Elements of Chemical Reaction Engineering (3rd Edition) PDF
Preview Elements of Chemical Reaction Engineering (3rd Edition)
W CD-ROM , INCLUDED Elements of Chemical Reaction n 0 0 hngineering H. Scott Fogler Elements of Chemical Reaction Engineering Third Edition H. SCOTT FOGL,ER Arne and Catherine Vennema Professor of Chemical Engineelring The University of Michigan, Ann Arbor Prentice-Hall of India D u m Ma8Rd New Delhi - 110 001 2004 This Indian Reprint-Rs. 425.00 (Original US. Edition-&. 3805.00) ELEMENTS OF CHEMICAL REACTION ENGINEERING, 3rd Ed. (with CD-ROM) by H. Scott Fogler 0 1999 by Prentice-Hall, Inc., (now known as Pearson Education, Inc.), Upper Saddle River, New Jersey 07458, U.S.A. All rights resewed. No part of this book may be reproduced in any form, by mimeograph or any other means, without permission in writing from the publisher. ISBN-81 -203-2234-7 Published by Asoke K. Ghosh, Prentice-Hall of India Private Limited, M-97, Connaught Circus, New Delhi-110001 and Printed by Syfldicate Binders, A-20, Hosiery Complex, Noida, Phase-ll Extension, Noida-201305 (N.C.R. Delhi). Dedicated to the memory of Professors Giuseppe Parravano Joseph J. Martin Donald L. Katz of the University of Michigan whose standards and lifelong achievements serve to inspire us Contents PREFACE 1 MOLEBALANCES xv 1 1.1 Definition of the Rate of Reaction, -rA 2 1.2 The General Mole Balance Equation 6 1.3 BatchReactors 8 1.4 Continuous-Flow Reactors 10 1.4.1 Continuous-Stirred Tank Reactor 10 1.4.2 Tubular Reactor 11 1.4.3 Packed-Bed Reactor 14 Summary 25 Questions and Problems 25 CD-ROM Material 31 Supplementary Reading 31 1.5 Industrial Reactors 16 2 CONVERSION AND REACTOR SIZING 2.1 Definition of Conversion 33 2.2 Design Equations 34 2.2.1 Batch Systems 34 2.2.2 Flow Systems 37 Applications of the Design Equations for Continuous-Flow Reactors 40 2.3 2.4 Reactors in Series 48 2.5 Some Further Definitions 56 Summary 59 33 vii viii Questions and Problems 62 CD-ROM Material 66 Supplementary Reading 67 3 RATE LAWS AND STOICHIOMETRY 3.1 3.2 3.3 3.4 3.5 Basic Definitions 68 3.1.1 The Reaction Rate Constant 69 3.1.2 The Reaction Order and the Rate Law 73 3.1.3 Elementary Rate Laws and Molecularity 75 3.1.4 Reversible Reactions 77 3.1.5 Nonelementary Rate Laws and Reactions 81 Present Status of Our Approach to Reactor Sizing andDesign 83 Stoichiometric Table 84 3.3. I Batch Systems 84 3.3.2 Constant- Volume Reaction Systems 87 3.3.3 Flow Systems 90 3.3.4 Volume Change with Reaction 92 Expressing Concentrations in Terms Other Than Conversion 105 Reactions with Phase Change 107 Summary 111 Questions and Problems 114 CD-ROM Material 123 Supplementary Reading 123 4 ISOTHERMAL REACTOR DESIGN 4.1 4.2 4.3 4.4 4.5 4.6 4.7 Design Structure for Isothermal Reactors Scale-up of Liquid-Phase Batch Reactor Data to the Design ofaCSTR 129 4.2.1 Batch Operation 129 4.2.2 Design of CSTRs 137 Tubular Reactors 147 Pressure Drop in Reactors 153 4.4.1 