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.

Modelagem e avaliação comparativa dos métodos Luus-Jaakola e R2W aplicados na estimativa de parâmetros cinéticos de adsorção

As técnicas inversas têm sido usadas na determinação de parâmetros importantes envolvidos na concepção e desempenho de muitos processos industriais. A aplicação de métodos estocásticos tem aumentado nos últimos anos, demonstrando seu potencial no estudo e análise dos diferentes sistemas em aplicações de engenharia. As rotinas estocásticas são capazes de otimizar a solução em uma ampla gama de variáveis do domínio, sendo possível a determinação dos parâmetros de interesse simultaneamente. Neste trabalho foram adotados os métodos estocásticos Luus-Jaakola (LJ) e Random Restricted Window (R2W) na obtenção dos ótimos dos parâmetros cinéticos de adsorção no sistema de cromatografia em batelada, tendo por objetivo verificar qual método forneceria o melhor ajuste entre os resultados obtidos nas simulações computacionais e os dados experimentais. Este modelo foi resolvido empregando o método de Runge- Kutta de 4 ordem para a solução de equações diferenciais ordinárias.

Pata contractions and coupled type fixed points

A new coupled fixed point theorem related to the Pata contraction for mappings having the mixed monotone property in partially ordered complete metric spaces is established. It is shown that the coupled fixed point can be unique under some extra suitable conditions involving mid point lower or upper bound properties. Also the corresponding convergence rate is estimated when the iterates of our function converge to its coupled fixed point.

Determinação de integrais primeiras liouvillianas em equações diferenciais ordinárias de segunda ordem

Nesta Tese desenvolvemos várias abordagens "Darbouxianas"para buscar integrais primeiras (elementares e Liouvillianas) de equações diferenciais ordinárias de segunda ordem (2EDOs) racionais. Os algoritmos (semi-algoritmos) que desenvolvemos seguem a linha do trabalho de Prelle e Singer. Basicamente, os métodos que buscam integrais primeiras elementares são uma extensão da técnica desenvolvida por Prelle e Singer para encontrar soluções elementares de equações diferenciais ordinárias de primeira ordem (1EDOs) racionais. O procedimento que lida com 2EDOs racionais que apresentam integrais primeiras Liouvillianas é baseado em uma extensão ao nosso método para encontrar soluções Liouvillianas de 1EDOs racionais. A ideia fundamental por tras do nosso trabalho consiste em que os fatores integrantes para 1-formas polinomiais geradas pela diferenciação de funções elementares e Liouvillianas são formados por certos polinômios denominados polinômios de Darboux. Vamos mostrar como combinar esses polinômios de Darboux para construir fatores integrantes e, de posse deles, determinar integrais primeiras. Vamos ainda discutir algumas implementações computacionais dos semi-algoritmos.

Desenvolvimento e avaliação de novas abordagens de modelagem de processos de separação em leito móvel simulado

