307 views

Uploaded by cegarcia

Applied Parameter Estimation for Chemical Engineers (Chemical Industries) by Peter Englezos

- SummerSchoolIP10_4
- Aren et al 2014
- Bioreaction Engineering Principles
- lecture-static-04_014.pdf
- AppendixA_case9_multiple_ECM_with_metered_baseline_data_(A-7).pdf
- Molecular Thermodynamics of Fluid Phase Equilibria 3Ed
- MAE 3272 - Lecture 2 Notes - Errors
- DK5985_ch08Engineers (Chemical Industries) by Peter Englezos [Cap 8]
- Pythagoras
- Engineering Optimization, 2nd Ed, Wiley (2006)
- So_You_Think_Youre_An_Estimator.pdf
- Levenberg Marquardt Algorithm
- Analysis and Structural Design
- Fundamentals of Process Control
- Matlab Process Control
- 1673.pdf
- Nuevos Métodos y Big Data en Estudios sobre Cáncer Colorrectal
- The Impact of Environmental Policy on Foreign Trade
- La Sorprendente Historia de La Ecuacuion Robergs
- The centrifugal and centripetal force influence on spatial competition of agricultural land in Bandung Metropolitan Region

You are on page 1of 21

CHEMICAL ENGINEERS

Peter Englezos

University of British Columbia Vancouver, Canada

Nicolas Kalogerakis

Technical University of Crete Chania, Greece

MARCEL

ISBN: 0-8247-9561-X

Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016

tel: 212-696-9000; fax: 212-685-4540

Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland

tel: 41-61-261-8482; fax: 41-61-261-8896

The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above.

Copyright 2001 by Marcel Dekker, Inc. All Rights Reserved.

Neither this book nor any part may be reproduced or transmitted in any form or by any

means, electronic or mechanical, including photocopying, microfilming, and recording, or

by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10 9 8 7 6 5 4 3 2 1

PRINTED IN THE UNITED STATES OF AMERICA

CHEMICAL INDUSTRIES

1. Fluid Catalytic Cracking with Zeolite Catalysts, Paul B. Venuto and E. Thomas Habib, Jr. 2. Ethylene: Keystone to the Petrochemical Industry, Ludwig Kniel, Olaf Winter, and Karl Stork 3. The Chemistry and Technology of Petroleum, James G. Speight 4. The Desulfurization of Heavy Oils and Residua, James G. Speight 5. Catalysis of Organic Reactions, edited by William R. Moser 6. Acetylene-Based Chemicals from Coal and Other Natural Resources, Robert J. Tedeschi 7. Chemically Resistant Masonry, Walter Lee Sheppard, Jr. 8. Compressors and Expanders: Selection and Application for the Process Industry, Heinz P. Bloch, Joseph A. Cameron, Frank M. Danowski, Jr., Ralph James, Jr., Judson S. Swearingen, and Marilyn E. Weightman 9. Metering Pumps: Selection and Application, James P. Poynton 10. Hydrocarbons from Methanol, Clarence D. Chang 11. Form Flotation: Theory and Applications, Ann N. Clarke and David J. Wilson 12. The Chemistry and Technology of Coal, James G. Speight 13. Pneumatic and Hydraulic Conveying of Solids, O. A. Williams 14. Catalyst Manufacture: Laboratory and Commercial Preparations, Alvin B. Stiles 15. Characterization of Heterogeneous Catalysts, edited by Francis Delannay 16. BASIC Programs for Chemical Engineering Design, James H. Weber 17. Catalyst Poisoning, L. Louis Hegedus and Robert W. McCabe 18. Catalysis of Organic Reactions, edited by John R. Kosak 19. Adsorption Technology: A Step-by-Step Approach to Process Evaluation and Application, edited by Frank L. Slejko 20. Deactivation and Poisoning of Catalysts, edited by Jacques Oudar and Henry Wise 21. Catalysis and Surface Science: Developments in Chemicals from Methanol, Hydrotreating of Hydrocarbons, Catalyst Preparation, Monomers and Polymers, Photocatalysis and Photovoltaics, edited by Heinz Heinemann and Gabor A. Somorjai 22. Catalysis of Organic Reactions, edited by Robert L. Augustine

