Chemical Reaction Engineering Third Edition Octave Levenspiel Department of Chemical Engineering Oregon State University John Wiley & Sons New York Chichester Weinheim Brisbane Singapore Toronto ACQUISITIONS EDITOR Wayne Anderson MARKETING MANAGER Katherine Hepburn PRODUCTION EDITOR Ken Santor SENIOR DESIGNER Kevin Murphy ILLUSTRATION COORDINATOR Jaime Perea ILLUSTRATION Wellington Studios COVER DESIGN Bekki Levien This book was set in Times Roman by Bi-Comp Inc. and printed and bound by the Hamilton Printing Company. The cover was printed by Phoenix Color Corporation. This book is printed on acid-free paper.
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ISBN 0-471-25424-X(cloth : alk.281-dc21 97-46872 CIP Printed in the United States of America Preface Chemical reaction engineering is that engineering activity concerned with the exploitation of chemical reactions on a commercial scale. Its goal is the successful design and operation of chemical reactors, and probably more than any other activity it sets chemical engineering apart as a distinct branch of the engi- neering profession. In a typical situation the engineer is faced with a host of questions: what information is needed to attack a problem, how best to obtain it, and then how to select a reasonable design from the many available alternatives? The purpose of this book is to teach how to answer these questions reliably and wisely. To do this I emphasize qualitative arguments, simple design methods, graphical procedures, and frequent comparison of capabilities of the major reactor types.
This approach should help develop a strong intuitive sense for good design which can then guide and reinforce the formal methods. This is a teaching book; thus, simple ideas are treated first, and are then extended to the more complex. Also, emphasis is placed throughout on the development of a common design strategy for all systems, homogeneous and heterogeneous. This is an introductory book.
The pace is leisurely, and where needed, time is taken to consider why certain assumptions are made, to discuss why an alternative approach is not used, and to indicate the limitations of the treatment when applied to real situations. Although the mathematical level is not particularly difficult (elementary calculus and the linear first-order differential equation is all that is needed), this does not mean that the ideas and concepts being taught are particularly simple. To develop new ways of thinking and new intuitions is not easy. Regarding this new edition: first of all I should say that in spirit it follows the earlier ones, and I try to keep things simple.
In fact, I have removed material from here and there that I felt more properly belonged in advanced books. But I have added a number of new topics-biochemical systems, reactors with fluidized solids, gadliquid reactors, and more on nonideal flow. The reason for this is my feeling that students should at least be introduced to these subjects so that they will have an idea of how to approach problems in these important areas. iii i~ Preface I feel that problem-solving-the process of applying concepts to new situa- tions-is essential to learning.
Consequently this edition includes over 80 illustra- tive examples and over 400 problems (75% new) to help the student learn and understand the concepts being taught. This new edition is divided into five parts. For the first undergraduate course, I would suggest covering Part 1 (go through Chapters 1 and 2 quickly-don't dawdle there), and if extra time is available, go on to whatever chapters in Parts 2 to 5 that are of interest. For me, these would be catalytic systems (just Chapter 18) and a bit on nonideal flow (Chapters 11 and 12).
For the graduate or second course the material in Parts 2 to 5 should be suitable. Finally, I'd like to acknowledge Professors Keith Levien, Julio Ottino, and Richard Turton, and Dr. Amos Avidan, who have made useful and helpful comments. Also, my grateful thanks go to Pam Wegner and Peggy Blair, who typed and retyped-probably what seemed like ad infiniturn-to get this manu- script ready for the publisher.
