Estimation of catalyst activity profiles and deactivation parameters from reactor operating data with applications to naphtha reforming

Techniques are developed for estimating activity profiles in fixed bed reactors and catalyst deactivation parameters from operating reactor data. These techniques are applicable, in general, to most industrial catalytic processes. The catalytic reforming of naphthas is taken as a broad example to illustrate the estimation schemes and to signify the physical meaning of the kinetic parameters of the estimation equations. The work is described in two parts. Part I deals with the modeling of kinetic rate expressions and the derivation of the working equations for estimation. Part II concentrates on developing various estimation techniques.

Part I: The reactions used to describe naphtha reforming are dehydrogenation and dehydroisomerization of cycloparaffins; isomerization, dehydrocyclization and hydrocracking of paraffins; and the catalyst deactivation reactions, namely coking on alumina sites and sintering of platinum crystallites. The rate expressions for the above reactions are formulated, and the effects of transport limitations on the overall reaction rates are discussed in the appendices. Moreover, various types of interaction between the metallic and acidic active centers of reforming catalysts are discussed as characterizing the different types of reforming reactions.

Part II: In catalytic reactor operation, the activity distribution along the reactor determines the kinetics of the main reaction and is needed for predicting the effect of changes in the feed state and the operating conditions on the reactor output. In the case of a monofunctional catalyst and of bifunctional catalysts in limiting conditions, the cumulative activity is sufficient for predicting steady reactor output. The estimation of this cumulative activity can be carried out easily from measurements at the reactor exit. For a general bifunctional catalytic system, the detailed activity distribution is needed for describing the reactor operation, and some approximation must be made to obtain practicable estimation schemes. This is accomplished by parametrization techniques using measurements at a few points along the reactor. Such parametrization techniques are illustrated numerically with a simplified model of naphtha reforming.

To determine long term catalyst utilization and regeneration policies, it is necessary to estimate catalyst deactivation parameters from the the current operating data. For a first order deactivation model with a monofunctional catalyst or with a bifunctional catalyst in special limiting circumstances, analytical techniques are presented to transform the partial differential equations to ordinary differential equations which admit more feasible estimation schemes. Numerical examples include the catalytic oxidation of butene to butadiene and a simplified model of naphtha reforming. For a general bifunctional system or in the case of a monofunctional catalyst subject to general power law deactivation, the estimation can only be accomplished approximately. The basic feature of an appropriate estimation scheme involves approximating the activity profile by certain polynomials and then estimating the deactivation parameters from the integrated form of the deactivation equation by regression techniques. Different bifunctional systems must be treated by different estimation algorithms, which are illustrated by several cases of naphtha reforming with different feed or catalyst composition.

Acoplamento de técnicas espectrométricas com métodos quimiométricos de classificação e calibração multivariada em alimentos

Este trabalho de pesquisa descreve três estudos de utilização de métodos quimiométricos para a classificação e caracterização de óleos comestíveis vegetais e seus parâmetros de qualidade através das técnicas de espectrometria de absorção molecular no infravermelho médio com transformada de Fourier e de espectrometria no infravermelho próximo, e o monitoramento da qualidade e estabilidade oxidativa do iogurte usando espectrometria de fluorescência molecular. O primeiro e segundo estudos visam à classificação e caracterização de parâmetros de qualidade de óleos comestíveis vegetais utilizando espectrometria no infravermelho médio com transformada de Fourier (FT-MIR) e no infravermelho próximo (NIR). O algoritmo de Kennard-Stone foi usado para a seleção do conjunto de validação após análise de componentes principais (PCA). A discriminação entre os óleos de canola, girassol, milho e soja foi investigada usando SVM-DA, SIMCA e PLS-DA. A predição dos parâmetros de qualidade, índice de refração e densidade relativa dos óleos, foi investigada usando os métodos de calibração multivariada dos mínimos quadrados parciais (PLS), iPLS e SVM para os dados de FT-MIR e NIR. Vários tipos de pré-processamentos, primeira derivada, correção do sinal multiplicativo (MSC), dados centrados na média, correção do sinal ortogonal (OSC) e variação normal padrão (SNV) foram utilizados, usando a raiz quadrada do erro médio quadrático de validação cruzada (RMSECV) e de predição (RMSEP) como parâmetros de avaliação. A metodologia desenvolvida para determinação de índice de refração e densidade relativa e classificação dos óleos vegetais é rápida e direta. O terceiro estudo visa à avaliação da estabilidade oxidativa e qualidade do iogurte armazenado a 4C submetido à luz direta e mantido no escuro, usando a análise dos fatores paralelos (PARAFAC) na luminescência exibida por três fluoróforos presentes no iogurte, onde pelo menos um deles está fortemente relacionado com as condições de armazenamento. O sinal fluorescente foi identificado pelo espectro de emissão e excitação das substâncias fluorescentes puras, que foram sugeridas serem vitamina A, triptofano e riboflavina. Modelos de regressão baseados nos escores do PARAFAC para a riboflavina foram desenvolvidos usando os escores obtidos no primeiro dia como variável dependente e os escores obtidos durante o armazenamento como variável independente. Foi visível o decaimento da curva analítica com o decurso do tempo da experimentação. Portanto, o teor de riboflavina pode ser considerado um bom indicador para a estabilidade do iogurte. Assim, é possível concluir que a espectroscopia de fluorescência combinada com métodos quimiométricos é um método rápido para monitorar a estabilidade oxidativa e a qualidade do iogurte