O Leito Móvel Simulado (LMS) é um processo de separação de compostos por adsorção muito eficiente, por trabalhar em um regime contínuo e também possuir fluxo contracorrente da fase sólida. Dentre as diversas aplicações, este processo tem se destacado na resolução de petroquímicos e principalmente na atualidade na separação de misturas racêmicas que são separações de um grau elevado de dificuldade. Neste trabalho foram propostas duas novas abordagens na modelagem do LMS, a abordagem Stepwise e a abordagem Front Velocity. Na modelagem Stepwise as colunas cromatográficas do LMS foram modeladas com uma abordagem discreta, onde cada uma delas teve seu domínio dividido em N células de mistura interligadas em série, e as concentrações dos compostos nas fases líquida e sólida foram simuladas usando duas cinéticas de transferência de massa distintas. Essa abordagem pressupõe que as interações decorrentes da transferência de massa entre as moléculas do composto nas suas fases líquida e sólida ocorram somente na superfície, de forma que com essa suposição pode-se admitir que o volume ocupado por cada molécula nas fases sólida e líquida é o mesmo, o que implica que o fator de residência pode ser considerado igual a constante de equilíbrio. Para descrever a transferência de massa que ocorre no processo cromatográfico a abordagem Front Velocity estabelece que a convecção é a fase dominante no transporte de soluto ao longo da coluna cromatográfica. O Front Velocity é um modelo discreto (etapas) em que a vazão determina o avanço da fase líquida ao longo da coluna. As etapas são: avanço da fase líquida e posterior transporte de massa entre as fases líquida e sólida, este último no mesmo intervalo de tempo. Desta forma, o fluxo volumétrico experimental é utilizado para a discretização dos volumes de controle que se deslocam ao longo da coluna porosa com a mesma velocidade da fase líquida. A transferência de massa foi representada por dois mecanismos cinéticos distintos, sem (tipo linear) e com capacidade máxima de adsorção (tipo Langmuir). Ambas as abordagens propostas foram estudadas e avaliadas mediante a comparação com dados experimentais de separação em LMS do anestésico cetamina e, posteriormente, com o fármaco Verapamil. Também foram comparados com as simulações do modelo de equilíbrio dispersivo para o caso da Cetamina, usado por Santos (2004), e para o caso do Verapamil (Perna 2013). Na etapa de caracterização da coluna cromatográfica as novas abordagens foram associadas à ferramenta inversa R2W de forma a determinar os parâmetros globais de transferência de massa apenas usando os tempos experimentais de residência de cada enantiômero na coluna de cromatografia líquida de alta eficiência (CLAE). Na segunda etapa os modelos cinéticos desenvolvidos nas abordagens foram aplicados nas colunas do LMS com os valores determinados na caracterização da coluna cromatográfica, para a simulação do processo de separação contínua. Os resultados das simulações mostram boa concordância entre as duas abordagens propostas e os experimentos de pulso para a caracterização da coluna na separação enantiomérica da cetamina ao longo do tempo. As simulações da separação em LMS, tanto do Verapamil quando da Cetamina apresentam uma discrepância com os dados experimentais nos primeiros ciclos, entretanto após esses ciclos iniciais a correlação entre os dados experimentais e as simulações. Para o caso da separação da cetamina (Santos, 2004), a qual a concentração da alimentação era relativamente baixa, os modelos foram capazes de predizer o processo de separação com as cinéticas Linear e Langmuir. No caso da separação do Verapamil (Perna, 2013), onde a concentração da alimentação é relativamente alta, somente a cinética de Langmuir representou o processo, devido a cinética Linear não representar a saturação das colunas cromatográficas. De acordo como o estudo conduzido ambas as abordagens propostas mostraram-se ferramentas com potencial na predição do comportamento cromatográfico de uma amostra em um experimento de pulso, assim como na simulação da separação de um composto no LMS, apesar das pequenas discrepâncias apresentadas nos primeiros ciclos de trabalho do LMS. Além disso, podem ser facilmente implementadas e aplicadas na análise do processo, pois requer um baixo número de parâmetros e são constituídas de equações diferenciais ordinárias.

The post-processed Galerkin method applied to non-linear shell vibrations

We present the results of a computational study of the post-processed Galerkin methods put forward by Garcia-Archilla et al. applied to the non-linear von Karman equations governing the dynamic response of a thin cylindrical panel periodically forced by a transverse point load. We spatially discretize the shell using finite differences to produce a large system of ordinary differential equations (ODEs). By analogy with spectral non-linear Galerkin methods we split this large system into a 'slowly' contracting subsystem and a 'quickly' contracting subsystem. We then compare the accuracy and efficiency of (i) ignoring the dynamics of the 'quick' system (analogous to a traditional spectral Galerkin truncation and sometimes referred to as 'subspace dynamics' in the finite element community when applied to numerical eigenvectors), (ii) slaving the dynamics of the quick system to the slow system during numerical integration (analogous to a non-linear Galerkin method), and (iii) ignoring the influence of the dynamics of the quick system on the evolution of the slow system until we require some output, when we 'lift' the variables from the slow system to the quick using the same slaving rule as in (ii). This corresponds to the post-processing of Garcia-Archilla et al. We find that method (iii) produces essentially the same accuracy as method (ii) but requires only the computational power of method (i) and is thus more efficient than either. In contrast with spectral methods, this type of finite-difference technique can be applied to irregularly shaped domains. We feel that post-processing of this form is a valuable method that can be implemented in computational schemes for a wide variety of partial differential equations (PDEs) of practical importance.