Pressure Drop and the Rate Law 153 4.4.2 Flow Through a Packed Bed 154 4.4.3 Spherical Packed-Bed Reactors 168 4.4.4 Pressure Drop in Pipes 173 Synthesizing a Chemical Plant 174 Using CA (liquid) and FA (gas) in the Mole Balances and Rate Laws 176 4.6.1 CSTRs, PFRs, PBRs, and Batch Reactors 177 4.6.2 Membrane Reactors 182 Unsteady-State Operation of Reactors 187 125 Contents 68 125 Contents ix 4.7.1 Startup of a CSTR 189 4.7.2 Semibatch Reactors 190 4.7.3 Reactive Distillation 197 4.8 Recycle Reactors 200 Summary 202 ODE Solver Algorithm 204 Questions and Problems 205 Journal Critique Problems 219 Some Thoughts on Critiquing What You Read CD-ROM Material 220 Supplementary Reading 222 220 5 COLLECTION AND ANAL'YSIS OF RATE DATA 5.1 5.2 5.3 5.4 5.5 5.6 5.7 Batch Reactor Data 224 .5.1.1 Differential Method of Rate Analysis 224 .5.1.2 Integral Method 235 Method of Initial Rates 239 Method of Half-Lives 242 Differential Reactors 243 ]Least-Square Analysis 250 .5.5.1 Linearization of the Rate Law 250 5.5.2 Nonlinear Least-Squares Analysis 252 .5.5.3 Weighted Least-Squares Analysis 261 ]Experimental Planning (CD-ROM) 262 ]Evaluation of Laboratory Reactors (CD-ROM) 5.7.1 Integral (Fixed-Bed) Reactor 264 -5.7.2 Stirred Batch Reactor 264 5.7.3 Stirred Contained Reactor (SCSR) 265 -5.7.4 ]Continuous-Stirred Tank Reactor (CSTR) 265 5.7.5 Straight-Through Transport Reactor 266 5.7.6 Recirculating Transport Reactor 266 5.7.7 Summary of Reactor Ratings 267 !summary 268 Questions and Problems 269 Journal Critique Problems 279 CD-ROM Material 280 Supplementary Reading 280 263 6 MULTIPLE REACTIONS 223 2;82 6.1 Maximizing the Desired Product in Parallel Reactions 284 ti. 1.1 6.1.2 Maximizing the Rate Selectivity Parameter S jbr One Reactant 285 Maximizing the Rate Selectivity Parameter S for Two Reactants 288 __ X 6.2 6.3 6.4 6.5 6.6 Contents Maximizing the Desired Product in Series Reactions Algorithm for Solution to Complex Reactions 291 295 6.3.1 Mole Balances 295 6.3.2 Net Rates of Reaction 296 6.3.3 Rate Laws 297 6.3.4 6.3.5 Stoichiometry: Concentrations 300 6.3.6 Combining Step 301 6.3.7 Multiple Reactions in a CSTR 307 Sorting It All Out 314 TheFunPart 315 The Attainable Region CD-ROM 316 Summary 318 Questions and Problems 320 Journal Critique Problems 335 CD-ROM Material 335 Supplementary Reading 336 Stoichiometry: Relative Rates of Reaction 7 NONELEMENTARY REACTION KINETICS 7.1 7.2 7.3 7.4 7.5 Fundamentals 340 7.1.1 Active Intermediates 340 7.1.2 Pseudo-Steady-State Hypothesis (PSSH) Searching for a Mechanism 344 7.2.1 General Considerations 344 7.2.2 Reaction Pathways 352 Polymerization 354 7.3.1 Step Polymerization 356 7.3.2 Chain Polymerizations Reactions 360 7.3.3 Modeling a Batch Polymerization Reactor 7.3.4 Molecular Weight Distribution 370 7.3.5 Anionic Polymerization 375 Enzymatic Reaction Fundamentals 383 7.4.1 Dejhitions and Mechanisms 383 7.4.2 Michaelis-Menten Equation 386 7.4.3 Batch Reactor Calculations 389 