Análise da tectônica de colocação de diques cretácicos na região de São Sebastião, SP

O trabalho foi desenvolvido no litoral norte do estado de São Paulo, onde ocorrem boas exposições de rochas intrusivas da porção meridional do Enxame de Diques da Serra do Mar, de idade eocretácica. O objetivo principal da dissertação é caracterizar os regimes tectônicos associados à colocação e à deformação de diques máficos na área de São Sebastião (SP) e sua distribuição espacial, a partir de interpretações de imagens de sensores remotos, análise de dados estruturais de campo e descrição petrográfica das rochas ígneas. A área apresenta grande complexidade no tocante ao magmatismo, uma vez que ocorrem diques de diabásios toleítico e alcalino, lamprófiro e rochas alcalinas félsicas como fonolitos, traquitos e sienitos, estes sob a forma diques, sills e plugs. Os diabásios toleíticos tem idades em torno 134 Ma, correlatas com o início do rifteamento sul-atlântico, enquanto que as rochas alcalinas datam de 86 Ma e estão relacionadas com um magmatismo intraplaca posterior. Os lineamentos estruturais orientam-se majoritariamente na direção ENE-WSW, paralela às foliações metamórficas e zonas de cisalhamento observadas no campo e descritas na literatura, referentes ao Domínio Costeiro da Faixa Ribeira. Os diques se orientam na direção NE-SW, com azimute semelhante porém ângulos de mergulho discordantes da foliação em grande parte da área, onde as foliações são de baixo ângulo. Um segundo conjunto de lineamentos orientado NW-SE ocorre como um importante conjunto de fraturas que cortam tanto as rochas do embasamento proterozóico quanto as rochas alcalinas neocretácicas. Diques com esta orientação são escassos. Um terceiro conjunto NNE-SSW ocorre na porção oeste da área, associado à presença de diques de diabásio que por vezes mostram indicadores de movimentação sinistral. A análise cinemática dos diques mostra um predomínio de distensão pura durante sua colocação, com um tensor de compressão mínima de orientação NW-SE, ortogonal ao principal trend dos diques. Componentes direcionais, por vezes ambíguas, são comumente observadas, com um discreto predomínio de componente sinistral. O mesmo padrão cinemático é observado para os diques toleíticos e para os alcalinos, sugerindo que o campo de tensões local pouco variou durante o Cretáceo. Embora o embasamento não tenha sido diretamente reativado durante a colocação dos diques, sua anisotropia pode ter controlado de certa forma a orientação do campo de tensões local durante o Cretáceo. Os mapas geofísicos da bacia de Santos existentes na literatura sugerem certo paralelismo entre as estruturas observadas na área de estudo e aquelas interpretadas na bacia. As estruturas NNE-SSW são paralelas ao trend das sub-bacias e ao gráben de Merluza, enquanto que as estruturas NW-SE são paralelas a zonas de transferência descritas na literatura.

Simulation of an apodizer's effect for high-density optical storage

The effect of an apodizer with two parallel taper refractive surfaces is theoretically investigated for high-density optical storage. The apodizer may modulate an incident Gaussian beam into an annular beam. Simulation shows that with the increasing inner radius of the modulated beam, the focal spot shrinks obviously. The depolarization effect gets strong simultaneously, which induces the circular symmetry loss of the focal spot. In this process, pattern density of the orthogonal and longitudinal diffractive fields increases remarkably.

Physiological modules for generating discrete and rhythmic movements: action identification by a dynamic recurrent neural network

In this study we employed a dynamic recurrent neural network (DRNN) in a novel fashion to reveal characteristics of control modules underlying the generation of muscle activations when drawing figures with the outstretched arm. We asked healthy human subjects to perform four different figure-eight movements in each of two workspaces (frontal plane and sagittal plane). We then trained a DRNN to predict the movement of the wrist from information in the EMG signals from seven different muscles. We trained different instances of the same network on a single movement direction, on all four movement directions in a single movement plane, or on all eight possible movement patterns and looked at the ability of the DRNN to generalize and predict movements for trials that were not included in the training set. Within a single movement plane, a DRNN trained on one movement direction was not able to predict movements of the hand for trials in the other three directions, but a DRNN trained simultaneously on all four movement directions could generalize across movement directions within the same plane. Similarly, the DRNN was able to reproduce the kinematics of the hand for both movement planes, but only if it was trained on examples performed in each one. As we will discuss, these results indicate that there are important dynamical constraints on the mapping of EMG to hand movement that depend on both the time sequence of the movement and on the anatomical constraints of the musculoskeletal system. In a second step, we injected EMG signals constructed from different synergies derived by the PCA in order to identify the mechanical significance of each of these components. From these results, one can surmise that discrete-rhythmic movements may be constructed from three different fundamental modules, one regulating the co-activation of all muscles over the time span of the movement and two others elliciting patterns of reciprocal activation operating in orthogonal directions.