Copyright 2001 by Taylor & Francis Group, LLC

23. Modern Control Techniques for the Processing Industries, T. H. Tsai, J. W. Lane, and C. S. Lin 24. Temperature-Programmed Reduction for Solid Materials Characterization, Alan Jones and Brian McNichol 25. Catalytic Cracking: Catalysts, Chemistry, and Kinetics, Bohdan W. Wojciechowski and Avelino Corma 26. Chemical Reaction and Reactor Engineering, edited by J. J. Carberry and A. Varma 27. Filtration: Principles and Practices, Second Edition, edited by Michael J. Matteson and Clyde Orr 28. Corrosion Mechanisms, edited by Florian Mansfeld 29. Catalysis and Surface Properties of Liquid Metals and Alloys, Yoshisada Ogino 30. Catalyst Deactivation, edited by Eugene E. Petersen and Alexis T. Bell 31. Hydrogen Effects in Catalysis: Fundamentals and Practical Applications, edited by Zoltan Paal and P. G. Menon 32. Flow Management for Engineers and Scientists, Nicholas P. Cheremisinoff and Paul N. Cheremisinoff 33. Catalysis of Organic Reactions, edited by Paul N. Rylander, Harold Greenfield, and Robert L. Augustine 34. Powder and Bulk Solids Handling Processes: Instrumentation and Control, Koichi linoya, Hiroaki Masuda, and Kinnosuke Watanabe 35. Reverse Osmosis Technology: Applications for High-Purity-Water Production, edited by Bipin S. Parekh 36. Shape Selective Catalysis in Industrial Applications, N. Y. Chen, William E. Garwood, and Frank G. Dwyer 37. Alpha Olefins Applications Handbook, edited by George R. Lappin and Joseph L. Sauer 38. Process Modeling and Control in Chemical Industries, edited by Kaddour Najim 39. Clathrate Hydrates of Natural Gases, E. Dendy Sloan, Jr. 40. Catalysis of Organic Reactions, edited by Dale W. Blackburn 41. Fuel Science and Technology Handbook, edited by James G. Speight 42. Octane-Enhancing Zeolitic FCC Catalysts, Julius Scherzer 43. Oxygen in Catalysis, Adam Bielanski and Jerzy Haber 44. The Chemistry and Technology of Petroleum: Second Edition, Revised and Expanded, James G. Speight 45. Industrial Drying Equipment: Selection and Application, C. M. van't Land 46. Novel Production Methods for Ethylene, Light Hydrocarbons, and Aromatics, edited by Lyle F. Albright, Billy L. Crynes, and Siegfried Nowak 47. Catalysis of Organic Reactions, edited by William E. Pascoe 48. Synthetic Lubricants and High-Performance Functional Fluids, edited by Ronald L. Shubkin 49. Acetic Acid and Its Derivatives, edited by Victor H. Agreda and Joseph R. Zoeller 50. Properties and Applications of Perovskite-Type Oxides, edited by L. G. Tejuca and J. L. G. Fierro

51. Computer-Aided Design of Catalysts, edited by E. Robert Becker and Carmo J. Pereira 52. Models for Thermodynamic and Phase Equilibria Calculations, edited by Stanley I. Sandier 53. Catalysis of Organic Reactions, edited by John R. Kosak and Thomas A. Johnson 54. Composition and Analysis of Heavy Petroleum Fractions, Klaus H. Altgelt and Mieczyslaw M. Boduszynski 55. NMR Techniques in Catalysis, edited by Alexis T. Bell and Alexander Pines 56. Upgrading Petroleum Residues and Heavy Oils, Murray R. Gray 57. Methanol Production and Use, edited by Wu-Hsun Cheng and Harold H. Kung 58. Catalytic Hydroprocessing of Petroleum and Distillates, edited by Michael C. Oballah and Stuart S. Shih 59. The Chemistry and Technology of Coal: Second Edition, Revised and Expanded, James G. Speight 60. Lubricant Base Oil and Wax Processing, Avilino Sequeira, Jr. 61. Catalytic Naphtha Reforming: Science and Technology, edited by George J. Antos, Abdullah M. Aitani, and Jose M. Parera 62. Catalysis of Organic Reactions, edited by Mike G. Scares and Michael L. Prunier 63. Catalyst Manufacture, Alvin B. Stiles and Theodore A. Koch 64. Handbook of Grignard Reagents, edited by Gary S. Silverman and Philip E. Rakita 65. Shape Selective Catalysis in Industrial Applications: Second Edition, Revised and Expanded, N. Y. Chen, William E. Garwood, and Francis G. Dwyer 66. Hydrocracking Science and Technology, Julius Scherzer and A. J. Gruia 67. Hydrotreating Technology for Pollution Control: Catalysts, Catalysis, and Processes, edited by Mario L. Occelli and Russell Chianelii 68. Catalysis of Organic Reactions, edited by Russell E. Malz, Jr. 69. Synthesis of Porous Materials: Zeolites, Clays, and Nanostructures, edited by Mario L. Occelli and Henri Kessler 70. Methane and Its Derivatives, Sunggyu Lee 71. Structured Catalysts and Reactors, edited by Andrzei Cybulski and Jacob Moulijn 72. Industrial Gases in Petrochemical Processing, Harold Gunardson 73. Clathrate Hydrates of Natural Gases: Second Edition, Revised and Expanded, E. Dendy Sloan, Jr. 74. Fluid Cracking Catalysts, edited by Mario L. Occelli and Paul O'Connor 75. Catalysis of Organic Reactions, edited by Frank E. Herkes 76. The Chemistry and Technology of Petroleum, Third Edition, Revised and Expanded, James G. Speight 77. Synthetic Lubricants and High-Performance Functional Fluids, Second Edition: Revised and Expanded, Leslie R. Rudnick and Ronald L. Shubkin

