailed. The algorithm, based on the minimization of a high-order statistics criterion, uses on-line estimation of the residue statistics. Experimental results emphasize on the interest of this approach.

The Role of Surfactant Properties of Extractants in Hydrometallurgical LiquidLiquid Extraction Processes

The amphiphilic nature of metal extractants causes the formation of micelles and other microscopic aggregates when in contact with water and an organic diluent. These phenomena and their effects on metal extraction were studied using carboxylic acid (Versatic 10) and organophosphorus acid (Cyanex 272) based extractants. Special emphasis was laid on the study of phase behaviour in a pre neutralisation stage when the extractant is transformed to a sodium or ammonium salt form. The pre neutralised extractants were used to extract nickel and to separate cobalt and nickel. Phase diagrams corresponding to the pre neutralisation stage in a metal extraction process were determined. The maximal solubilisation of the components in the system water(NH3)/extractant/isooctane takes place when the molar ratio between the ammonia salt form and the free form of the extractant is 0.5 for the carboxylic acid and 1 for the organophosphorus acid extractant. These values correspond to the complex stoichiometry of NH4A•HA and NIi4A, respectively. When such a solution is contacted with water a microemulsion is formed. If the aqueous phase contains also metal ions (e.g. Ni²+), complexation will take place on the microscopic interface of the micellar aggregates. Experimental evidence showing that the initial stage of nickel extraction with pre neutralised Versatic 10 is a fast pseudohomogeneous reaction was obtained. About 90% of the metal were extracted in the first 15 s after the initial contact. For nickel extraction with pre neutralised Versatic 10 it was found that the highest metal loading and the lowest residual ammonia and water contents in the organic phase are achieved when the feeds are balanced so that the stoichiometry is 2NH4+(org) = Nit2+(aq). In the case of Co/Ni separation using pre neutralised Cyanex 272 the highest separation is achieved when the Co/extractant molar ratio in the feeds is 1 : 4 and at the same time the optimal degree of neutralisation of the Cyanex 272 is about 50%. The adsorption of the extractants on solid surfaces may cause accumulation of solid fine particles at the interface between the aqueous and organic phases in metal extraction processes. Copper extraction processes are known to suffer of this problem. Experiments were carried out using model silica and mica particles. It was found that high copper loading, aromacity of the diluent, modification agents and the presence of aqueous phase decrease the adsorption of the hydroxyoxime on silica surfaces.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

On the numerical simulation of machining processes

Numerical simulation of machining processes can be traced back to the early seventies when finite element models for continuous chip formation were proposed. The advent of fast computers and development of new techniques to model large plastic deformations have favoured machining simulation. Relevant aspects of finite element simulation of machining processes are discussed in this paper, such as solution methods, material models, thermo-mechanical coupling, friction models, chip separation and breakage strategies and meshing/re-meshing strategies.

Development of a Phase Separation Strategy in Macrocyclization Reactions

La réaction de macrocyclisation est une transformation fondamentale en chimie organique de synthèse. Le principal défi associcé à la formation de macrocycles est la compétition inhérente avec la réaction d’oligomérisation qui mène à la formation de sousproduits indésirables. De plus, l’utilisation de conditions de dilutions élevées qui sont nécessaires afin d’obtenir une cyclisation “sélective”, sont souvent décourageantes pour les applications à l’échelle industrielle. Malgré cet intérêt pour les macrocycles, la recherche visant à développer des stratégies environnementalement bénignes, qui permettent d’utiliser des concentrations normales pour leur synthèse, sont encore rares. Cette thèse décrit le développement d’une nouvelle approche générale visant à améliorer l’efficacité des réactions de macrocyclisation en utilisant le contrôle des effets de dilution. Une stratégie de “séparation de phase” qui permet de réaliser des réactions à des concentrations plus élevées a été developpée. Elle se base sur un mélange de solvant aggrégé contrôlé par les propriétés du poly(éthylène glycol) (PEG). Des études de tension de surface, spectroscopie UV et tagging chimique ont été réalisées afin d’élucider le mécanisme de “séparation de phase”. Il est proposé que celui-ci fonctionne par diffusion lente du substrat organique vers la phase ou le catalyseur est actif. La nature du polymère co-solvant joue donc un rôle crutial dans le contrôle de l’aggrégation et de la catalyse La stratégie de “séparation de phase” a initiallement été étudiée en utilisant le couplage oxidatif d’alcynes de type Glaser-Hay co-catalysé par un complexe de cuivre et de nickel puis a été transposée à la chimie en flux continu. Elle fut ensuite appliquée à la cycloaddition d’alcynes et d’azotures catalysée par un complexe de cuivre en “batch” ainsi qu’en flux continu.