Helmholtz Fermi surface harmonics: an efficient approach for treating anisotropic problems involving Fermi surface integrals

We present a new efficient numerical approach for representing anisotropic physical quantities and/or matrix elements defined on the Fermi surface (FS) of metallic materials. The method introduces a set of numerically calculated generalized orthonormal functions which are the solutions of the Helmholtz equation defined on the FS. Noteworthy, many properties of our proposed basis set are also shared by the FS harmonics introduced by Philip B Allen (1976 Phys. Rev. B 13 1416), proposed to be constructed as polynomials of the cartesian components of the electronic velocity. The main motivation of both approaches is identical, to handle anisotropic problems efficiently. However, in our approach the basis set is defined as the eigenfunctions of a differential operator and several desirable properties are introduced by construction. The method is demonstrated to be very robust in handling problems with any crystal structure or topology of the FS, and the periodicity of the reciprocal space is treated as a boundary condition for our Helmholtz equation. We illustrate the method by analysing the free-electron-like lithium (Li), sodium (Na), copper (Cu), lead (Pb), tungsten (W) and magnesium diboride (MgB2)

Análisis de la interferencia inducida en el electrocardiograma y señal de impedancia por compresiones torácicas sobre un maniquí.

[EN]This paper presents a project within that research field. The project consists on the development of an experimental environment comprised by a sensorized practice manikin and a management software system. Manikin model allows the simulation of cardiac arrest episodes on laboratory settings. The management software system adds the capacity to compute and analyze the characteristics of the artifact induced on the electrocardiogram and the thoracic impedance signals by chest compressions during cardiopulmonary resuscitation due to variations of the electrode-skin interface. The main reason for choosing this kind of model is the impossibility to use real people because of the risk of thoracic injuries during chest compression. Moreover, this platform could be used for training in reanimation techniques for real situations. Even laypeople with minimal training can perform cardiopulmonary resuscitation. This can reduce the response time to an emergency while the healthcare personnel arrives, which is key to improve outcomes, since with every minute the chances of survival decrease approximately 10%. It is not necessary to have medical knowledge to perform cardiopulmonary resuscitation, which could increase chances of survival for a patient with an early reanimation since In this context, this paper details the technique solution for the manikin sensorisation to acquire the electrocardiogram, the impedance signal measured between the defibrillation pads placed on the patient’s chest, the compression depth, the compression force and the acceleration experienced by the chest in the three orthogonal axes. Moreover, it is possible to inject a previously recorded electrocardiogram signal.

Robust design optimization of gas turbine compression systems

Gas turbine compression systems are required to perform adequately over a range of operating conditions. Complexity has encouraged the conventional design process for compressors to focus initially on one operating point, usually the most commonor arduous, to draw up an outline design. Generally, only as this initial design is refined is its offdesign performance assessed in detail. Not only does this necessarily introduce a potentially costly and timeconsuming extra loop in the design process, but it also may result in a design whose offdesign behavior is suboptimal. Aversion of nonintrusive polynomial chaos was previously developed in which a set of orthonormal polynomials was generated to facilitate a rapid analysis of robustness in the presence of generic uncertainties with good accuracy. In this paper, this analysis method is incorporated in real time into the design process for the compression system of a three-shaft gas turbine aeroengine. This approach to robust optimization is shown to lead to designs that exhibit consistently improved system performance with reduced sensitivity to offdesign operation.

Directional algebraic reconstruction technique for electrical impedance tomography

We assume that the resistance matrix can be found in electrical impedance tomography from the assumption of linear dependence between the voltages and the currents and with the help of the resistance matrix and the transfer impedance between the electrodes, a directional algebraic reconstruction technique is proposed. The goal is to reconstruct the resistivity distribution by weighting the matrices that are obtained by calculating the orthogonal distance of the underlying mesh elements from the neighbouring port resistivity lines. These weighting matrices, which only depend on the topology of the underlying mesh, can be calculated offline and result in a computationally efficient online procedure with a reasonable image reconstruction performance. Simulation results are provided to validate this approach.

温度梯度法生长Nd：YAG激光晶体的核心分布

用温度梯度法生长了直径为75mm大尺寸的Nd：YAG激光晶体，通过退火排除了生长过程中进入晶体的碳原子．用正交偏光显微镜观察了晶体的核心分布以及生长条纹．测试了室温下的吸收谱并利用吸收谱研究了Nd离子在YAG晶体中的分布．比较了温度梯度法与提拉法生长晶体的区别．