B. Wayne
Bequette
Process Dynamics
Modeling,
Analysis,
and
Simulation
Prentice Hall International Series in the Physical and Chemical Engineering Sciences
PRENTICE IIALL INTERNATIONAL SERIES IN THE PHYSICAL AND CHEMICAL ENGINEERING SCIENCES
NEAL R. !\i\lUNDSON, SE!{IES liDITOR, Un/verst!.\' t?!1foIlS!Ofl
AnVISORY E1JJTORS
AN[)J{l~AS ACRIVOS, S{(l!!(oI'r! Unil'ersify
JOHN DMII,ER, University (d'IVlillllesO{{/
H. SC'(rlT FOGIJ]{, Unil'CI"sity (~rMichigan
'T'1l0MAS J. IIANKATTY, University (?( fllil/oi,\' JOHN M. P[~AUSN[TZ,Univcrsily (?FCa!i;(omia
L. E::. SCRIVEN, University 1?(Minl/csota
Bi\LZlllSER, S;\:'·IUEJ.S, Mm 1::l.uASSEN
Br',QUFTrl::
BWUU.:R, CiROSS\\i\NN, AND WESTERBERG
CROWL and 1,()(JVA1{
Chemical !'.lIgilleaing ThennodYl/tllllics
Process Oynamics: A1odcling, Analysis, and Simulatio/l
Sy.l"tcmafh' iHethods rd' Chemica! Process J)esij{11
Chemica! Process Sq(ety
DFNN
Process' Fl/lid lvlec!wlI/c"S
[;'OGLER {:lemcfI!s q(Cllcmical Rcaction Engineering, 2nd I~'dition HANNA AND SANDA[J COll/putatiolla! Methods ill ChclIIical Engineering IIJ~IMI~LBLAU Basic Principles {{lid C(llcl/larions ill Chemical Engincering, 6th editioll
HINES i\!>il) MADDOX
Mass Tnl/lsjt'r
KYLE
Chemical and Proces ,.
'1henllodyl1amics, 2nd edition
NEWMAN
PR;\tJSNll/., LICIITFNTIlMJ',R, and DL A/.l'VEDO
(~rFlllidPIUlseEqlli/ihria, 2nd cdition PHrNTlC:E Elec!rochcmical Ellgincering Principles STEPHANOI'OULOS Chemical Process COlltrol TI~STER AND MOllF.!J. Thermodynamics (lnd Its /\pplicatio/ls, 3rd edition TURTON Analysis, SrI/thesis, and Design (~rChell/iCflIProcesses
Efectmchc/Ilical Systcms, 2nd edition
Molecular Thermodynamics
PROCESS DYNAMICS
Modeling, Analysis, and Simulation
B. Wayne Bequette
Rensselaer Polytechnic Institute
To join a Prentice Hall PTR Internet mailing list, point to:
http://www.prenhall.com/maiUists/
Prentice Hall PTR Upper Saddle River, New Jersey 07458
Library of Congl'l'ss Catalogil1g~il1PllblicatitmData
Bequette, B, Wayne. Process dynamics: modeling, analysis, and simulation / B, Wayne Bequette.
p.
ern.
Includes bibliographical references and index,
_{I}_{S}_{B}_{N} O,11206889~3
1. Chemical procc%es.
TPI55,7.B45
1998
I. Tille.
(j6()',2X4'OI185dc21 
97 
36053 
elP 
Acquisitions editor: Bernard M. Coodwin Cover design direcloc Jerry Votta Manufacturing manager: Alexis R. Heydt lvlilfketing Jnanllger: tvli1es Williams Compositor/Production services: Pinc Tree Composition, Inc.
(D 1998 by Prentice Hall PTR PrenticeHall, Inc. A Simon & Schuster Company Upper S,\dd\c River, Nnv Jersey 07458 .
Prentice Hall books arc widely"used by corporations anu govel'lllllent agencies for training, marketing, and resale.
The publisherofkrs discoullts on this hook when ordered in bulk quantities. For more information contact:
Corporate Sales Department Phone: 8003823419 Pax: 2012367141 Email: corpsalcs@prenhall.com
Or write:
Prentice Ifall PTR Corp. Sales Dept One Lake Sircet Upper Saddle Rivcr, New Jersey 07458
AI! rights reserved. Nl.J part of this book mily be rcpf(l(luced, ill any forlll or by any means, without permission in writing from the publisher.
Printed in the United St,l!cs of Alllerica
10
9
8
ISBN:
7
6
5
4
J
2
0132068893
PrenticeHall Intcrnational (UK) Limited, LOlldoll PrcnticcHall oj" Australia Ply. Limited, Sydlley
PrenliceHall Canada Inc
PrcntieeFlall HispanOimlcricana, 5.A., Mexico PrenticeHall of India Private Limited. N('\\, IJdhi PrenliceHall of Japan, Inc" lilkyo Simon & Schuster Asia Pte. Ltd., Singapore Editora PrcnticcHall do Brasil. LtdH., Rio de .falleiro
Toronto
CONTENTS
Preface
XVII
1
SECTION I
PROCESS MODELING
Introduction
1.1
1.2
3
Motivation
4
Models
1.2.1 How Models Are Used
3
1.3 Systems
10
5
1.3.1 Simulation 10
1.3.2 Linear Systems Analysis
1.3.3 A Broader View of Analysis
1.4 Background of the Reader
12
11
11
1
1.5 How To Use This Textbook 
12 
1.5.1 Sections 12 

1.5.2 Numerical Solutions 
13 
1.5.3 Motivating Examples and Modules
1.6 Courses Where This Textbook Can Be Used
Summary
Further Reading Student Exercises
14
14
15
13
13
vii
viii
Contents
2 
Process Modeling 16 