And to you, the reader, if you find errors-no, when you find errors-or sections of this book that are unclear, please let me know. Octave Levenspiel Chemical Engineering Department Oregon State University Corvallis, OR, 97331 Fax: (541) 737-4600 Contents Notation /xi Chapter 1 Overview of Chemical Reaction Engineering I1 Part I Homogeneous Reactions in Ideal Reactors I11 Chapter 2 Kinetics of Homogeneous Reactions I13 2.1 Concentration-Dependent Term of a Rate Equation I14 2.2 Temperature-Dependent Term of a Rate Equation I27 2.3 Searching for a Mechanism 129 2.4 Predictability of Reaction Rate from Theory 132 Chapter 3 Interpretation of Batch Reactor Data I38 3.1 Constant-volume Batch Reactor 139 3.2 Varying-volume Batch Reactor 167 3.3 Temperature and Reaction Rate 172 3.4 The Search for a Rate Equation I75 Chapter 4 Introduction to Reactor Design 183 vi Contents Chapter 5 Ideal Reactors for a Single Reaction 190 5.1 Ideal Batch Reactors I91 52. Steady-State Mixed Flow Reactors 194 5.3 Steady-State Plug Flow Reactors 1101 Chapter 6 Design for Single Reactions I120 6.1 Size Comparison of Single Reactors 1121 6.2 Multiple-Reactor Systems 1124 6.4 Autocatalytic Reactions 1140 Chapter 7 Design for Parallel Reactions 1152 Chapter 8 Potpourri of Multiple Reactions 1170 8.1 Irreversible First-Order Reactions in Series 1170 8.2 First-Order Followed by Zero-Order Reaction 1178 8.3 Zero-Order Followed by First-Order Reaction 1179 8.4 Successive Irreversible Reactions of Different Orders 1180 8.6 Irreversible Series-Parallel Reactions 1181 8.7 The Denbigh Reaction and its Special Cases 1194 Chapter 9 Temperature and Pressure Effects 1207 9.2 Multiple Reactions 1235 Chapter 10 Choosing the Right Kind of Reactor 1240 Part I1 Flow Patterns, Contacting, and Non-Ideal Flow I255 Chapter 11 Basics of Non-Ideal Flow 1257 11.1 E, the Age Distribution of Fluid, the RTD 1260 11.2 Conversion in Non-Ideal Flow Reactors 1273 Contents Yii Chapter 12 Compartment Models 1283 Chapter 13 The Dispersion Model 1293 13.2 Correlations for Axial Dispersion 1309 13.3 Chemical Reaction and Dispersion 1312 Chapter 14 The Tanks-in-Series Model 1321 14.1 Pulse Response Experiments and the RTD 1321 14.2 Chemical Conversion 1328 Chapter 15 The Convection Model for Laminar Flow 1339 15.1 The Convection Model and its RTD 1339 15.2 Chemical Conversion in Laminar Flow Reactors 1345 Chapter 16 Earliness of Mixing, Segregation and RTD 1350 16.1 Self-mixing of a Single Fluid 1350 16.2 Mixing of Two Miscible Fluids 1361 Part 111 Reactions Catalyzed by Solids 1367 Chapter 17 Heterogeneous Reactions - Introduction 1369 Chapter 18 Solid Catalyzed Reactions 1376 18.1 The Rate Equation for Surface Kinetics 1379 18.2 Pore Diffusion Resistance Combined with Surface Kinetics 1381 18.3 Porous Catalyst Particles I385 18.4 Heat Effects During Reaction 1391 18.5 Performance Equations for Reactors Containing Porous Catalyst Particles 1393 18.6 Experimental Methods for Finding Rates 1396 18.7 Product Distribution in Multiple Reactions 1402 viii Contents Chapter 19 The Packed Bed Catalytic Reactor 1427 Chapter 20 Reactors with Suspended Solid Catalyst, Fluidized Reactors of Various Types 1447 20.1 Background Information About Suspended Solids Reactors 1447 20.2 The Bubbling Fluidized Bed-BFB 1451 20.3 The K-L Model for BFB 1445 20.4 The Circulating Fluidized Bed-CFB 1465 20.5 The Jet Impact Reactor 1470 Chapter 21 Deactivating Catalysts 1473 21.1 Mechanisms of Catalyst Deactivation 1474 21.2 The Rate and Performance Equations 1475 21.3 Design 1489 Chapter 22 GIL Reactions on Solid Catalyst: Trickle Beds, Slurry Reactors, Three-Phase Fluidized Beds 1500 22.1 The General Rate Equation 1500 22.2 Performanc Equations for