Copyright 2001 by Taylor & Francis Group, LLC

78. The Desulfurization of Heavy Oils and Residua, Second Edition, Revised and Expanded, James G. Speight 79. Reaction Kinetics and Reactor Design: Second Edition, Revised and Expanded, John B. Butt 80. Regulatory Chemicals Handbook, Jennifer M. Spero, Bella Devito, and Louis Theodore 81. Applied Parameter Estimation for Chemical Engineers, Peter Englezos and Nicolas Kalogerakis 82. Catalysis of Organic Reactions, edited by Michael E. Ford

The Chemical Process Industries Infrastructure: Function and Economics, James R. Couper, O. Thomas Beasley, and W. Roy Penney Elements of Transport Phenomena, Joel Plawsky

Preface

Engineering sciences state relations among measurable properties so that a technological system or process can be analyzed mathematically (Ferguson, 1992). The term model is adopted here to refer to the ensemble of equations that describes and interrelates the variables and parameters of a system or process (Basmadjan, 1999). In chemical, biochemical, environmental and petroleum engineering these models are based on the principles of chemistry, physics, thermodynamics, kinetics and transport phenomena. As most engineering calculations cannot be based on quantum mechanics as of yet, the models contain a number of quantities the value of which is not known a priori. It is customary to call these quantities adjustable parameters. The determination of suitable values for these adjustable parameters is the objective of parameter estimation, also known as data regression. A classic example of parameter estimation is the determination of kinetic parameters from a set of data. Parameter estimation is essentially an optimization problem whereby the unknown parameters are obtained by minimizing a suitable objective function. The structure of this objective function has led to the development of particularly efficient and robust methods. The aim of this book is to provide students and practicing engineers with straightforward tools that can be used directly for the solution of parameter estimation problems. The emphasis is on applications rather than on formal development of the theories. Students who study chemical, biochemical, environmental or petroleum engineering and practicing engineers in these fields will find the book useful. The following table summarizes how the book can be used:

Preface

Subject Regression Analysis & Applications Chemical Kinetics & Reactor Design Biochemical Engineering Petroleum Reservoir Engineering Computational Thermodynamics Optimization Methods

Chapters from this book All chapters 1,2,3,4,6,8, 10, 11, 12, 16 1,2,3,4,6,7,8, 11, 12, 17 1,2,3,6,8, 10, 11, 18 1,2,4,8,9, 11,12,14, 15 1,2,3,4,5,6,7,8,9, 10, 11, 12

With this book the reader can expect to learn how to formulate and solve parameter estimation problems, compute the statistical properties of the parameters, perform model adequacy tests, and design experiments for parameter estimation or model discrimination. A number of books address parameter estimation (Bard, 1974; Bates and Watts, 1988; Beck and Arnold, 1977; Draper and Smith, 1981; Gans, 1992; Koch, 1987; Lawson and Hanson, 1974; Seber and Wild, 1989; Seinfeld and Lapidus, 1974; Sorenson, 1980). However, the majority of these books emphasize statistics and mathematics or system identification and signal processing. Furthermore, most of the existing books pay considerable attention to linear and nonlinear regression for models described by algebraic equations. This book was conceived with the idea of focusing primarily on chemical engineering applications and on systems described by nonlinear algebraic and ordinary differential equations with a particular emphasis on the latter. In Chapter 1, the main areas where chemical engineers encounter parameter estimation problems are introduced. Examples from chemical kinetics, biochemical engineering, petroleum engineering, and thermodynamics are briefly described. In Chapter 2, the parameter estimation problem is formulated mathematically with emphasis on the choice of a suitable objective function. The subject of linear regression is described in a succinct manner in Chapter 3. Methodologies for solving linear regression problems with readily available software such as Microsoft Excel and SigmaPlot for Windows are presented with examples. In Chapter 4 the Gauss-Newton method for systems described by algebraic equations is developed. The method is illustrated by examples with actual data from the literature. Other methods (indirect, such as Newton, Quasi-Newton, etc., and direct, such as the Luus-Jaakola optimization procedure) are presented in Chapter 5. In Chapter 6, the Gauss-Newton method for systems described by ordinary differential equations (ODE) is developed and is illustrated with three examples formulated with data from the literature. Simpler methods for estimating parameters in systems described by ordinary differential equations known as shortcut methods are presented in Chapter 7. Such methods are particularly suitable for systems in the field of biochemical engineering. Chapter 8 provides practical guidelines for the implementation of the GaussNewton method. Issues such as generating initial guesses and tackling the issues of overstepping and matrix ill-conditioning are presented. In addition, guidelines