A dynamic knowledge-based decision support system to handle solids separation problems in activated sludge systems: development and validation

El sistema de fangs activats és el tractament biològic més àmpliament utilitzat arreu del món per la depuració d'aigües residuals. El seu funcionament depèn de la correcta operació tant del reactor biològic com del decantador secundari. Quan la fase de sedimentació no es realitza correctament, la biomassa no decantada s'escapa amb l'efluent causant un impacte sobre el medi receptor. Els problemes de separació de sòlids, són actualment una de les principals causes d'ineficiència en l'operació dels sistemes de fangs activats arreu del món. Inclouen: bulking filamentós, bulking viscós, escumes biològiques, creixement dispers, flòcul pin-point i desnitrificació incontrolada. L'origen dels problemes de separació generalment es troba en un desequilibri entre les principals comunitats de microorganismes implicades en la sedimentació de la biomassa: els bacteris formadors de flòcul i els bacteris filamentosos. Degut a aquest origen microbiològic, la seva identificació i control no és una tasca fàcil pels caps de planta. Els Sistemes de Suport a la Presa de Decisions basats en el coneixement (KBDSS) són un grup d'eines informàtiques caracteritzades per la seva capacitat de representar coneixement heurístic i tractar grans quantitats de dades. L'objectiu de la present tesi és el desenvolupament i validació d'un KBDSS específicament dissenyat per donar suport als caps de planta en el control dels problemes de separació de sòlids d'orígen microbiològic en els sistemes de fangs activats. Per aconseguir aquest objectiu principal, el KBDSS ha de presentar les següents característiques: (1) la implementació del sistema ha de ser viable i realista per garantir el seu correcte funcionament; (2) el raonament del sistema ha de ser dinàmic i evolutiu per adaptar-se a les necessitats del domini al qual es vol aplicar i (3) el raonament del sistema ha de ser intel·ligent. En primer lloc, a fi de garantir la viabilitat del sistema, s'ha realitzat un estudi a petita escala (Catalunya) que ha permès determinar tant les variables més utilitzades per a la diagnosi i monitorització dels problemes i els mètodes de control més viables, com la detecció de les principals limitacions que el sistema hauria de resoldre. Els resultats d'anteriors aplicacions han demostrat que la principal limitació en el desenvolupament de KBDSSs és l'estructura de la base de coneixement (KB), on es representa tot el coneixement adquirit sobre el domini, juntament amb els processos de raonament a seguir. En el nostre cas, tenint en compte la dinàmica del domini, aquestes limitacions es podrien veure incrementades si aquest disseny no fos òptim. En aquest sentit, s'ha proposat el Domino Model com a eina per dissenyar conceptualment el sistema. Finalment, segons el darrer objectiu referent al seguiment d'un raonament intel·ligent, l'ús d'un Sistema Expert (basat en coneixement expert) i l'ús d'un Sistema de Raonament Basat en Casos (basat en l'experiència) han estat integrats com els principals sistemes intel·ligents encarregats de dur a terme el raonament del KBDSS. Als capítols 5 i 6 respectivament, es presenten el desenvolupament del Sistema Expert dinàmic (ES) i del Sistema de Raonament Basat en Casos temporal, anomenat Sistema de Raonament Basat en Episodis (EBRS). A continuació, al capítol 7, es presenten detalls de la implementació del sistema global (KBDSS) en l'entorn G2. Seguidament, al capítol 8, es mostren els resultats obtinguts durant els 11 mesos de validació del sistema, on aspectes com la precisió, capacitat i utilitat del sistema han estat validats tant experimentalment (prèviament a la implementació) com a partir de la seva implementació real a l'EDAR de Girona. Finalment, al capítol 9 s'enumeren les principals conclusions derivades de la present tesi.

Energy separation of neutrons scattered at small angles from silicon using time-of-flight techniques

The time-of-flight technique is used on a small-angle neutron scattering instrument to separate the energies of the scattered neutrons, in order to determine the origin of the temperature-dependent scattering observed from silicon at Q > similar to 0.1 angstrom(-1). A quantitative analysis of the results in comparison with the phonon dispersion curves, determined by Dolling using a triple-axis neutron spectrometer, shows that the temperature-dependent scattering can be understood in terms of Umklapp processes whereby neutrons gain energy from phonons.

Inference on microsatellite mutation processes in the invasive mite, Varroa destructor, using reversible jump Markov chain Monte Carlo

Varroa destructor is a parasitic mite of the Eastern honeybee Apis cerana. Fifty years ago, two distinct evolutionary lineages (Korean and Japanese) invaded the Western honeybee Apis mellifera. This haplo-diploid parasite species reproduces mainly through brother sister matings, a system which largely favors the fixation of new mutations. In a worldwide sample of 225 individuals from 21 locations collected on Western honeybees and analyzed at 19 microsatellite loci, a series of de novo mutations was observed. Using historical data concerning the invasion, this original biological system has been exploited to compare three mutation models with allele size constraints for microsatellite markers: stepwise (SMM) and generalized (GSM) mutation models, and a model with mutation rate increasing exponentially with microsatellite length (ESM). Posterior probabilities of the three models have been estimated for each locus individually using reversible jump Markov Chain Monte Carlo. The relative support of each model varies widely among loci, but the GSM is the only model that always receives at least 9% support, whatever the locus. The analysis also provides robust estimates of mutation parameters for each locus and of the divergence time of the two invasive lineages (67,000 generations with a 90% credibility interval of 35,000-174,000). With an average of 10 generations per year, this divergence time fits with the last post-glacial Korea Japan land separation. (c) 2005 Elsevier Inc. All rights reserved.