an Excess of B 1503 22.3 Performance Equations for an Excess of A 1509 22.4 Which Kind of Contactor to Use 1509 22.5 Applications 1510 Part IV Non-Catalytic Systems I521 Chapter 23 Fluid-Fluid Reactions: Kinetics I523 23.1 The Rate Equation 1524 Chapter 24 Fluid-Fluid Reactors: Design 1.1 Straight Mass Transfer 1543 24.2 Mass Transfer Plus Not Very Slow Reaction 1546 Chapter 25 Fluid-Particle Reactions: Kinetics 1566 25.1 Selection of a Model 1568 25.2 Shrinking Core Model for Spherical Particles of Unchanging Size 1570 Contents ix 25.3 Rate of Reaction for Shrinking Spherical Particles 1577 25.5 Determination of the Rate-Controlling Step 1582 Chapter 26 Fluid-Particle Reactors: Design 1589 Part V Biochemical Reaction Systems I609 Chapter 27 Enzyme Fermentation 1611 27.1 Michaelis-Menten Kinetics (M-M kinetics) 1612 27.2 Inhibition by a Foreign Substance-Competitive and Noncompetitive Inhibition 1616 Chapter 28 Microbial Fermentation-Introduction and Overall Picture 1623 Chapter 29 Substrate-Limiting Microbial Fermentation 1630 29.2 Mixed Flow Fermentors 1633 29.3 Optimum Operations of Fermentors 1636 Chapter 30 Product-Limiting Microbial Fermentation 1645 30.1 Batch or Plus Flow Fermentors for n = 1 I646 30.2 Mixed Flow Fermentors for n = 1 1647 Appendix 1655 Name Index 1662 Subject Index 1665 Notation Symbols and constants which are defined and used locally are not included here. SI units are given to show the dimensions of the symbols.
interfacial area per unit volume of tower (m2/m3),see Chapter 23 activity of a catalyst, see Eq. stoichiometric coefficients for reacting substances A, B,. A cross sectional area of a reactor (m2), see Chapter 20 A, B,. reactants A, B, C, D, Geldart classification of particles, see Chapter 20 C concentration (mol/m3) CM Monod constant (mol/m3),see Chapters 28-30; or Michae- lis constant (mol/m3), see Chapter 27 c~ heat capacity (J/mol.K) CLA,C ~ A mean specific heat of feed, and of completely converted product stream, per mole of key entering reactant (J/ mol A + all else with it) d diameter (m) d order of deactivation, see Chapter 22 dimensionless particle diameter, see Eq.1 axial dispersion coefficient for flowing fluid (m2/s), see Chapter 13 molecular diffusion coefficient (m2/s) ge effective diffusion coefficient in porous structures (m3/m solids) ei(x) an exponential integral, see Table 16.1 xi ~ i iNotation enhancement factor for mass transfer with reaction, see Eq.6 concentration of enzyme (mol or gm/m3),see Chapter 27 dimensionless output to a pulse input, the exit age distribu- tion function (s-l), see Chapter 11 E, E*, E** RTD for convective flow, see Chapter 15 Eoo, Eoc? ECO, Ecc RTD for the dispersion model, see Chapter 13 Ei(x) an exponential integral, see Table 16.1 8 effectiveness factor (-), see Chapter 18 f fraction of solids (m3 solid/m3vessel), see Chapter 20 A volume fraction of phase i (-), see Chapter 22 F feed rate (molls or kgls) F dimensionless output to a step input (-), see Fig.12 G* free energy (Jlmol A) h heat transfer coefficient (W/m2.K),see Chapter 18 h height of absorption column (m), see Chapter 24 H height of fluidized reactor (m), see Chapter 20 H phase distribution coefficient or Henry's law constant; for gas phase systems H = plC (Pa.m3/mol),see Chapter 23 mean enthalpy of the flowing stream per mole of A flowing (Jlmol A + all else with it), see Chapter 9 enthalpy of unreacted feed stream, and of completely con- verted product stream, per mole of A (Jlmol A + all else), see Chapter 19 heat of reaction at temperature T for the stoichiometry as written (J) heat or enthalpy change of reaction, of formation, and of combustion (J or Jlmol) k reaction rate constant (mol/m3)'-" s-l, see Eq.