Copyright 2001 by Taylor & Francis Group, LLC

Preface

vii

are provided on how to utilize "prior" information and selecting a suitable weighting matrix. The models described by ODE require special attention to deal with stiffness and enlargement of the region of convergence. Chapter 9 deals with estimation of parameters subject to equality and inequality constraints whereas Chapter 10 examines systems described by partial differential equations (PDE). Examples are provided in Chapters 14 and 18. Procedures on how to make inferences on the parameters and the response variables are introduced in Chapter 11. The design of experiments has a direct impact on the quality of the estimated parameters and is presented in Chapter 12. The emphasis is on sequential experimental design for parameter estimation and

for model discrimination. Recursive least squares estimation, used for on-line data analysis, is briefly covered in Chapter 13. Chapters 14 to 18 are entirely devoted to applications. Examples and problems for solution by the reader are also included. In Chapter 14 several applications of the Gauss-Newton method are presented for the estimation of adjustable parameters in cubic equations of state. Parameter estimation in activity coefficient models is presented in Chapter 15. Chemical kinetics has traditionally been the main domain for parameter estimation studies. Examples formulated with models described by algebraic equations or ODE are presented in Chapter 16. The increasing involvement of chemical engineers in biotechnology motivated us to devote a chapter to such applications. Thus Chapter 17 includes examples from enzyme kinetics and mass transfer coefficient determination in bioreactors. The last chapter (Chapter 18) is devoted to applications in petroleum engineering. Thus the modeling of drilling data is a linear regression problem whereas oil reservoir simulation presents an opportunity to demonstrate the application of the GaussNewton method for systems described by partial differential equations. It is a pleasure to acknowledge those individuals who helped us indirectly in preparing this book: our colleagues Professors L.A. Behie, P.R. Bishnoi, R.A. Heidemann and R.G. Moore and our graduate students who over the years as part of their M.Sc. and Ph.D. thesis have gathered and analyzed data. We sincerely thank Professor Hoffman of the Institute of Technical Chemistry, Friedrich-Alexander University, Germany for providing us with the raw data for the hydrogenation of 3-hydroxypropanol. Professor Englezos acknowledges the support of the University of British Columbia for a sabbatical leave during which a major part of this book was completed. Professor Englezos also acknowledges the support from the Technical University of Crete and Keio University where he spent parts of his leave. Professor Kalogerakis acknowledges the support of the Technical University of Crete in completing this book; Professor Luus for his encouragement and help with direct search procedures; and all his colleagues at the University of Calgary for the many discussions and help he received over the years.

Copyright 2001 by Taylor & Francis Group, LLC

Preface

Finally, both of us would like to sincerely thank our wives Kalliroy Kalogerakis and Evangeline Englezos for their patience and understanding while we devoted many hours to completing this book.

Contents

Preface

1 Introduction 2 Formulation of the Parameter Estimation Problem 2.1 Structure of the Mathematical Model 2.1.1 Algebraic Equation Models 2.1.2 Differential Equation Models 2.2 The Objective Function 2.2.1 Explicit Estimation 2.2.1.1 Simple or Unweighted Least Squares (LS) Estimation 2.2.1.2 Weighted Least Squares (WLS) Estimation 2.2.1.3 Generalized Least Squares (GLS) Estimation 2.2.1.4 Maximum Likelihood (ML) Estimation 2.2.1.5 The Determinant Criterion 2.2.1.6 Incorporation of Prior Information About the Parameters 2.2.2 Implicit Estimation 2.3 Parameter Estimation Subject to Constraints 3 Computation of Parameters in Linear Models - Linear Regression 3.1 The Linear Regression Model 3.2 The Linear Least Squares Objective Function 3.3 Linear Least Squares Estimation 3.4 Polynomial Curve Fitting 3.5 Statistical Inferences

1 7 7 7 11 13 14 15 15 15 15 19 19 19 22 23 23 26 27 29

32

Contents

3.5.1 Inference on the Parameters 3.5.2 Inference on the Expected Response Variables 3.6 Solution of Multiple Linear Regression Problems 3.6.1 Procedure for Using Microsoft Excel for Windows 3.6.2 Procedure for Using SigmaPlot for Windows 3.7 Solution of Multiresponse Linear Regression Problems

32 33 35 35 42 46

3.8 Problems on Linear Regression 3.8.1 Vapor Pressure Data for Pyridine and Piperidine 3.8.2 Vapor Pressure Data for R142b and R152a

Gauss-Newton Method for Algebraic Models 4.1 Formulation of the Problem 4.2 The Gauss-Newton Method 4.2.1 Bisection Rule 4.2.2 Convergence Criteria 4.2.3 Formulation of the Solution Steps for the Gauss-Newton Method: Two Consecutive Chemical Reactions 4.2.4 Notes on the Gauss-Newton Method 4.3 Examples 4.3.1 Chemical Kinetics: Catalytic Oxidation of 3-Hexanol 4.3.2 Biological Oxygen Demand (BOD) 4.3.3 Numerical Example 1 4.3.4 Chemical Kinetics: Isomerization of Bicyclo [2,1,1] Hexane 4.3.5 Enzyme Kinetics 4.3.6 Catalytic Reduction of Nitric Oxide 4.3.7 Numerical Example 2 4.4 Solutions 4.4.1 Numerical Example 1 4.4.2 Numerical Example 2 Other Nonlinear Regression Methods for Algebraic Models 5.1 Gradient Minimization Methods 5.1.1 Steepest Descent Method 5.1.2 Newton's Method 5.1.3 Modified Newton's Method 5.1.4 Conjugate Gradient Methods 5.1.5 Quasi-Newton or Variable Metric or Secant Methods 5.2 Direct Search or Derivative Free Methods 5.2.1 LJ Optimization Procedure 5.2.2 Simplex Method 5.3 Exercises