2.1 Background 17 

2.2 Balance Equations 17 

2.2.1 Integral Balances 18 

2.2.2 Instantaneous Balances 20 

2.3 Material Balances 20 

2.3.1 
Simplifying Assumptions 25 

2.4 Constitutive Relationships 
27 

2.4.1 Gas Law 27 

2.4.2 Chemical Reactions 
27 

2.4.3 Equilibrium Relationships 28 

2.4.4 Flowthrough Valves 29 

2.5 Material and Energy Balances 30 

2.5.1 
Review of Thermodynamics 31 

2.6 
Distributes Parameter Systems 34 

2.7 
Dimensionless Models 35 

2.8 
Explicit Solutions to Dynamic Models 36 

2.9 
General Form of Dynamic Models 37 

2.9.1 State Variables 37 

_{2}_{.}_{9}_{.}_{2} Input Variables 

2.9.3 Parameters 38 

2.9.4 Vector Notation 38 

Summary 40 Further Reading 40 Student Exercises 41 

SECTION II NUMERICAL TECHNIQUES 49 

3 
Algebraic Equations 
51 
3.1 Notations 51
3.2 General Form for a linear System of Equations 51
3.3 Nonlinear Functions of a Single Variable
54
3.3.1 Convergence Tolerance 55
3.3.2 Direct Substitution 55
3.3.3 Interval Halving (Bisection) 58
3.3.4 False Position (Reguli Falsi) 60
3.3.5 Newton's Method (or NewtonRaphson) 60
3.4 MATLAB Routines for Solving Functions of a Single Variable
3.4.1 fzero 63
3.4.2 roots 64
3.5 Multivariable Systems
64
63
3.5.1 Newton's Method for Multivariable Problems 66
3.5.2
QuasiNewton Methods 69
Contents
ix
3.6 MATlAB Routines for Systems of Nonlinear Algebraic Equations Summary 71
Further Reading
Student Exercises
Appendix
78
4 Numerical Integration
4.1 Background
4.2 Euler Integration
80
72
73
80
81
4.2.1 Explicit Euler 
81 
4.2.2 Implicit Euler 
82 
70
4.2.3 Numerical Stability of Explicit and Implicit Methods 83
4.3 RungeKutta Integration
88
4.3.1 Second Order RungeKutta 89
4.3.2 FourthOrder RungeKutta 93
4.4 MATlAB Integration Routines
4.4.1 ode23 and ode45 95
Summary
Further Reading Student Exercises
97
97
98
94
SECTION III
LINEAR SYSTEMS ANALYSIS
103
5 linearization of Nonlinear Models: The StateSpace Formulation
5.1 State Space Models 106
105
5.5.1 General Form of State Space Models 108
5.2 Linearization of Nonlinear Models 109
5.2.1 Single Variable Example 109
5.5.2 One State Variable and One Input Variable 110
5.2.3 Linearization of Multistate Models 112
5.2.4 Generalization 114
5.3 Interpretation of Linearization
5.4 Solution of the ZeroInput Form
117
119
5.4.1 Effect of Initial Condition Direction (Use of Similarity Transform) 120
5.5 Solution of the General StateSpace Form 127
5.6 MATlAB Routines step and initial
127
5.6.1 The MATLAB step Function 129
5.6.2 The MATLAB initial Function 129
Summary
Further Reading
130
131
Student Exercises 131
_{x}
Contents
6 Solving Linear nth Order ODE Models
142
6.1 Background 143
6.2 Solving Homogeneous. Linear ODEs with Constant Coefficients
145
6.2.1 Distinct Eigenvalues 146
_{6}_{.}_{6}_{.}_{2} Repeated Eigenvalues 148
6.2.3 General Result for Complex Roots 152
_{6}_{.}_{3} Solving Nonhomogeneous. Linear ODEs with Constant Coefficients
6.4 Equations with TimeVarying Parameters
6.5 Routh Stability CriterionDetermining Stability Without Calculating
154
Eigenvalues 157
6.5.1 Routh Array 157
Summary 160 Further Reading Student Exercises
161
161
7 An Introduction to laplace Transforms
168
7.1 Motivation 168
7.2 Definition of the Laplace Transform
7.3 Examples of Laplace Transforms
169
170
7.3.1 
Exponential Function 170 
_{7}_{.}_{3}_{.}_{3} 
TimeDelay (Dead Time) 172 
7.3.4 
Derivations 173 
_{7}_{.}_{3}_{.}_{5} 
Integrals 173 
7.3.6 
Ramp Function 174 
7.3.7 
Pulse 174 
7.3.8 
Unit Impulse 176 
7.3.9 
Review 177 
7.4 Final and Initial Value Theorems 177
7.5 Application Examples 178
7.5.1 Partial Fraction Expansion 179
7.6 Table of Laplace Transforms 185 Summary 187 Further Reading 187 Student Exercises 187
152
8 Transfer Function Analysis of FirstOrder Systems 190
8.1
_{8}_{.}_{2} Responses of FirstOrder Systems
Perspective 191
8.2.1 Step Inputs
8.2.2 Impulse Inputs
193
198
191
8.3 Examples of SelfRegulating Processes
200
8.4
Integrating Processes
206
Contents
xi
8.5 LeadLag Models
208
8.5.1 Simulating LeadLag Transfer Functions 
209 

Summary 
211 

Student Exercises 
211 

9 Transfer Function Analysis of HigherOrder Systems 
215 
9.1 Responses of SecondOrder Systems
216
9.1.1 Step Responses
9.1.2 Underdamped Step Response Characteristics
9.1.3 Impulse Responses
9.1.4 Response to Sine Inputs
217
222
224
221
9.2 SecondOrder Systems with Numerator Dynamics
9.3 The Effect of PoleZero Locations on System
226
Step Responses
228
9.4 Pade Approximation for Deadtime
9.5 Converting the Transfer E;unction Model to StateSpace Form
9.6 MATLAB Routines for Step and Impulse Response
230
234
9.6.1 step
9.6.2 impulse
Summary
Student Exercises
234
236
236
237
10 Matrix Transfer Functions
247
10.1 A SecondOrder Example
10.2 The General Method
10.3 MATLAB Routine ss2tf
248
251
252
10.3.1 Discussion of the Results from Example 10.2
Summary 257 Student Exercises
257
255
11 Black Diagrams
261
11.1 Introduction to Block Diagrams
262
232
11.2 Block Diagrams of Systems in Series 
262 

11.3 PoleZero Cancellation 
263 

11.4 Systems in Series 
267 

11.4.1 Simulating Systems in Series 
267 
11.5 Blocks in Parallel
269
11.5.1 Conditions for Inverse Response
271
11.6 Feedback and Recycle Systems
11.7 Routh Stability Criterion Applied to Transfer Functions
273
11.7.1 Routh Array
277
276
11.8
SIMULINK 278
xii
Contents
Summary
Student Exercises
279
280
12 Linear Systems Summary
282
12.1 Background 283
12.2 Linear Boundary Value Problems
12.3 Review of Methods for Linear Initial Value Problems
283
287
12.3.1 Linearization 187
12.3.2 Direction Solution Techniques 288
12.3.3 Rewrite the StateSpace Model as a Single nth Order Ordinary Differential Equation 289
12.3.4 Use Laplace Transforms Directly on the StateSpace Model 290
12.4 Introduction to DiscreteTime Models
290
12.4.1 Discrete Transfer Function Models 291
12.5 Parameter Estimation of Discrete Linear Systems
Summary 
297 
References 
297 
Student Exercises
298
SECTION IV NONLINEAR SYSTEMS ANALYSIS
13 PhasePlane Analysis
303
13.1 Background 304
13.2 Linear System Examples
13.3 Generalization of PhasePlane Behavior
304
311
295
301
13.3.1 Slope Marks for Vector Fields 313
13.3.2 Additional Discussion 315
13.4 Nonlinear Systems
316
13.4.1 Limit Cycle Behavior 323
Summary
Further Reading Student Exercises
324
324
324
14 Introduction Nonlinear Dynamics: A Case Study of the Quadratic Map
14.1 Background 332
14.2 A Simple Population Growth Model
14.3 A More Realistic Population Model
332
334
331
14.3.1 Transient Response Results for the Quadratic (Logistic) Map 335
14.4 Cobweb Diagrams
14.5 Bifurcation and Orbit Diagrams
339
342
14.5.1
Observations from the Orbit Diagram (Figure 14.14) 342
Contents
xiii
14.6 Stability of FixedPoint Solutions
344
14.6.1 Application of the Stability Theorem to the Quadratic Map 344
14.6.2 Generalization of the Stability Results for the Quadratic Map 346
14.6.3 The Stability Theorem and Qualitative Behavior 346
14.7 Cascade of PeriodDoublings
14.7.1 Period2 348
14.7.2 Period4 351
14.7.3 Periodn
14.7.4 Feigenbaum's Number
348
353
14.8 Further Comments on Chaotic Behavior
354
Summary
References and Further Reading
Student Exercises
Appendix: Matlab MFiles Used in This Module
354
355
356
15 Bifurcation Behavior of Single ODE Systems
15.1 Motivation 360
15.2 Illustration of Bifurcation Behavior
15.3 Types of Bifurcations
15.3.1 Dynamic Responses
362
365
361
Summary 376
References and Further Reading
Student Exercises Appendix 379
377
376
360
16 Bifurcation Behovior of TwoState Systems
381
358
16.1 Background 381
16.2 SingleDimensional Bifurcations in the PhasePlane 382
16.3 limit Cycle Behavior 
384 
16.4 The Hopf Bifurcation 
388 
16.4.1 Higher Order Systems (n > 2)
Summary 392 Further Reading 392 Student Exercises 392
17 Introduction to Chaos: The Lorenz Equations
17.1 Introduction 396
17.2 Background
17.3 The Lorenz Equations
396
397
391
395
17.3.1 SteadyState (Equilibrium) Solutions
398
_{x}_{i}_{v}
Contents
17.4 
Stability Analysis of the Lorenz Equations 399 

17.4.1 Stability of the Trivial Solution 399 

17.4.2 Stability of the Nontrivial Solutions 400 

17.4.3 Summary of Stability Results 301 

17.5 
Numerical Study of the Lorenz Equations 402 

17.5.1 Conditions for a Stable Trivial (No Flow) Solution 402 

17.5.2 Stable Nontrivial Solutions 403 

17.5.3 Chaotic Conditions 405 

17.6 
Chaos in Chemical Systems 
407 

17.7 
Other Issues in Chaos 409 

Summary 410 

References and Further Reading 
410 

Student Exercises 411 

Appendix 412 

SECTION IV 
REVIEW AND LEARNING MODULES 
413 

Module 1 
Introduction to MATlAB 
415 

M1.1 
Background 416 

M1.2 
Using This Tutorial 
416 

M1.3 
Entering Matrices 
417 

M1.4 
The MATLAB Workspace 
419 

M1.5 
Complex Variables 
421 

M1.6 
Some MATLAB Operations 
421 

M1.7 
Plotting 422 

M1.8 
More Matrix Stuff 
426 

M1.9 
FOR Loops and IFTHEN Statements 427 

M1.10 
mfiles 428 

M1.11 
Diary 430 

M1.12 
Toolboxes 430 

M1.13 
Limitations to Student MATLAB 431 

M1.14 
Contacting Mathworks 431 

Student Exercises 432 

Module 2 
Review of Matrix Algebra 
435 
M2.1 
Motivation and Notation 
436 

M2.2 
Common Matrix Operations 
436 

M2.3 
Square Matrices 
440 

M2.4 
Other Matrix Operations Summary 450 
448 
Student Exercises
450
Contents
xv
Module 3 
Linear Regression 452 