Classical plume theory: 1937-2010 and beyond

Developing a theoretical description of turbulent plumes, the likes of which may be seen rising above industrial chimneys, is a daunting thought. Plumes are ubiquitous on a wide range of scales in both the natural and the man-made environments. Examples that immediately come to mind are the vapour plumes above industrial smoke stacks or the ash plumes forming particle-laden clouds above an erupting volcano. However, plumes also occur where they are less visually apparent, such as the rising stream of warmair above a domestic radiator, of oil from a subsea blowout or, at a larger scale, of air above the so-called urban heat island. In many instances, not only the plume itself is of interest but also its influence on the environment as a whole through the process of entrainment. Zeldovich (1937, The asymptotic laws of freely-ascending convective flows. Zh. Eksp. Teor. Fiz., 7, 1463-1465 (in Russian)), Batchelor (1954, Heat convection and buoyancy effects in fluids. Q. J. R. Meteor. Soc., 80, 339-358) and Morton et al. (1956, Turbulent gravitational convection from maintained and instantaneous sources. Proc. R. Soc. Lond. A, 234, 1-23) laid the foundations for classical plume theory, a theoretical description that is elegant in its simplicity and yet encapsulates the complex turbulent engulfment of ambient fluid into the plume. Testament to the insight and approach developed in these early models of plumes is that the essential theory remains unchanged and is widely applied today. We describe the foundations of plume theory and link the theoretical developments with the measurements made in experiments necessary to close these models before discussing some recent developments in plume theory, including an approach which generalizes results obtained separately for the Boussinesq and the non-Boussinesq plume cases. The theory presented - despite its simplicity - has been very successful at describing and explaining the behaviour of plumes across the wide range of scales they are observed. We present solutions to the coupled set of ordinary differential equations (the plume conservation equations) that Morton et al. (1956) derived from the Navier-Stokes equations which govern fluid motion. In order to describe and contrast the bulk behaviour of rising plumes from general area sources, we present closed-form solutions to the plume conservation equations that were achieved by solving for the variation with height of Morton's non-dimensional flux parameter Γ - this single flux parameter gives a unique representation of the behaviour of steady plumes and enables a characterization of the different types of plume. We discuss advantages of solutions in this form before describing extensions to plume theory and suggesting directions for new research. © 2010 The Author. Published by Oxford University Press on behalf of the Institute of Mathematics and its Applications. All rights reserved.

Reconstruction of arbitrary biochemical reaction networks: A compressive sensing approach

Reconstruction of biochemical reaction networks (BRN) and genetic regulatory networks (GRN) in particular is a central topic in systems biology which raises crucial theoretical challenges in system identification. Nonlinear Ordinary Differential Equations (ODEs) that involve polynomial and rational functions are typically used to model biochemical reaction networks. Such nonlinear models make the problem of determining the connectivity of biochemical networks from time-series experimental data quite difficult. In this paper, we present a network reconstruction algorithm that can deal with ODE model descriptions containing polynomial and rational functions. Rather than identifying the parameters of linear or nonlinear ODEs characterised by pre-defined equation structures, our methodology allows us to determine the nonlinear ODEs structure together with their associated parameters. To solve the network reconstruction problem, we cast it as a compressive sensing (CS) problem and use sparse Bayesian learning (SBL) algorithms as a computationally efficient and robust way to obtain its solution. © 2012 IEEE.

Seafloor interaction with steel catenary risers

This paper describes the key features of a seafloor-riser interaction model. The soil is represented in terms of non-linear load-deflection (P- y) relationships, which are also able to account for soil stiffness degradation due to cyclic loading. The analytical framework considers the riser-seafloor interaction problem in terms of a pipe resting on a bed of springs, and requires the iterative solution of a fourth-order ordinary differential equation. A series of simulations is used to illustrate the capabilities of the model. Thanks to the non-linear soil springs with stiffness degradation it is possible to simulate the trench formation process and estimate moments in a riser. Copyright © 2008 by The International Society of Offshore and Polar Engineers (ISOPE).