Copyright 2001 by Taylor & Francis Group, LLC

46

46

47

49 49 50 52 52

53 55 55 55 56 57 58

60 61 62 64 65 66

67 67 69 71 76 76 77 78 79 81 83

Contents

Gauss-Newton Method for Ordinary Differential Equation (ODE) Models 6.1 Formulation of the Problem 6.2 The Gauss-Newton Method 6.2.1 Gauss-Newton Algorithm for ODE Models 6.2.2 Implementation Guidelines for ODE Models 6.3 The Gauss-Newton Method - Nonlinear Output Relationship 6.4 The Gauss-Newton Method - Systems with Unknown Initial Conditions 6.5 Examples 6.5.1 A Homogeneous Gas Phase Reaction 6.5.2 Pyrolytic Dehydrogenation of Benzene to Diphenyl and Triphenyl 6.5.3 Catalytic Hydrogenation of 3 -Hydroxypropanal (HPA) to l,3-Propanediol(PD) 6.6 Equivalence of Gauss-Newton with Quasilinearization Method 6.6.1 The Quasilinearization Method and its Simplification 6.6.2 Equivalence to Gauss-Newton Method 6.6.3 Nonlinear Output Relationship

84 84

85

88 88 92 93 96

96

98 102 111 111 114 114

7 Shortcut Estimation Methods for ODE Models 7.1 ODE Models with Linear Dependence on the Parameters 7.1.1 Derivative Approach 7.1.2 Integral Approach 7.2 Generalization to ODE Models with Nonlinear Dependence on the Parameters 7.3 Estimation of Apparent Rates in Biological Systems 7.3.1 Derivative Approach 7.3.2 Integral Approach 7.4 Examples 7.4.1 Derivative Approach - Pyrolytic Dehydrogenation of Benzene Practical Guidelines for Algorithm Implementation 8.1 Inspection of the Data 8.2 Generation of Initial Guesses 8.2.1 Nature and Structure of the Model 8.2.2 Asymptotic Behavior of the Model Equations 8.2.3 Transformation of the Model Equations 8.2.4 Conditionally Linear Systems 8.2.5 Direct Search Approach 8.3 Overstepping 8.3.1 An Optimal Step-Size Policy

Copyright 2001 by Taylor & Francis Group, LLC

119 120

122

123 129 129

133 133 135 135 135 136 138 139 139 140

Contents

8.4 Ill-Conditioning of Matrix A and Partial Remedies 8.4.1 Pseudoinverse 8.4.2 Marquardt's Modification 8.4.3 Scaling of Matrix A 8.5 Use of "Prior" Information 8.6 Selection of Weighting Matrix Q in Least Squares Estimation 8.7 Implementation Guidelines for ODE Models 8.7.1 Stiff ODE Models 8.7.2 Increasing the Region of Convergence 8.7.2.1 An Optimal Step-Size Policy 8.7.2.2 Use of the Information Index 8.7.2.3 Use of Direct Search Methods 8.8 Autocorrelation in Dynamic Systems

141 143 144 145 146 147 148 148 150 150 152 155 156

Constrained Parameter Estimation 9.1 Equality Constraints 9.1.1 Lagrange Multipliers 9.2 Inequality Constraints 9.2.1 Optimum Is Internal Point 9.2.1.1 Reparameterization 9.2.1.2 Penalty Function 9.2.1.3 Bisection Rule 9.2.2 The Kuhn-Tucker Conditions

(PDE) Models 10.1 Formulation of the Problem 10.2 The Gauss-Newton Method for PDE Models 10.3 The Gauss-Newton Method for Discretized PDE Models 10.3.1 Efficient Computation of the Sensitivity Coefficients 167 167 169 172 173

11 Statistical Inferences 11.1 Inferences on the Parameters 11.2 Inferences on the Expected Response Variables 11.3 Model Adequacy Tests 11.3.1 Single Response Models 11.3.2 Multivariate Models 12 Design of Experiments 12.1 Preliminary Experimental Design

Copyright 2001 by Taylor & Francis Group, LLC

Contents

12.2 Sequential Experimental Design for Precise Parameter Estimation 12.2.1 The Volume Design Criterion 12.2.2 The Shape Design Criterion 12.2.3 Implementation Steps