M3.1 
Motivation 452 

M3.2 
Least Squares Solution for a Line 454 

M3.3 
Solution for the Equation of a Line Using MatrixVector Notation 455 

M3.4 
Generalization of the Linear Regression Technique 
456 

M3.5 
MATLAB Routines polyfit and polyval 458 

Module 4 
Introduction to SIMUlINK 464 

M4.1 
Introduction 464 

M4.2 
Transfer FunctionBased Simulation 
466 

M4.3 
Printing SIMULINK Windows 469 

Module 5 
Stirred Tank Heaters 
471 

M5.1 
Introduction 471 

M5.2 
Developing the Dynamic Model 
472 

M5.3 
SteadyState Conditions 475 

M5.4 
StateSpace Model 475 

M5.5 
Laplace Domain Model 
477 

M5.6 
Step Responses: Linear versus Nonlinear Models 
478 

M5.7 
Unforced System Responses: Perturbations 

in Initial Conditions 
483 

Module 6 
Absorption 490 

M6.1 
Background 490 

M6.2 
The Dynamic Model 
491 

M6.3 
SteadyState Analysis 
495 

M6.4 
Step Responses 
496 

M6.5 
Unforced Behavior 501 

Module 7 
Isothermal Continuous Stirred Tank Chemical Reactors 
506 

M7.1 
Introduction 506 

M7.2 
FirstOrder Irreversible Reaction 
507 

M7.3 
Van de Vusse Reaction 
516 

Module 8 
Biochemical Reactors 
529 

M8.1 
Background 529 

M8.2 
Modeling Equations 
530 

M8.3 
SteadyState Solution 
534 

M8.4 
Dynamic Behavior 535 
xvi
Contents
M8.5 
linearization 536 

M8.6 
PhasePlane Analysis 
539 

M8.7 
Understanding Multiple SteadyStates 540 

M8.8 
Bifurcation Behavior 
549 
Module 9 
Diabatic Continuous Stirred Tank Reactors 
559 