7.4.4 Inhibition of Enzyme Reactions 391 7.4.5 Multiple Enzyme and Substrate Systems Bioreactors 393 7.5.1 Cell Growth 394 7.5.2 Rate Laws 396 7.5.3 Stoichiometry 398 7.5.4 Mass Balances 400 7.5.5 Chemostats 404 7.5.6 Design Equations 404 7.5.7 Wash-out 406 297 342 368 392 339 Contenits xi 7.5.8 Oxygen-Limited Fermentation 407 7.5.9 Scale-up 407 Summary 408 Questions and Problems 410 CD-ROM Material 423 Journal Critique Problems 424 Supplementary Reading 424 8 STEADY-STATE NONISOTHERMAL REACTOR DESIGN 8.1 8.2 8.3 8.4 8.5 8.6 8.7 Rationale 426 The Energy Balance 427 8.2.1 First Law Thermodynamics 427 8.2.2 Evaluating the Work Term 429 8.2.3 8.2.4 Dissecting the Enthalpies 432 8.2.5 Relating 8Hh(T), 8Hoh, and 8Cp 434 8.2.6 Constant of Mean Heat Capacities 435 8.2.7 Variable Heat Capacities 436 8.2.8 Heat Added to the Reactor, Q 438 Nonisothermal Continuous-Flow Reactors 440 8.3.1 Application to the CSTR 441 8.3.2 Adiabatic Tubular Reactor 451 8.3.3 Steady-State Tubular Reactor with Heat Exchange 458 Equilibrium Conversion 468 8.4.1 Adiabatic Temperature and Equilibrium 19.4.2 Optimum Feed Temperature 476 Nonadiabatic Reactor Operation: Oxidation of Sulfur Dioxide Example 478 8.5.1 Manufacture of Sulfuric Acid 478 (3.5.2 Catalyst Quantities 481 K.5.3 Reactor Configuration 482 8.5.4 Operating Conditions 482 bvlultiple Steady States 490 EL6.I Heat-Removed Term, R(T) 491 616.2 Heat of Generation, G(T) 492 8.6.3 Ignition-Extinction Curve 493 8.6.4 Runaway Reactions 497 8.6.5 Steady-State Bifircation Analysis 498 Monisothermal Multiple Chemical Reactions 500 8.7.1 Plug-Flow Reactors 500 8.7.2 CSTR 504 Summary 507 Dissecting the Steady-State Molar Flow Rates to Obtain the Heat of Reaction 430 Conversion 468 8426 Contents xii Questions and Problems 511 Journal Critique Problems 530 CD-ROM Material 530 Supplementary Reading 532 9 UNSTEADY-STATE NONISOTHERMAL REACTOR DESIGN 9.1 9.2 9.3 9.4 9.5 9.6 The General Equation 534 Unsteady Operation of CSTRs and Semibatch Reactors 9.2.1 Batch Reactors 537 9.2.2 Adiabatic Operation of a Batch Reactor 537 9.2.3 Transient CSTR, Batch, and Semibatch Reactors with Heat Exchanger-Ambient Temperature Not Spatially Uniform 548 535 Approach to the Steady State 553 Control of Chemical Reactors 558 9.4.1 Falling Ofthe Steady State 558 9.4.2 Adding a Controller to a CSTR 561 Nonisothermal Multiple Reactions 566 Unsteady Operation of PIug-Flow Reactors Summary 571 Questions and Problems 572 CD-ROM Material 579 Supplementary Reading 579 570 10 CATALYSIS AND CATALYTIC REACTORS 10.1 Catalysts 581 IO. I . 1 Dejinitions 582 IO. 1.2 Catalyst Properties 583 10.2 Steps in a Catalytic Reaction 591 10.2.1 Adsorption Isotherms 594 10.2.2 Surface Reaction 599 10.2.3 Desorption 601 10.2.4 The Rate-Limiting Step 601 Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step 603 10.3.1 Is the Adsorption of Cumene Rate-Limiting ? 606 10.3.2 Is the Surface Reaction Rate-Limiting? 609 10.3.3 Is the Desorption of Benzene Rate-Limiting? 