12.3 Sequential Experimental Design for Model Discrimination 12.3.1 The Divergence Design Criterion 12.3.2 Model Adequacy Tests for Model Discrimination

191 192 193

12.4 Sequential Experimental Design for ODE Systems 12.4.1 Selection of Optimal Sampling Interval and Initial State for

195

196

12.4.2 Selection of Optimal Sampling Interval and Initial State for Model Discrimination 12.4.3 Determination of Optimal Inputs for Precise Parameter Estimation and Model Discrimination 12.5 Examples 12.5.1 Consecutive Chemical Reactions 12.5.2 Fed-batch Bioreactor 12.5.3 Chemostat Growth Kinetics

196

200 200 202 202 207 213

13 Recursive Parameter Estimation 13.1 Discrete Input-Output Models 13.2 Recursive Least Squares (RLS) 13.3 Recursive Extended Least Squares (RELS)

14 Parameter Estimation in Nonlinear Thermodynamic Models: Cubic

Equations of State 14.1 Equations of State 14.1.1 Cubic Equations of State 14.1.2 Estimation of Interaction Parameters 14.1.3 Fugacity Expressions Using the Peng-Robinson EoS 14.1.4 Fugacity Expressions Using the Trebble-Bishnoi EoS 14.2 Parameter Estimation Using Binary VLB Data 14.2.1 Maximum Likelihood Parameter and State Estimation

223

Implicit Maximum Likelihood Parameter Estimation Implicit Least Squares Estimation Constrained Least Squares Estimation 14.2.5.1 Simplified Constrained Least Squares Estimation

233

234 236 236 237

238

Distributed Data

xiv

Contents

14.2.6 A Systematic Approach for Regression of Binary VLB Data 14.2.7 Numerical Results 14.2.7.1 The n-Pentane-Acetone System 14.2.7.2 The Methane-Acetone System 14.2.7.3 The Nitrogen-Ethane System

240

242 244 244 245 246

14.2.7.4 The Methane-Methanol System 14.2.7.5 The Carbon Dioxide-Methanol System 14.2.7.6 The Carbon Dioxide-n-Hexane System 14.2.7.7 The Propane-Methanol System 14.2.7.8 The Diethylamine-Water System 14.3 Parameter Estimation Using the Entire Binary Phase Equilibrium Data 14.3.1 The Objective Function 14.3.2 Covariance Matrix of the Parameters 14.3.3 Numerical Results 14.3.3.1 The Hydrogen Sulfide-Water System 14.3.3.2 The Methane-n-Hexane System 14.4 Parameter Estimation Using Binary Critical Point Data 14.4.1 The Objective Function 14.4.2 Numerical Results 14.5 Problems 14.5.1 Data for the Methanol-Isobutane System 14.5.2 Data for the Carbon Dioxide-Cyclohexane System

15 Parameter Estimation in Nonlinear Thermodynamic Models: Activity

Coefficients 15.1 Electrolyte Solutions 15.1.1 Pitzer's Model Parameters for Aqueous Na2SiO3 Solutions 15.1.2 Pitzer's Model Parameters for Aqueous Na2SiO3 - NaOH Solutions 15.1.3 Numerical Results 15.2 Non-Electrolyte Solutions 15.2.1 The Two-Parameter Wilson Model 15.2.2 The Three-Parameter NRTL Model 15.2.3 The Two-Parameter UNIQUAC Model 15.2.4 Parameter Estimation: The Objective Function Problems 15.3.1 Osmotic Coefficients for Aqueous Solutions of KC1 Obtained by the Isopiestic Method

255 255 257 258

258

259 261 261 264 266 266

266

Contents

280

15.3.3 The Benzene (l)-i-Propyl Alcohol (2) System 281 15.3.4 Vapor-Liquid Equilibria of Coal-Derived Liquids: Binary Systems with Terralin 282 15.3.5 Vapor-Liquid Equilibria of Ethylbenzene (l)-o-Xylene (2) at 26.66 kPa 283

16 Parameter Estimation in Chemical Reaction Kinetic Models 16.1 Algebraic Equation Models 16.1.1 Chemical Kinetics: Catalytic Oxidation of 3-Hexanol 16.1.2 Chemical Kinetics: Isomerization of Bicyclo [2,1,1] Hexane 16.1.3 Catalytic Reduction of Nitric Oxide 16.2 Problems with Algebraic Models 16.2.1 Catalytic Dehydrogenation of sec-butyl Alcohol 16.2.2 Oxidation of Propylene 16.2.3 Model Reduction Through Parameter Estimation in the s-Domain 16.3 Ordinary Differential Equation Models 16.3.1 A Homogeneous Gas Phase Reaction 16.3.2 Pyrolytic Dehydrogenation of Benzene to Diphenyl and Triphenyl 16.3.3 Catalytic Hydrogenation of 3-Hydroxypropanal (HPA) to l,3-Propanediol(PD) 16.3.4 Gas Hydrate Formation Kinetics 16.4 Problems with ODE Models 16.4.1 Toluene Hydrogenation 16.4.2 Methylester Hydrogenation 16.4.3 Catalytic Hydrogenation of 3-Hydroxypropanal (HPA) to 1,3-Propanediol (PD) - Nonisothermal Data