M9.1 
Background 560 

M9.2 
The Modeling Equations 
561 

M9.3 
SteadyState Solution 
563 

M9.4 
Dynamic Behavior 565 

M9.5 
linearization of Dynamic Equations 
567 

M9.6 
PhasePlane Analysis 
571 

M9.7 
Understanding Multiple SteadyState Behavior 572 

M9.8 
Further Complexities 
580 

M9.9 
Dimensionless Model 
584 

Module 10 
Ideal Binary Distillation 597 
M10.1 
Background 597 

M10.2 
Conceptual Description of Distillation 
599 

M10.3 
Dynamic Material Balances 
601 

M10.4 
Solving the SteadyState Equations 
603 

M10.5 
Solving the Nonlinear Dynamic Equations 
605 

M10.6 
StateSpace Linear Distillation Models 
606 

M10.7 
Multiplicity Behavior 
608 
Index
617
PREFACE
An understanding of the dynamic behavior of chemical processes is ilnportant from bolh process design and process control perspectives. _{I}_{t} is easy to design a chemical process, based on stcady~state considerations, which is practically uncontrollable when the process dynamics arc considered. The current status of computational hardware and software has made it easy to interactively simulate the dyo<:unic behavior of chemical processes.
It is comJllon for process dynamics to he included as the introductory portion of a
process control textbook, however, there afC a number of limitations to this approach. Since the emphasis of most or the textbooks is on process control, there is too little space to give adequate depth to modeling, analysis, and sinwlatioll of dynamic systems. The focus tends to he on transfer function~based models that arc used for control systenl de sign. The prime motivation for my textbook is then to provide a more comprehensive treatment of process dynamics, including modeling, analysis, and simulation. This text book evolved from notes dcvelopcd for a course on dynamic systems that I have becn teaching at Rcnsselaer since 199 I. Vie have been fortunate to have a two~semestcr se~ qucnee in dynamics and control, allowing more depth to the coverage of each topic. Topics covered here that arc not covered in a traditional text include nonlinear dy namics and the usc of MA TLAB for numerical analysis and simulation. Also, a signifi~ cant portion of the text consists of review and learning modules. I~ach learning module provides model development, stcady~statc solutions, nonlinear dynamic results, linear~ ization, state space and transfer function analysis and simulation. The motivation for this approach is to allow the student to "tic~togelher" all of the concepts, rather than {rcat~ ing the III independently (and not understanding the connections between the different methods).
xvii
xviii
Preface
An important feature of this text is the usc of MATLAB software. A set of Infiles used in many of the examples and in the learning nlodules is available via the world wide wcb at the following locations:
http:/wwwhpi.cdu/hel}ueb/Process_Dynamics
hHp:/www.mathworks.com/education/thirdparty.htmI
Additional learning modules will also be available at the RPI location. A few acknowledgments arc in order. A special thanks to Professor Jim Turpin at the University of Arkansas, who taught me the introductory course in process dynamics and control. Ilis love of teaching should be an inspiration to us all. Many thanks to one of my graduate students, Lou Russo, who not only made a numher of suggestions to improve the text, but also sparked an interest in many of the undergraduates that h;:lVe taken the course. The {(Isk of developing a solutions manual has heen carried out by Venkatcsh Natarajan, Brian Aufderheide, l<amcsh Rao, Vinay Prasad, and Kevin Schott. Prelinllnary dratls of' many chapters werc developed over cappuccinos at the Daily Grind in Albany and Troy, Bass Ale served at the El Dorado in ~rroy promoted discus sions about tcaching (and other somewhat unrelated topics) with my graduate students; the effect of the many Buffalo wings is still unclear. Final revisions to the textbook were done under the influence of cappuccinos at Cafe Avanti in Chicago (while there is a lot or effort in devcloping interactive classroom environments at Rensselaer, my ideal study en vironment looks much like a cofree shop), Teaching and learning should be dynamic processes. r would appreciate any com ments and suggestions that yOll have on this textbook. I will use the WWW site to provide updated examples, additional problems with· solutions, and suggestions for teaching and studying process dynamics.
B, Wayne RequeUe
SECTION I
PROCESS MODELING
INTRODUCTION
_{1}
This chapter provides a motivation for process modeling and the study of dynamic chemi cal processes. It also provides an overview of the structure of the textbook. After studying this chapter, the student should he able to answer the following questions:
What is a process model?
• Why develop a process model?
• What is the difference between lumped parameter and distributed parameter sys toms?
• What numerical package forms the basis for the examples in this text?
• What arc the major objectives of this textbook?
The major sections arc:
1.1 Moti valion
1.2 Models
1.3 Systems
1.4 Background or the Reader
1.5 How to Use This Texthook
1.6 Courses Where This Textbook Can Be Used
1.1
MOTIVATION
Robert Reich in nze Work {~lNations has classified three broad categories of employment in the United States. In order of increasing educational requirement these categories are:
3
1
Chap.
Introduction
4
services. To di
symbolicanalytic
services, and
inperson
services,
production
routine
rectly quote from Reich:
They sim
symbols.
manipulal1ng
by
and broker problems
identify,
"Symbolic analysts solve,
experimented with,
COlll
rearranged, juggled,
be
that
into abstract inmges
call
reality
plify
The
transformed hack into reality.
ma
eventually,
_{a}_{n}_{d} _{t}_{h}_{e}_{n}_{,}
municatcd to other spc<:iaJists,
Illay
be
tools
The
experience.
by
sharpened
tools,
analytic
with
done
nipulations
arc
psycho·
princiules,
.rcief/rifle
gimmicks,
argmllcllts, financial
legal
lIlathematical algorithms,
or deduction,
persuade or to amuse, systems of induction
or any
_{l}_{o}_{g}_{i}_{c}_{a}_{l} _{i}_{n}_{s}_{i}_{g}_{h}_{t}_{s} ahoUl how
to
(italics added for emphasis)
puulcs."
other sct of techniques for _{d}_{o}_{i}_{n}_{g} _{c}_{o}_{n}_{c}_{e}_{p}_{t}_{u}_{a}_{l}
engineers
Process
s)'mholic analysts.
engineers)
(and particularly
are
process
Engineers
_{f}_{o}_{r} _{m}_{a}_{t}_{h}_{e}_{m}_{a}_{t}_{i}_{c}_{a}_{l} _{m}_{o}_{d}_{e}_{l}_{s} _{t}_{h}_{a}_{t} _{c}_{h}_{a}_{r}_{a}_{c}_{t}_{e}_{r}_{i}_{z}_{e}
usc fundamental scientific principles as a hasis
Symbols are used to represent _{p}_{h}_{y}_{s}_{i}_{c}_{a}_{l} _{v}_{a}_{r}_{i}_{a}_{b}_{l}_{e}_{s}_{,} _{s}_{u}_{c}_{h}
the behavior of a chemical process.
_{I}_{n}_{p}_{u}_{t} _{i}_{n}_{f}_{o}_{r}_{m}_{a}_{t}_{i}_{o}_{n} _{i}_{s} _{s}_{p}_{e}_{c}_{i}_{f}_{i}_{e}_{d} _{a}_{n}_{d} _{n}_{u}_{m}_{e}_{r}_{i}_{c}_{a}_{l} _{a}_{l}_{}
_{a}_{s} _{p}_{r}_{e}_{s}_{s}_{u}_{r}_{e}_{,} temperature _{o}_{r} _{c}_{o}_{n}_{c}_{e}_{n}_{t}_{r}_{a}_{t}_{i}_{o}_{n}_{.}
_{P}_{r}_{o}_{c}_{e}_{s}_{s}_{:} _{e}_{n}_{g}_{i}_{n}_{e}_{e}_{r}_{s}
system).
a physical
solve the _{r}_{n}_{o}_{d}_{e}_{l}_{s} _{(}_{s}_{i}_{m}_{u}_{l}_{a}_{t}_{i}_{n}_{g}
_{a}_{r}_{c} _{l}_{l}_{s}_{e}_{d}
gorithms
to
of _{t}_{h}_{e}_{s}_{e} _{s}_{i}_{m}_{u}_{l}_{a}_{t}_{i}_{o}_{n}_{s} to make decisions or recommendations regarding
analyze the results
of _{a} _{p}_{r}_{o}_{c}_{e}_{s}_{s}_{.}
_{t}_{h}_{e} _{d}_{e}_{s}_{i}_{g}_{n} or operation
in
pmcc:':ises
work with chemical manufactUling
one way
Most chemical engineers
troubleshooting in
for technical
responsible
process ergincers
Often they
or another.
arc
de
responsible
Some
1'01'
operations nf _{a} _{p}_{a}_{r}_{t}_{i}_{c}_{l}_{d}_{a}_{r} _{c}_{h}_{e}_{m}_{i}_{c}_{a}_{l}
process.
daytndeiY
the
~Ire
(such
temperature
or pre.s
variables
that process
as
_{s}_{i}_{g}_{n}_{i}_{n}_{g} _{f}_{e}_{e}_{d}_{b}_{a}_{c}_{k} control
systems so
_{f}_{o}_{r} _{r}_{e}_{d}_{e}_{s}_{i}_{g}_{n}_{i}_{n}_{g}
responsihle
a
be
Others
values.
_{a}_{t} _{d}_{e}_{s}_{i}_{r}_{e}_{d}
may
maintained