610 10.3.4 Summary of the Cumene Decomposition 612 10.3.5 Rate Laws Derived from the Pseudo-Steady-State Hypothesis 616 10.3 10.4 Design of Reactors for Gas-Solid Reactions 619 10.4.1 Basic Guidelines 619 10.4.2 The Design Equations 619 534 581 Contents xiii 10.5 Heterogeneous Data Analysis for Reactor Design 620 10.5.1 10.5.2 10.5.3 10.5.4 Deducing a Rate Law from the Experimental Data 622 Finding a Mechanism Consistent with Experimental Observations 623 Evaluation of the Rate Law Parameters Reactor Design 627 624 10.6 Chemical Vapor Deposition 631 10.7 Catalyst Deactivation 634 10.7.1 Types of Catalyst Deactivation 636 10.7.2 Temperature-Time Trajectories 647 10.7.3 Moving-Bed Reactors 649 10.7.4 Straight-nrough Transport Reactors 655 10.7.5 Determining the Order of Deactivation 660 Device Fabricatim 662 10.8.1 Etching 664 Summary 665 Questions and Problems 668 Journal Critique Problems 682 CD-ROM Material 683 Supplementary Reading 684 10.8 Reaction Engineering in Microelectronic 11 EXTEERNAL DIFFUSION EFFECTS ON HETEROGENEOUS REACTIONS 1 1.1 Mass Transfer Fundamentals 687 11.1.1 Dejnitions 687 11.1.2 MolarFlux 687 11.1.3 FickS Firs1 Law 688 11.2.1 Evaluating the Molar Flux 689 11.2.2 Boundary Conditions 692 11.2.3 Modeling Diffusion Without Reaction 692 11.2.4 Temperature and Pressure Dependence 11.2.5 Modeling Diffusion with Chemical Reaction 698 11.3.1 Mass Transfer CoefJicient 699 11.3.2 Mass Transfer to a Single Particle 702 11.3.3 Mass Transfer-Limited Reactions in Packed Beds 706 11.3.4 Mass Transfer-Limited Reaction on Metallic Su~aces 714 11.4 What If ... ? (Parameter Sensitivity) 715 1 1.5 The Shrinking Core Model 719 11.2 Binary Diffusion 689 OfD,, 697 1 1.3 External Resistance to Mass Transfer 699 686 xiv Contents 11.5. I Catalyst Regeneration 720 11.5.2 Dissolution of Monodispersed Solid Particles 724 11.5.3 Flow and Dissolution in Porous Media 726 Summary 728 Questions and Problems 729 Journal Article Problem 735 Journal Critique Problems 735 CD-ROM Material 735 Supplementary Reading 736 12 DIFFUSION AND REACTION IN POROUS CATALYSTS 12.1 Diffusion and Reaction in Spherical Catalyst Pellets 739 Derivation of the Differential Equation Describing DifSusion and Reaction 741 Solution to the Diflerential Equation for a First-Order Reaction 746 12.1.1 Effective Diffusivity 739 12.1.2 12.1.3 Writing the Equation in Dimensionless Form 743 12.1.4 12.2 Internal Effectiveness Factor 747 12.3 Falsified Kinetics 753 12.4 Overall Effectiveness Factor 755 12.5 Estimation of Diffusion- and Reaction-Limited Regimes 758 12.5. I Weisz-Prater Criterion for Internal Diffusion 758 12.5.2 Mears' Criterion for External Difision 761 12.6 Mass Transfer and Reaction in a Packed Bed 761 12.7 Determination of Limiting Situations from Reaction Data 767 12.8 Multiphase Reactors 768 12.8.1 Slurry Reactors 769 12.8.2 Trickle Bed Reactors 783 12.9 Fluidized-Bed Reactorsc,,.RoM 786 12.10 The Overall View 