Optimization algorithms and ODE's in MDO

There is a need for a stronger theoretical understanding of Multidisciplinary Design Optimization (MDO) within the field. Having developed a differential geometry framework in response to this need, we consider how standard optimization algorithms can be modeled using systems of ordinary differential equations (ODEs) while also reviewing optimization algorithms which have been derived from ODE solution methods. We then use some of the framework's tools to show how our resultant systems of ODEs can be analyzed and their behaviour quantitatively evaluated. In doing so, we demonstrate the power and scope of our differential geometry framework, we provide new tools for analyzing MDO systems and their behaviour, and we suggest hitherto neglected optimization methods which may prove particularly useful within the MDO context. Copyright © 2013 by ASME.

Hybrid numerical methods for exponential models of growth

A series of novel numerical methods for the exponential models of growth are proposed. Based on these methods, hybrid predictor-corrector methods are constructed. The hybrid numerical methods can increase the accuracy and the computing speed obviously, as well as enlarge the stability domain greatly. (c) 2005 Published by Elsevier Inc.

On the soft wall guiding potentials in realistic quantum waveguides

A transfer matrix method is presented for the study of electron conduction in a quantum waveguide with soft wall lateral confinement. By transforming the two-dimensional Schrodinger equation into a set of second order ordinary differential equations, the total transfer matrix is obtained and the scattering probability amplitudes are calculated. The proposed method is applied to the evaluation of the electron transmission in two types of cavity structure with finite-height square-well confinement. The results obtained by our method, which are found to be in excellent agreement with those from another transfer matrix method, suggest that the infinite square-well potential is a good approximation to finite-height square-well confinement for electrons propagating in the ground transverse mode, but softening of the walls has an obvious effect on the electron transmission and mode-mixing for propagating in the excited transverse mode. (C) 1996 American Institute of Physics.

Analysis for temperature and pressure fields in process of hydrate dissociation by depressurization

An improved axisymmetric mathematic modeling is proposed for the process of hydrate dissociation by depressurization around vertical well. To reckon in the effect of latent heat of gas hydrate at the decomposition front, the energy balance equation is employed. The semi-analytic solutions for temperature and pressure fields are obtained by using Boltzmann-transformation. The location of decomposition front is determined by solving initial value problem for system of ordinary differential equations. The distributions of pressure and temperature along horizontal radiate in the reservoir are calculated. The numeric results indicate that the moving speed of decomposition front is sensitively dependent on the well pressure and the sediment permeability. Copyright (C) 2010 John Wiley & Sons, Ltd.

NONLINEAR GRAVITY-WAVES IN DEEP-WATER

In consideration of the problem on the boundary condition of nonlinear free water wave, coordinate transform is used to handle the free boundary. Supposing the solution form be the traveling wave, the ordinary differential equations of the one-order autonomous system with two variables are caused, then expanding the nonlinear terms at the equilibrium point with the Taylor expansion, we obtained the solution to traveling wave. The linear approximate equation near the equilibrium point is the small amplitude wave. A new nonlinear periodic traveling wave and nonlinear dispersion relation are shown when expanding to the second-order terms. A conclusion that the expansion of dispersion relation does not contain any odd-power terms of wave steepness and because of the nonlinear effort an oscillate structure is produced in the vertical direction is drawn.

Elliptic Object Detection Based on Shape Preserving and Active Contour

本文通过形状约束方程(组)与一般主动轮廓模型结合,将目标形状与主动轮廓模型融合到统一能量泛函模型中,提出了一种形状保持主动轮廓模型即曲线在演化过程中保持为某一类特定形状。模型通过参数化水平集函数的零水平集控制演化曲线形状,不仅达到了分割即目标的目的,而且能够给出特定目标的定量描述。根据形状保持主动轮廓模型,建立了一个用于椭圆状目标检测的统一能量泛函模型,导出了相应的Euler-Lagrange常微分方程并用水平集方法实现了椭圆状目标检测。此模型可以应用于眼底乳头分割,虹膜检测及相机标定。实验结果表明,此模型不仅能够准确的检测出给定图像中的椭圆状目标,而且有很强的抗噪、抗变形及遮挡性能。