he
.sure) can
of _{t}_{h}_{e}_{s}_{e} _{r}_{e}_{s}_{p}_{o}_{n}_{s}_{i}_{b}_{i}_{l}_{i}_{t}_{i}_{e}_{s} _{r}_{e}_{q}_{u}_{i}_{r}_{e} _{a}_{n} _{u}_{n}_{}
All
provide more profitahility.
chemical process
to
of chemical processes.
derstanding of _{t}_{h}_{e} _{t}_{i}_{m}_{e}_{}_{d}_{e}_{p}_{e}_{n}_{d}_{e}_{n}_{t}_{(}_{d}_{y}_{n}_{a}_{m}_{i}_{c}_{)} _{b}_{e}_{h}_{a}_{v}_{i}_{o}_{r}
1.2 MODELS
of
understanding
_{i}_{n} _{d}_{e}_{v}_{e}_{l}_{o}_{p}_{i}_{n}_{g}
this textbook is _{t}_{o} _{a}_{s}_{s}_{i}_{s}_{t} _{y}_{o}_{u}
an
of
'fhe _{p}_{r}_{i}_{m}_{a}_{r}_{y} _{o}_{b}_{j}_{e}_{c}_{t}_{i}_{v}_{e}
assessing _{t}_{h}_{e} _{d}_{y}_{n}_{a}_{m}_{i}_{c} be
for
A requirement
of c1\<?mical
the dynamic behavior havior is a
processes.
of _{t}_{h}_{e} _{c}_{h}_{e}_{m}_{i}_{c}_{a}_{l} process under considera
model
mathematical
time~dcpendent
a def'ini
Before proceeding, it _{i}_{s} _{w}_{o}_{r}_{t}_{h} consulting with _{t}_{w}_{o} _{d}_{i}_{f}_{f}_{e}_{r}_{e}_{n}_{t} dictionaries for
tion.
!nodel.
of
tion
Mode!
Didionary Definitions:
"a small
it
Used as
means
a noun,
which means
modus,
a measure.
fro1l11he Latin
is derived
Model
Dictiof/wy).
_{N}_{e}_{w} _{W}_{o}_{r}_{l}_{d}
(Webster's
representation of a pl<lIllled or existing object"
whose behavior is
conditions,
or physical system, obeying certain specified
"/\ mathematical
analogous in some
it is
which
or social
system to
biological,
a physical,
understand
used
to
and Techn;cal
(McGrawlIill Dietiof/ar.v
way"
Tl~rms),
(~f,)'cie1/t!fic
Sec. 1.2
Models
5
Notice that both definitions stress that a model is a representation of a system or ohject. In this textbook, when we usc the term model, we will be referring to a mathematical model. We prefer to usc the following definition f~)rmodel (more specifically, a process model).
Working Definition:
Pmccss Model
A process model is a set of equations (including the necessary input data to solve the equations) that allows us to predict the behavior of a chemical process system.
The emphasis in this text is on the development and lise offundamental or firstprinciples models. By fundamental, we mean models that are based on known physicalchemical rc~ lationships. This includes the conservation of mass and conservation of energy, I as well as reaction kinetics, transport phenomena, and thermodynamic (phllse equilibrium, etc.) relatiomdlips. Another common model is the empirical model. An empirical model might be used if the process is too complex for a fundamental model (either in the fonnulation of the model, or the numerical solution of the model), or if the empirical model has satisfactory predictive capability. An example of an empirical model is a simple least squares fit of an equation lo experimental data. Generally, we would prefer to use models based on fundamental knowledge _{o}_{f} chemicalphysical relationships. Fundamental models will generally he accurate over .a mueh larger range of conditions than empirical models. Empirical models may be useful for "interpolation" but are generally not useful lilr "extrapolation"; that is, an empirical model will only be useful over the range of conditions used for the "fit" of the data. It should be nOled that it is rare for a single process model to exist. A model is only an approximate representation of an actual process. The complexity of a process model will depend on the final usc of the model. If only an approximate answer is needed, then a simplified model can often be lIsed.
1.2.1 How Models Are Used
As we have noted, given a set of input data, a model is used to predict the output "re sponse." A model can be used to solve the following types of problems:
Marketing: If the price of a product is increased, how much will the demand de crease?
• Allocation: If we have several sources for raw materials, and several manufacturing
101' course, the real conservalioll law is that of massenergy, but we will neglect the inter
change of mass and energy due to nuclear reactions.
_{6}
Introduction
_{C}_{h}_{a}_{p}_{.} _{1}
plants, how do we distrihute the raw materials among the plants, and decide what products each plant produces?
Synthesis: What process (sequence of reactors, separation devices, etc.) can he used
to manufacture a product?
• Design: What type and size of equipment is necessary to produce a product?
Operation: What operating conditions willmaxirnizc the yield of a product?
Control: How can a process input be manipulated to maintain a measured process output at a desired value?
Safety: If an equipment failure occurs, what will he the impact on the operating per sonnel and other process equipment?
Environmental: IIow long will it take to "biodegrade" soil contaminated with haz ardolls waste?
Many or the rnodels cited above arc based on a steadystate analysis. This book will cxtend the steadystate material and energy balance concepts, generally prescnted in an introductory textbook on chemical engineering principles, to dynamic systems (systems where the variables change with time). As an example of the increasing importance of knowledge of dynamic behavior, consider process design. In the past, chemical process design was based solely on steadystatc analysis. A problem with performing only a steadystate design is that it is possible to design a process with desirable steadystate characteristics (minimal energy consumption, etc.) but which is dynamically inoperable. Hence, it is important to consider the dynamic operability characteristics of a process dur ing the design phase. Also, batch processes that arc commonly used in the pharmaceutical or specialty chemicals industries arc inherently dynamic and cannot bc simulated with steadystate models. In the previous discussion we have characterized models as stcadystate or dy
_{n}_{a}_{m}_{i}_{c}_{.} Another characterization is in ter111s 01" lumped porarneter system.)· or distributed
_{p}_{a}_{r}_{a}_{m}_{e}_{t}_{e}_{r} _{s}_{y}_{s}_{t}_{e}_{m}_{s}_{.} A lumped parameter systcm assumes that a variable or interest (tem perature, for example) changes only with one independent variable (time, For cxamjJlc, but not space). A typical example of a lumped parameter system is a perfectly mixed (stirred) tank, where the temperature is uniform throughollt the tank. A distrihuted para meter system has more than one independent variable; for example, temperature may vary with both spatial position and time.
EXAMPLE 1.1
A Lumped Parameter System
Consider a perfectly insulated, wellstirred tank where a hot liquid stream at 60 ^{u} C is mixed with a cold liquid stream at lone (Figure 1.1). The wc11~mixed assumption means that the fluid tem perature in the tank is uniform and equal to the temperature at the exit from the t<mk. This is all example of a lumped parameter system, since the temperature docs not vary with spatial pOSition.
Sec. 1.2
Models
7
Hot
Cold
iii
FIGURE 1.1
Outlet
Stirred lank.
Consider now the ~leadystale behavior of this process. If the only stream was the hot fluid, thell the outlet temperature wOl/ld be eqllal to the hot fluid temperature if the tank were per
fectly insulated. Similarly, if the only stream was the cold stream, then the outlet temperature
would be equal to the cold lluid temperature. A combination of the two streams yields an out let tClJlpcrutufc that is intermediate between the cold and hot temperatures, as shown in Fig
ure
] .2.
o
60
f? 50
'0
@
.2
~
'"
Q.
~
40
30
l
ID
8 20
10 _{o}
FIGURE 1.2
_~~.l.
l~~~~~~~~
0.2
0.4
0.6
Hot Flow, fraction
0.8
Relationship between hot flow and outlet temperature.
We sec that there is a linear steadystate relationship between the hot flow (fraction) and the out let temperature. Now we consider the dynamic response to a change in the fraction of hot flow. Figure 1.3 compares outlet temperature responses for various step changes in hot flow fraction at t :::: 2.5
8
Introduction
Chap. 1
minutes. We sec that the changes afC symmetric, with the same speed of response. We will find later that these responses afC indicative of a lincar system.
o
'"
_{4}_{5}
40
+20%
~ 35 f~"~~~~Q~o~~~~
ci:
E