787 12.1 1 Chemical Vapor Deposition Reactors 789 summary 793 Questions and Problems 795 Journal Article Problems 804 Journal Critique Problems 805 CD-ROM Material 805 Supplementary Reading 806 13 DISTRIBUTIONS OF RESIDENCE TIMES FOR CHEMICAL REACTORS 738 809 13.1 General Characteristics 809 13.1.1 Residence-Erne Distribution Function 811 Contents xv 13.2 Measurement of the RTD 812 13.2.1 Pulse Input 813 13.2.2 Step Tracer Experiment 818 13.3 Characteristics of the RTD 819 13.3.1 Integral Relationships 819 13.3.2 Mean Residence Time 821 13.3.3 Other Moments of the RTD 823 13.3.4 Normalized RTD Function, E(0) 825 13.3.5 Zntemal-Age Distribution Z(a) 826 13.4.1 RTDs in Batch and Plug-Flow Reactors 829 13.4.2 Single-CSTR RTD 829 13.4.3 Laminar Flow Reactor 831 13.4.4 PFWCSTR Series RTD 833 13.5 Reactor Modeling with the RTD 836 13.6 Zero-Par(meter Models 838 13.4 RTD in Ideal Reactors 829 13.6. I Segregation Model 838 13.6.2 Maximum Mixedness 844 13.6.3 Heat Effects 851 13.7 Using Software Packages 851 13.8 RTD and Multiple Reactions 854 13.8.1 Segregation Model 854 13.8.2 Maximum Mixedness 855 Questions and Problems 861 CD-ROM Material 868 Supplementary Reading 869 summary 860 14 MODELS FOR N(0NIDEAL REACTORS 14.1 Some Guidelines 871 14.2 One-Parameter Models 872 14.2. I Tanks-in-Series Model 873 14.2.2 Dispersion Model 877 Two-Parameter Models-Modeling Real Reactors with Combi- nations of Ideal Reactors 893 14.3.1 Real CSTR Modeled Using Bypassing and Dead Space 893 14.3.1A Solving the Model System for CA and X 894 14.3.1B Using a Tracer to Determine the Model Parameters in CSTR-wirh-Dead-Space-and-Bypass Model 895 14.3.2 Real CSTR Modeled with an Exchange Volume 899 14.3.2A Solving the Model System for CA and X 900 14.3 871 xvi Contents Appendix A Appendix B Appendix C Appendix D Appendix E Appendix F Appendix G Appendix H 14.3.28 Use of Software Packages to Determine the Model Parameters 901 Other Models of Nonideal Reactors Using CSTRs andPFRs 904 Summary 907 Questions and Problems 909 CD-ROM Material 916 Supplementary Reading 917 Using a Tracer to Determine the Model Parameters in a CSTR with an Exchange Volume 900 14.4 14.5 14.6 Using the RTD Versus Needing a Model 904 NUMERICAL TECHNIQUES A. 1 Useful Integrals in Reactor Design 921 A.2 Equal-Area Graphical Differentiation 922 A.3 Solutions to Differential Equations 924 A.4 Numerical Evaluation of Integrals 924 A S Software Packages 926 IDEAL GAS CONSTANT AND CONVERSION FACTORS 921 927 THERMODYNAMIC RELATIONSHIPS INVOLVING THE EQUILIBRIUM CONSTANT 929 MEASUREMENT OF SLOPES ON SEMILOG PAPER 935 SOFTWARE PACKAGES 936 NOMENCLATURE 938 MOLECULAR DYNAMICS OF CHEMICAL REACTIONS 941 G. 1 Collision Theory 941 G.2 Transition State Theory 944 G.3 Molecular Dynamics 948 OPEN-ENDED PROBLEMS 953 H. 1 Design of Reaction Engineering Experiment 953 H.2 Effective Lubricant Design 953 H.3 Peach Bottom Nuclear Reactor 953
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