300 302

302

303

307 314

316 317 318 320

17 Parameter Estimation in Biochemical Engineering Models 322 17.1 Algebraic Equation Models 322 17.1.1 Biological Oxygen Demand 322 17.1.2 Enzyme Kinetics 323 17.1.3 Determination of Mass Transfer Coefficient (kLa) in a Municipal Wastewater Treatment Plant (with PULSAR aerators) 327 17.1.4 Determination of Monoclonal Antibody Productivity in a Dialyzed Chemostat 330 17.2 Problems with Algebraic Equation Models 338 17.2.1 Effect of Glucose to Glutamine Ratio on MAb Productivity in

a Chemostat

Copyright 2001 by Taylor & Francis Group, LLC

338

Contents

17.2.2 Enzyme Inhibition Kinetics 17.2.3 Determination of kLa in Bubble-free Bioreactors 17.3 Ordinary Differential Equation Models

17.3.1 Contact Inhibition in Microcarrier Cultures of MRC-5 Cells 17.4 Problems with ODE Models 17.4.1 Vero Cells Grown on Microcarriers (Contact Inhibition) 17.4.2 Effect of Temperature on Insect Cell Growth Kinetics

344

18 Parameter Estimation in Petroleum Engineering 353 18.1 Modeling of Drilling Rate Using Canadian Offshore Well Data 353 18.1.1 Application to Canadian Offshore Well Data 355 18.2 Modeling of Bitumen Oxidation and Cracking Kinetics Using Data from Alberta Oil Sands 358 18.2.1 Two-Component Models 358 18.2.2 Three-Component Models 359 18.2.3 Four-Component Models 362 18.2.4 Results and Discussion 364 18.3 Automatic History Matching in Reservoir Engineering 371 18.3.1 A Fully Implicit, Three Dimensional, Three-Phase Simulator with Automatic History-Matching Capability 371 18.3.2 Application to a Radial Coning Problem (Second SPE Comparative Solution Problem) 373 18.3.2.1 Matching Reservoir Pressure 373 18.3.2.2 Matching Water-Oil Ratio, Gas-Oil Ratio or Bottom Hole Pressure 374 18.3.2.3 Matching All Observed Data 374 18.3.3 A Three-Dimensional, Three-Phase Automatic HistoryMatching Model: Reliability of Parameter Estimates 376 18.3.3.1 Implementation and Numerical Results 378 18.3.4 Improved Reservoir Characterization Through Automatic History Matching 380 18.3.4.1 Incorporation of Prior Information and Constraints on the Parameters 382 18.3.4.2 Reservoir Characterization Using Automatic History Matching 384 18.3.5 Reliability of Predicted Well Performance Through Automatic History Matching 385 18.3.5.1 Quantification of Risk 388 18.3.5.2 Multiple Reservoir Descriptions 388 18.3.5.3 Case Study-Reliability of a Horizontal Well Performance 389

Contents

References Appendix 1 A. 1.1 The Trebble-Bishnoi Equation of State A. 1.2 Derivation of the Fugacity Expression A. 1.3 Derivation of the Expression for (91nfj/3xj)TiPjX

Appendix 2 A.2.1 Listings of Computer Programs A.2.2 Contents of Accompanying CD A.2.3 Computer Program for Example 16.1.2 A.2.4 Computer Program for Example 16.3.2

Index

434

- SummerSchoolIP10_4Uploaded bygladys
- Aren et al 2014Uploaded byIndah Novita
- Bioreaction Engineering PrinciplesUploaded bySaman
- lecture-static-04_014.pdfUploaded byAshoka Vanjare
- AppendixA_case9_multiple_ECM_with_metered_baseline_data_(A-7).pdfUploaded bygrunger30
- Molecular Thermodynamics of Fluid Phase Equilibria 3EdUploaded bykalloy01
- MAE 3272 - Lecture 2 Notes - ErrorsUploaded byaoeusnthid
- DK5985_ch08Engineers (Chemical Industries) by Peter Englezos [Cap 8]Uploaded bycegarcia
- PythagorasUploaded byAleks
- Engineering Optimization, 2nd Ed, Wiley (2006)Uploaded byRILG_EE
- So_You_Think_Youre_An_Estimator.pdfUploaded bydanish_1985
- Levenberg Marquardt AlgorithmUploaded byNithin Mohan
- Analysis and Structural DesignUploaded byDemçe Florjan
- Fundamentals of Process ControlUploaded byrukhan427559
- Matlab Process ControlUploaded byHarsha
- 1673.pdfUploaded byGabri
- Nuevos Métodos y Big Data en Estudios sobre Cáncer ColorrectalUploaded byjmgt100
- The Impact of Environmental Policy on Foreign TradeUploaded bynimida
- La Sorprendente Historia de La Ecuacuion RobergsUploaded byLuciano
- The centrifugal and centripetal force influence on spatial competition of agricultural land in Bandung Metropolitan RegionUploaded byochaholic
- Vol ImpliedUploaded byjkomkov1414
- bab 3Uploaded bysalsa
- Linear Regression 12Uploaded byashigaik
- Diss 066Uploaded byAla Thajil
- 160Uploaded byAli Sarmad
- Partially Linear Models of Parameter Estimation--Hardle, Liang, GaoUploaded byparagjdutta
- EDXChemA2_TYA_0001Uploaded bylegend789
- Beaver_1968_Uploaded byaimran_amir
- instructorsmanualforprinciplesofeconometricsfourtheditionwilliame-150910183908-lva1-app6892.pdfUploaded byAsrafuzzaman Robin
- Laboratory 1 Linear RegressionUploaded bypattysuarez