230 

20% 

25 

^{2}^{0} o 
, 
,.' 

_{5} 
10 
15 
20 
25 
30 
FIGlJRE 1.3
time, min
Response of temperature to various changes in the hoI llow fraction.
EXAMPLE 1.2
A Histributed Parameter System
A simplified representation of a counterflow heat exchanger is shown in Figure lA. A cold water stream flows through one side of the excbanger and is heated by energy transfcrcd fro!ll a condensing steam ,,,trcam. This is a distributed parameter systcnl because the tClnperature of the water stream can change with lime and position.
Water in
~IF=: Steam in
FIGURE 1.4
Counterflow heat exchanger.
The steady~slate tell1perature profile (water temperature as a function of position) is shown in Figure 1.5. Notice that rate of change of the water temperature \vith respect to distance decreases as the water tcmpenlturc approaches the steam teinpcrature (I OOOe). This is because the tcmper
Sec, 1,2
Models
9
ature gradient rOf heat transfer decreases as the water temperature increases. The outlet water
temperature as a function of inlet water temperature is shown in Figure 1.6.
0
'"
"
"
100
80
ci. 60
E
JE
40
^{2}^{0} _{a}
0.2
Flf;LJlU: 1.5
0.4
0.6
Z, distance
0.8
W::tter temperature as it function of position.
0
'" '"
"
J'
_{E}
~
0
100
98
96
^{9}^{4}
92
90
88
^{8}^{6} _{a}
FIGURE 1.6
_{2}_{0}
40
60
inlet temperature, deg C
80
100
Outlet water temperature;Is a function of inlet water temperature.
10
Introduction
Chap. 1
Mathematical models consist of the following types of equations (including combina
tions)
Algebraic equations
Ordinary differential equations
Partial differential equations
The emphasis in this textbook is on developing models that consist of ordinary dif ferential equations. These equations generally result from macroscopic balances around processes, with an assumption of a perfectly mixed system. To find the steadystate solu tion of a set of ordinary differential equations, we must solve a set of algebraic equations. Partial ditTerential equation models result from microscopic b<tlanccs and arc not covered in this textbook. One of the main techniques for solving partial differential equations is !:nlsed on converting a partial differential equation to a set of ordinary differential equa tions. Techniques deYeloped in this textbook can then be lIsed to solve these problems,
1.3
SYSTEMS
We have been using the term system yery loosely. Consider the following definition.
Dctinition:
Svstem
A combination of several pieces of equipment integrated to perform a specific function; thus a fire (arlillery) control system may include a tracking radar, computer, and gun (McGrawHill Dictio
limy (?f5;ciellt!fic and Technical Tenns).
The example in the definition presellted is of interest to electrical, aeronautical, and rnili tary engineers. I'or our purposes, a system witl be composed of chemical unit operations, such as chemical reactors, heat exchangers, and separation devices, which arc used to pro ducc a chemical product. Indeed, we will oftcn consider a single unit operation to be a system composed of inputs, states (to be defined later) and outputs. A series of modules in Section V of this textbook cover the behavior of a number of specific unit operations.
1.3.1
Simulation
One of the goals of this textbook is to develop numerical analysis techniques that allow liS to "simulate" the behavior of a chemical process, Typically, steadystate simulation of a lumped parameter system involves the solution of algebraic equations, while dynamic simulation involves the solution of ordinary differential equations. We must be careful when using computer simulation. First of all, we must he able to say, Do the results of this
Sec. 1.3
Systems
11
simulation make sense? Common sense and "back of the envelope" calculations will tell us if the numerical results arc in the ballpark.
1.3.2 linear Systems Analysis
The mathematical tools that arc lIsed to study linear dynamic systems problems me known as linear systems analysis techniques. Traditionally, systems analysis techniques have been based on linear systems theory_ Two basic approaches arc typically used:
(i) Laplace transforms afC lIsed to analyze the behavior of a single, linear, nth order o("cii nary differential equation, and (ii) state space techniques (based on the linear algebra techniques of eigenValue and eigenvector analysis) arc used to analyze the behavior of multiple firstorder linear ordinary differential equations. If a system of ordinary difreren~ tial equations is nonlinear, they can be linearized at a desired steadystate operating point.
1.3.3 A Broader View of Analysis
In this textbook we usc analysis in a broader context than linear systems analysis that may be applied to a model with a specific vallie for the pararnetcrs. Analysis means seeking a deeper understanding of a process than simply performing a simulation or solving a set of equations for a particular set of parameters and input values. Often we want to understand how the response of system variablc (tempera.ture, for example) changes whcn a parame tcr (c.g., heat transfer coefficient) or input (fJowrate or inlet temperature) changes. Rather than trying to obtain the understanding of the possible types of behavior hy merely run ning many simulations (varying parameters, etc.), we must decide which parameters (or inputs or initial conditions) are likely to vary, and use analysis techniques to determine if a qualitative change ofhehavior (number of solutions or stability of a solution) can occur. This qualitative change is illustrated in l';'igure 1.7 below, which shows possihle steadystate behavior for ajackcled chemical reactor. In l<'igure 1.7a there is a monotonic
Jacket Temperature
a. Monotonic
Jacket Temperature
b. MUltiplicity
FIGlJRE l.7 Two qualitatively differclll types of input/output behavior. Steadyslale reactor temperature as a function of steadystate jackct lelnpera
lurc.
_{1}_{2}
Introduction
Chap. 1
relationship between jacket temperature and reactor temperature, that is, as the s(cady~
state j;:lckct temperature increases, the steadystate reactor temperature increases. Figure
1.7b illustrates behavior known as output multiplicity, that is, there is a region of stcady
state jacket temperatures where a single j'H.:kct temIJcraturc can yield three possible reac tor temperatures. In Chapter 15 (and module 9) we show how to vary a reactor design pa~ wllleter to change from one type of behavior to another. Engineering problem solving can be a comhination of art and science. 'rile com plexity and accuracy of a solution will depend on the information available or what is dc~ sired in the final solution. If you arc simply performing a rough (back of the envelope) cost estirnatc for a process design, perhaps a simple stcady~statematerial and energy _{b}_{a}_{l}_{~} ance will suffice. On the other hand, if an optimum design integrating several unit opera
tions is required, then a more complex solution will be involved.
1.4 BACKGROUND OF THE READER
It is assumed that the reader of this textbook htls a sophomore or jUllior~levclchemical engineering background. In addition to the standard introductory chemistry, physics, and mathematics (including dilTerential equations) eourse,S, the 'student has taken an introduc tion to chemical engineering (material and energy haJ;:mces, reaction stoichiometry) cour,Se. This textbook can also be used by an engineer in industry who nceds to develop dy~ namic models to perform studies to improve a process or design controllers. Although a few years may have lapsed since the engineer took a differential equations course, the re view provided in this text should be sufficient for the development and solution of models based on differential equations. Also, this textbook can serve as review material for first year graduate student who is interested in process modeling, systems analysis, or numeri cal methods.
1.5 HOW TO USE THIS TEXTBOOK
The ultimate objective of this textbook is to be able to model, simulate, and (more impor tantly) understand the dynamic behavior of chemical processes.
1.5.1
Sections
In Section I (Chapters ] and 2) we show how to develop dynamic models for simple chemical processes. Numerical techniques for solving algebl'<ric and differential equations are covered in Section II (Chapters 3 and 4). Much of the textbook is based on linear sys tem analysis techniques, which arc presented in Section III (Chaptcrs 5 through l2). Non linear analysis techniques are prescnted in Section IV (Chapters 1317). Section V (Mod~
Sec. 1.6
Courses Where This Textbook Can Be Used
_{1}_{3}
uks 1 through lO) consists or a number of learning modules 10 reinforce the concepts dis cussed in Sections I through IV.
1.5.2 Numerical Solutions
It is much casier to learn a new topic by "doing" rather than simply reading about it. To understand the dynamic behavior of chemical processes, one needs to he able 10 solve dif ferential equations and plot response curves. We have used the MATLAB numerical
analysis package to solve equations in this text. AMATL.AB learning module is in the set
of modules in Section V (Module I) for readers who arc not l~ulliliarwith or need to be
reintroduced to MATLAB. MATLAB routines arc detailed within the chapter that they
arc used. Many of the examples haveMA"rLAB mfiles associated with them. It is recom~ mended that the reader modify these Illfiles to understand the effect of parameter changes on the numerical solution.
1.5.3 Motivating Examples and Modules
This textbook contains
the examples. You are c.ncouraged to work through each example to understand how a palticular technique can be applied. There is a limit to the complexity of an example that can he used when introducing a new technique; the examples presented in the chapters tend to be short and illustrate one or two numcricaltcchniqucs. 'fhere is a set of modules of t11odeb, in Section Y, that treats process examples in much more dclail. The objective of these modules is to provide a more complete treatment of modeling and simulation of a specific process. In each process modehng module, a numher of the techniques introduced in various chapters of the text arc applied to the problem at hancL
III any process examples. Often, new techniques arc introduced in
1.6 COURSES WHERE THIS TEXTBOOK CAN BE USED
This textbook is based on a required course that 1 have taught to chemical and environ mcntal engineering juniors at Renssclaer since 1991. This dynamic systems course (origi nally titled lumped parameler syslems) is a prerequisite to a required course on chemical process control, normally taken in the second semester of the junior year. This textbook can be used for the first term of a two~tcrm sequence in dynamics and control. I have not treated process control in this text because 1 feci that there is a need for more indepth coverage of process dynamics than is covered in most process control textbooks. This textbook can also be lIsed in courses such as process modeling or numerical methods for chemic111 engineers. Although directed towards undergraduates, this text can also be used in a firstyear graduate course on process modeling or process dynamics; in this case, much of the focus would be on Section IV (nonlinear analysis) and indepth studies of the modules.
14
Introduction
SUMMARY
At this point, the reader should be able to define or characterize the following
• Process model
Lumped or distributed parameter system
Analysis
Simulation
FURTHER
READING
The textbooks listed below are nice introductions to material and energy balances. The Rus sell and Denn book also provides an excellent introduction to models or dynamic systems.
Felder,
R.M.,
&
R.
ROllsseau.
(1986).
Processes, 2nd cd. New York: 'Wiley.
ElementalY
Principles
ql
Chemica!
Hinmlclblau, D.M. (1996). Basic Principles and Colclllation.'; ill Chemical E'/lJ;i /leering, 6th cd. Upper Saddle River, NJ: PrenticeHall.
Russell, T.R.F., &M.M. Denn. (1971).
Introduction
to Chemico! !'.'nginecrin/!.
Ihudysis, New York: Wiley.
A comprehensivc tutorial and reference for MA'fLAB is provided by Hanselman and Lit tlefield. Thc books by l~ttcr provide many excellent examples Llsing MATLAB to solve engineering problems.
lIanselman, D., & B. Littlefield. (1996). Maslerill,\!. MATLAB. Upper Saddle River, NJ: PrenticeHall.
Upper Saddle
[~lter, n.M. (199]). Engineering River, NJ: PrenticcIlall.
E~tter, D.M. (t096). Introduction to MA TLAU ,Ii)r engineers (/nd c)'CiCllfists. Uppcr
ProlJlem Soh'ing
Ivilh MATLAB.
Saddle Rivcl', NJ: Prenticerlalt.
The following book by Dcnn is a graduatelevel text that discusses the more philosophical issues involved in process modeling.
Denn, M.M. (1986). Process iV/odcling. New York: Longman.
An undergraduate control textbook with significant modeling and sitnulation is by Luy ben. Numerous FORTRAN examples are presented.
Luyben, \V.L. (1990). Process Modeling, 5'imulatioll alld Control for Chemical EI1 Rineers, 2nd cd. New York: McGrawHilL
Student Exercises
_{1}_{5}
A nmnber or control textbooks contain a limited amount of Illodeling. [~xal11p1cs include:
Seborg, D.E., TJ'·. Edgar, & D.A. Mellichamp. (1989). Process Dynamics and COIl trol. New York: Vhley.
Stephanopmdos, G. (l9X4). Chemical Process Control: An Introduction to Theory and Pract{(·e. r':nglewood Clift's, NJ: PrenticeHall.
The following book by Rameriz is more of all advanced undergraduHtelfirstycar graduate student text on numerical methods to solve chemical engineering problems. The emphasis
is on FORTRAN subroutines to be used with the IMSL nmlleriea! package.
Rameriz, W.F·, (1989).
Butterworths.
Computational 111ethods for Process SiJllulalioJl. Boston:
Issues in process modeling are discllssed by IIimlllelblau in Chapter :1 or the following book:
Bisio, A., & R.I
Kabel. (1985). S'c'oleujJ (~l('hemicol Processes. Nc\v York: V.,Iilcy.
The following book by Reich provides an excellent perspective on the glohal ecollomy and role played by U.S. workers
Reich, R.B. (1991). The Work qFNatiolls. New YOJ'k: Vintage Books,
STUDENT
EXERCISES
1. 
Review the matrix operation:; module (Section V). 
2. 
\Vork through the MATLAB module (Section V), 
3. 
Consider example 2. If there is a sudden increase in stearn prc.l;surc (and therefore, temperature) sketch the expected eoJd~sjde temperature profilel; at 0, 25, 50, 75, and loor;;;) or the distance through the heat exchanger. 
PROCESS MODELING
_{2}
In this chapter, a methodology for developing dynamic models of chcmicL11 processes is presented. After studying this chapter, the student should be able to:
\Vritc balance equations using the integral or instantaneous methods.
Incorporate appropriate constitutive relationships into the equations.
Determine the state, input and output variables, and parameters for a particular model (set of equations).
Determine the necessary in!~)tmatjonto solve it system of dynanlic equations.
Define dinlcnsionlcss variables and parameters to "scale" equations.
'file major sections arc:
2.1 Background
2.2 Balance Equations
2.3 Material Balances
2.4 Constitutive Relationships
2.5 Material and Energy Balances
2.6 DistribulcdParamclcr Systems
2.7
DimcllsionlcssModels
2.8 Explicit Solutions loDynamic Models
2.9 General ItOI'm or Dynamic Models
16
Sec. 2.2
Balance Equations
17
2.1 BACKGROUND
Many reasons for developing process modeLs were given in Chapter 1. Improving or un
derstanding chemical process operation is a m(~jor overall objective for developing a dy
namic process model. These models arc often used for (i) operator training, (ii) process
design, (iii) safely system analysis or design, or (iv) control system design.
Operator Training. The people responsible for the operation of a chemical manufacturing process arc known as process operators. A dynanlic process model catl be lIsed to perform simulations to train process operators, in the same fashion that flight sjm~ ulators arc used to train airplane pilots. Process operators call learn the proper response to upset conditions, before having to experience theill on the actual process.
Process Design. A dynamic process model call be llsed to properly design chcmical process equipment for a desired production rate. F'or example, a model of a batch chemical reactor can be used to determine the appropriate size of the reactor to pro~ duce a certain product at a desired rate.
Dynamic process models can aLso be used to design safety systems. For
example, they can be llsed to determine how long it will takc after a valve Ltils for a sys tem to reach a certain pressure.
Safety.
Control System Design. Feedback control systenls arc used to maintain process variables at desirable valucs. For cxample, a control system may measure a prod uct temperature (an output) and adjust the steam Ilowratc (an input) to maintain that de sired temperature. r'or complex systems, particularly those with many inputs and outputs, it is necessary to base the control system design on a process model. Also, before a COI11 plex control system is implemented on a process, it is normally tested by simulating the expected performance u~ing computer simulation.
2.2 BALANCE EQUATIONS
The emphasis in an introductory matcrial and energy balances tcxtbook is on steadystate balance cquations that have the rollowing form:
mass 01· energy]
I
cntcnng
a systcm

mass or e'l1crgy :
leaving
(l systcm
=
0
(2. I )
F~qlU1tion (2,1 )is deccptively simple becausc there may be many ins and outs, particulmly for component balances. The in and out terms would then include thc gcneration and con
_{1}_{8}
Process Modeling
Chap. 2
version of species by chemical reaction, respectively. In this text, we arc interested in dy
namic balances that have the form:
rate of mass (~rCT~crgyl
[
accumulation 111
a system
rate of mass or 1 , ale of mass or)
=
.energyentering
^{[}
a system

enelgy leavmg
a system
(2.2)
The rate of mass accumulation in a system has the form dM/dl where M is the total mass in the system. Similarly, the rate of energy accumulation has the form dEJdt where
E is the total energy in a system. H Hi is llsed to represent the moles of component i in a
system, then dN/dt represents the molar rate of accumulation of component i in the
systclll.
\Vhcn solving a problem, it is important to specify what is meant by system. In some cases the systcl1lmay be microscopic in nature (a e1i/Terential clement, for example), while in othcr cases it may be macroscopic in naturc (the liquid content of a mixing tank, for example). Also, when developing a dynamic model, we can take one of two general viewpoints. One viewpoint is based on an ifltegral balance, while the other is based on an instml{(lIIcoll.\· balance. Integral balances arc particularly useCul when developing models for distributed parameter systems, which result in partial differential equations; the focus in this text is on ordinary differential equationbased models. Another viewpoint is the in stantaneous balance where the time rate of change is written directly.
2.2.1 Integral Balances
An integral balance is developed by viewing a system at two different Sll<l!'S!lots in timc. Consider a finite time interval, D.t, and perform material balance over that time interval
[
.
mass or energy
inside the system
atl+tJ.1
I

[mass or energy
I
inside the system
all
mass or energy entering the system
r
from t to t
I
6.t

1
mass or energy leavmg the system
It om I to I + tJ.1
]
(2.3)
The rneanvalue theorems of integral and differential calculus are thcn used to reduce the equations to differential equations. F·'or example, consider the system shown ill F'igure 2.1 below, where one boundary represents thc mass in the systcm at time t, while the other boundary represents the mass in the system at _{t} _{+} _{i}_{1}_{t}_{.} An integral balance 011 thc total mass in the system is writtcn in the form:
Sec. 2.2
Balance Equations
19
mass in system at time =: t
)If
,r
mass in system at time:= t+!\ t
m _{O}_{U}_{f} (f)
FIGURE 2.1
Conceptual material
balance prohlem.
n~asscontained I rn~asscontained I 
III the system
In the system
all+Llt
all
=
mass culcI ing
the system
r from t to (
j
D.,
Mathematically, this is written:
MI, '"'  MI,
fiLii
J ';'i" iiI 
I
I ~I
J 11/"", lif
I

r mass ICdving
the system
hom I to t
I
nl
I
or
11,1/
MI'i"'  MI, = J(,izi"  ,iz,,,,,l dl
,
(2.4)
where M represents the total mass in the system, while filill andli1()111 represent the mass rates elltering and leaving the system, respectively. We can write the righthand side of
(2.4), using the mean value theorem of integral calculus, as:
f (';/ill  filma> dl
1+ !:J./
,
where 0 < (X < 1. Equation (2.4) can now be written:
dividing by dt,
MI"",
D
f
MI,
=
(
111'1/ 
lJlo"t
II
l!nM
and using the mean value theorem of dUferentia! calculus (0 < ~ < I) for the Icfthand side,
MI"",~MI,
/>1
,1M,
;it
[+IUI
20
Process Modeling
Chap. 2
which yields
dM
I
~i;I ~lIj.f = (1l1 _{i}_{J}_{i}  In""J II<d.l
I
Taking the limit as At goes to zero, we find
dM 
. 
. 
dl 
= mill  
111,,,,( 
^{(}^{2}^{.}^{5}^{)}
and representing the total mass as M = VP"h _{i}_{f}_{l} as FillPill andlilo!ll as FOII/p, where p is the mass density (mass/volume) and F is a volumetric nowrate (volume/time) we obtain the equation:
(2.6)
Note that we have assumed that the system is perfectly mixed, so that the density of mate rial leaving the system is equal to the density or material in the system.
2.2.2 Instantaneous Balances
Here we write the dynamic balance equations directly, based on an instantaneous ratc~of~ change:
I
I
the laic 01 accumulatIOn of
lmass III the system
which can be written directly as,
or
I
=.::
··
I
dM
df
dVp _{~}
d/
rate of
mass entering
the system
]

1
rate of
mass leaving
the system
1 ^{.}
(2. 7)
 
(2.8) 

J11 _{i}_{n} 
. 
l1I _{o} l1! 
(29) 
which is the same result obtained using an intcgral balancc. Although the integral balancc takes longer to arrivc at the same resull as the instantaneous balancc method, the integral balance method is probably clearer whcn dcvcloping distributed parameter (partial differ ential equationhased) models. An cxnmplc is shown in Section 2.6. Section 2.3 covers material balances and Section 2.5 covers material and energy balances. Section 2.4 discusses constitutive relationships.
2.3 MATERIAL BALANCES
'l'he simplcst modeling problems consist of material halances. [n this section we usc sev eral process exarnples to illustrate the modeling techniques used,
Sec. 2.3
Material Balances
21
 ~
_{}_{~}_{}_{}_{}_{}_{~}_{}_{}_{}_{}
EXAIVIPLE 2.1
Liquid Suq.:e Tank
Surge tanks arc often Llsed to "smooth" f10wratc fluctuations in liquid streams f!mvillg between chemical processes. Consider a liquid surge tank with one inlet (flowing from process I) and one outlet stream (flowing to process Ii) (Figure 2.2). Assume that the dellsity is constant. Find how
the volume of the tank varies as a function of time, if the inlet and outlet flowratcs vary. List the
s((ltc variables, [Jarometers, as weI! as the il/fJut and oll/Im/voriables. Give the necessary infor
mation to complete the quantitative solution to this prohlem.
FIGUnE 2.2
v
L
L,iquid surge tank.
••
F
The system is the liquid in the lank, the liquid surface is the top boundary of the system. 'rile fol lowing notation is used in the modeling equations:
F
F
,
~ inlet volumetric r10wrate (volume/time)
outlet volumctric f10wratc
~
V volumc of liquid in thc tank
P liquid dcnsity (mass/volullle)
Integral i\'lethod
Consider a fillite time intcrval, !J.l. Performing a material balance over that time interval,
J11dSS 01 \Vdlel] lllslde the lank
<it I
I
!J.t