- Estimación de SoftwareUploaded bycegarcia
- EstimaSWUploaded bycegarcia
- EstimaSWUploaded bycegarcia
- Caso: Estimaciones para software de aula virtualUploaded bycegarcia
- EstimaSwUploaded bycegarcia
- Estimación de Software 6Uploaded bycegarcia
- Caso001.docUploaded bycegarcia
- Caso001.docUploaded bycegarcia
- Procesos de desarrollo en ingenieríaUploaded bycegarcia
- EstimaSwUploaded bycegarcia
- 01 Sistemas [TGS][2xp,Sig,Img,h]Uploaded bycegarcia
- Caso006Uploaded bycegarcia
- ProgS&P19 [Ori,Sig,Img]Uploaded bycegarcia
- EstimaSWUploaded bycegarcia
- Análisis de Video Ricos y PobresUploaded bycegarcia
- EstimaSwUploaded bycegarcia
- TX-082Uploaded bycegarcia
- EstimaSwUploaded bycegarcia
- EX-09suf.docUploaded bycegarcia
- TX 131[Nolan]Uploaded bycegarcia
- TX 131[Nolan]Uploaded bycegarcia
- TX 131[Nolan]Uploaded bycegarcia
- ProgMiEd11[ACC115]Uploaded bycegarcia
- EstimaSw.docUploaded bycegarcia
- TX 091[Metzger]Uploaded bycegarcia
- TX 111[Metzger]Uploaded bycegarcia
- TX-091[Anexo-EstimPFs]Uploaded bycegarcia
- TX 121[Metzger]Uploaded bycegarcia
- TX-081.docUploaded bycegarcia
- TX 101[Metzger]Uploaded bycegarcia

- Chemical Kinetics and CombustionUploaded byDeepak Jay
- Kinetic Adsorption Study of Glucose Osmotic Agent onto Granular Activated Carbon in SET TechniqueUploaded byAmin Mojiri
- tmpCDB4.tmpUploaded byFrontiers
- Book Chapter05-Dilute-Acid Hydrolysis of Lignocellulosic BiomassUploaded bydurga_85
- Partial FR Expt3Uploaded byyay
- HFSUploaded bySunny Duggal
- Carbonation monitoring of beverage.pdfUploaded byCarLita Castro
- Esteban 2014Uploaded byArturo Hernández Morales
- catalytic removal of NOUploaded byichrak
- Kinetic Study of Wood Chips Decomposition by TGAUploaded byMaciej Markowski
- Principles of Physical ChemistryUploaded byZarsa Barda
- Microphase-Assisted Autocatalysis in a Solid-liquid Reaction With a Precipitating Product. TheoryUploaded byYULYP
- Enzim.pptUploaded byribi
- Cephalosporium acremoniumUploaded byNain Jasro
- Zhou 2014Uploaded byAzharuddin_kfupm
- Modeliranje toplinkih postupaka dobijanja magnezijaUploaded byisus nazarecanin
- Catalytic BleachingUploaded byCh Hammad Nazir
- chapter 2 - Chemical Kinetics.pdfUploaded bysab
- Chapter 2 Enzymes BiotechUploaded bydatUPstudentdoe
- CRE II L 10Uploaded byMehul Varshney
- Methanation of CO Over Nickel Mechanism and Kinetics (1)Uploaded byMax Ferrer
- New Microsoft Office Word DocumentUploaded bymintu009
- CHEG 320_Electrode Kinetics_extended NotesUploaded byAzzkikrasdf
- mtbe-dUploaded byParaZzzit
- MIT Solution Key of Reactions & Kinetics ExaminationUploaded byAstrialdelina
- Computational Exercise on Lewis acid base reactionsUploaded byAnna Legaspi
- Cataliza eterogenaUploaded byTibi Opruta
- Experiment 1 Chem 18Uploaded byWilson Turalde
- Four Challenges for Nickel Steam-reforming CatalystsUploaded byReza Rhi
- chemical-kinetics.pdfUploaded byAnita Gupta