[tlldSS 01 WdtCl lllSldc the td.nk
elt I
]

which we can write InalhcmaticaHy as:
mass of water] entering lank 
from I to t
1 ill
[lllass of walcr leaving tank
froJ11 ( to I
f
!:it
(',
.3.1
1\':'1
JFpdl
Jr:p dt
, ,
ESCOL/\ Dc Ei CIULlO i
(2.10)
22
Procoss Modeling
Chap.2
Bringing the righthand side terms under the same integral
vpl,
\<
. vpl, 
J(r,:p
1;"\/
Ii,) rlr
(2.11 )
We can lise the mean value theorem of integral calculus to write the righthand side of (2.11)
(where 0 So: 0'
:::;
1) as:
I
!j{
J(1';1'  I'p) dl
(2.12)
,
Substituting (2.12) into (2.11)
Vpll''''
vpll
Dividing by f),.t, we obtain
(2.13)
vpl, ,',
b.t
JlPI, ~ (r
IP
r
11
PI","
(214)
and using the lucan value theorem of differential calculus. as !\.r' ;. 0
InstantaneOllS Method
dVp
dt
(2.15)
Here we write the balance equations based on an inslautancOU:i rate ofchange:
the rate of ch,~ngc of I = I.mass n~l\vratc (}C
1
mass of water III tank
_water lllln tank
I I mass flowratc ofI
water out of tank_
The total mass of water tn fhe tank is Vp, the rate of change is dVp/dt, <:Inc! the density of the out let stream is equal to the tank contents:
dyp
dt
(2.16)
which is exactly what we derived using the intcf{ral method. Given the same set of assumptions the two methods should yield the sam<.~rnodel. You should usc the approach (integral or instanta neous) that makes the most sense to YOL!o In this. text we generally usc the illstantaneous ap proach since it requires the fewest number of steps. Notice the implicit assumption that the density of water in the tank docs not depend upon position (the perfect mixing assumption). This ai>sumption allows an ordinary differential cqlJa~ tion (ODE) formulation. \Ve refer to any system that can be modeled by ODEs as lumped para _{m}_{e}_{I}_{e}_{r} _{s}_{y}_{s}_{t}_{e}_{m}_{s}_{.} Also notice that the outlet stream density must be equal to the density of water in the tank. This knowledge also allows us to say that the density terms in (2.16) arc equal. This equation is then reduced 101
lit might he tempting to the reader to begin to direuly write "volume balance" exprt'ssions that look similar to (2.17). We wish to make it clear that therc is llO such thing as a volume balance and (2017) is only correct hecause of the constant density assumption. It is a good idea to always write a mass balance expn:s
_{s}_{i}_{o}_{n}_{,} such ::1S (2.16), before making as~;umpti()ns about the fluid density, which Jllay lead to (2.17).
Sec. 2.3
Mntcrial Balances
23
dV
dt
1;  F
(2.17)
Equation (2.17) is it lineDr ordinary dilTcwntial equation (ODE), which is trivial to solve if we know the inlet and outlet flowmtes as a fllnction of time, and if we know all initial condition for the volume in the wnk. In equation (2.17) we refer to Vas a slale variable, and F; nnc! F as input variah!cs (even though Fis an outlet stream flowratc). If dellsity remained in the equatioll, \VC would refer to it as a /NlrWJlctcF.
tn order to solve this problem \ve nlUst specify the inputs F/t) andF(t) and the initial con· dition \1(0).
Exanlple 2.1 provides all introduction to the notion of states, inputs, and parameters. This cxarnple illustrates how an overall material balance is llsed to find how the volume of a liquid phase system changes with time. It may he desirable to have tank height, II, rather than tank volume as the slate variable. If we aSSUlllC a constant tank crosssectional area, ll, we call express the tank volumc as V = Aft and the modeling eqU<:ltion as
dli
dl
_{A}
F
it
(2.18)
If we also know that the flowrate out of the tank is proportional to the square ront of the height of liquid in the tank, wc can usc the relationship (sec student exercisc 21)
F
=
[3VIi
where 13 is a J'lmv coefficient, to find
dli
dt
[3VIi
A
I
,(
A
(2.19)
(2.20)
For tbis model \ve refcr to h as the stole variablc, inlet nowrate (F) as the input variable and f3 and A as parameters. Notice that a single system (ill this case, the liquid surge tank) can have slightly dif ferent modeling equations and variables, depending on assumptions and thc objectives used whcn dcveJopiug the model.
EXAi\iIPI.,E 2.2
An Isothernwl Chemi<:al Rcactor
Assume that two chemical species,;\ and 8, arc in a solvent feedstream entering a Iiquid~phase chemical reactor that is maintained at a constant tcmperature (l"igurc 2.3). The two spec'lc::, react irreversibly to form a third species, F. Find the reactor concentration of each species as a ftlllC lion of time.
24
Process Modeling
Chap. 2
F.
I
^{C}
I
Overall Material Balance
FIGlJRE 2.3
Isothermal chemical reactor.
F
C
The overall mass balance is (since the tank is perfectly mixed)
(2.21)
ASSlIIllption:
The liquid phase density, p, is not a function of concentration, The tank (and out
let) density is then cqllallo the inlet density, so:
Pi
P
(2.22)
and we can write (2.21) as:
dV
tit
(2.23)
Component IVIaterial Balances
It is convenient to work in molar units when writing component balances, particularly if chemi cal reactions arc involved. Let (,'1\' ('/I. and C" represent the molar concentrations of A, H, and P
(moles/volume).
Assume that the stoichiometric equation for this reaction is
The component material balance equations are (assuming no component P is in the feed to the reactor):
(Ive _{A}
dt
dVC _{I}_{I}
dl
dVC,.
dl
(2.24)
(2.25)
(2.26)
Sec. 2.3
Material Balances
_{2}_{5}
Where 1~4' rr;, and I'p represent the rate of generatioll of species;\, II, and P per unit volume, and (~li and C'/li represent the inlet coneentallons of species A and N. Assume that the rate of reaction of A per unit volume is secondorder and 11 function of the concentration of both A and B. The reaction rate can be written
(2.27)
where k is the reaction rate constant and the minus sign indicates that A is consumed ill the reac tion. Each mole of A reacts with two moles of If (frotH the stoichiometric equation) and produces olle mote of I), so the rates of generation of Band P (per unit volume) arc:
Expanding the [cftlland side of (2.24),
dVC _{A}
df
f'
C
'/I
dV
dt
combining (2.23), (2.24), (2.27), and (2.30) we find:
(2.2X)
(2.29)
(2.30)
(2.31)
Similarly, the concentrations of n aud P call be written
dell
df
(2.32)
(2.33)
This model consists of four differential equations (2.23, 2.31, 2.32, 2.33) and, therefore, four state variables (V, c~\, C _{n} . and C,,). To solve these equations, we must specify the initial condi tions (V(O), CA(O), C/:I(t», and C,,(O)), the inputs (F _{i} . C _{A}_{i} , and e/li) as a function of time, and the parameter (k).
2.3.1 Simplifying Assumptions
The reactor model presented in Exalnple 2.2 has four differential equations. Often other simplifying assumptions arc made to reduce the number of differential equations, to make theln easier to analyze and faster to solve. For example, assmning a constant volume (dVldt:::: 0) reduces the number of equations by one. Also, it is common to feed an excess of one reactant to obtain nearly completc conversion of another reactant. If species B is maintained in a large excess, then CHis nearly constant. The reactioll rate cqual'101l can then be expressed:
_{I}_{'} _{.}_{1}
(2.34)
26
Process Modeling
Chap. 2
where
k _{l}
_{=}
kel/
(2.35)
The resulting differential equation~ are (since we assumed dVldt and dClldt::: 0)
de"
cit
(2.36)
(2.37)
Notice that if we only desire to know the concentration of species A we only need to solve
one differential equation, since the concentration or A is not dependent on the concentra tion of P.
EXAMPLE 2.3
Gas Surge Drum
Smgc drums are oncn used as intermediate storage capacity for gas streams that arc lransfclTcd
hctween chemical process units. COl1::idcr a drum depicted in Figure 2.4, where (fi is the inlet
Inola!" Ilowratc and q is the outlet molar tlowrate. Here we develop a model that describes how
the pressure in the tank varies with time.
q.
I
_{{}
p
FIGliRE 2.4
)
Gafi surge drum,
q
Let V = voJurne of the drum and V::: molar volume of the gas (volome/mole). 'rhe total amount of gas (moles) in the tank is then VI\/.
Assumption: The pressurevolume relationship is characterized hy the ideal gas law, so
PV= NT
(2.3H)
where P IS pressure, T is temperature (absolute scale), and R is the ideal gas constant. Equation (2.38) can be written
1
if
P
RT
and, therefore, the total amount of gas in the tank is
v
V
PV
NT = total amount (moles) of gas in the tank
(2.39)
(240)
the rate of accumlation of gas is then d(PV/NT)/dt. Assume that T is constant; since Vand Rare also constant; then the molar rate of accumlatioll of gas in the tank is:
Sec. 2.4
Constitutive Relationships
27
V
tiP
RT dt
~
'Ii

'I
(2.41)
where q,: is the molar rate of gas entering the drum and q is the molar rate of gas leaving the drum. Equation (2.41) can be written
dP
dt
RT
Bien plus que des documents.
Découvrez tout ce que Scribd a à offrir, dont les livres et les livres audio des principaux éditeurs.
Annulez à tout moment.