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Fundamentals of Chemical Reaction Engineering

384 Pages · 2006 · 17.93 MB · English

  • Fundamentals of Chemical Reaction Engineering

    Fundamentals of Chemical


    Reaction Engineering Fundal11entals of Chel11ical


    Reaction Engineering


    Mark E. Davis


    California Institute ofTechnology


    Robert J. Davis


    University ofVirginia


    Boston Burr Ridge, IL Dubuque, IA Madison, WI NewYork San Francisco St. Louis


    Bangkok Bogota Caracas Kuala Lumpur Lisbon London Madrid Mexico City


    Milan Montreal New Delhi Santiago Seoul Singapore Sydney Taipei Toronto 'ZZ


    McGraw-Hill Higher Education


    A Division ofThe MGraw-HillCompanies


    FUNDAMENTALSOFCHEMICALREACTIONENGINEERING


    PublishedbyMcGraw-Hili,abusinessunitofTheMcGraw-HiliCompanies,Inc., 1221Avenueofthe


    Americas,NewYork,NY 10020.Copyright©2003byTheMcGraw-HiliCompanies,Inc.Allrightsreserved.


    Nopartofthispublicationmaybereproducedordistributedinanyformorbyanymeans,orstoredina


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    UnitedStates.


    Thisbookisprintedonacid-freepaper.


    International 1234567890DOCroOC098765432


    Domestic 1234567890DOCroOC098765432


    ISBN 0-07-245007-X


    ISBN 0-07-119260-3(ISE)


    Publisher:ElizabethA.Jones


    Sponsoringeditor:SuzanneJeans


    Developmentaleditor:MajaLorkovic


    Marketingmanager:SarahMartin


    Projectmanager:JaneMohr


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    Coverdesigner: MaureenMcCutcheon


    Compositor: TECHBOOKS


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    Printer:R.R.Donnelley/Crawfordsville,IN


    Coverimage:Adaptedfrom artworkprovidedcourtesyofProfessorAhmedZewail'sgroupatCaltech.


    In1999,ProfessorZewailreceivedtheNobelPrizeinChemistryforstudiesonthetransitionstatesof


    chemicalreactionsusingfemtosecondspectroscopy.


    LibraryofCongressCataloging-in-PublicationData


    Davis,MarkE.


    Fundamentalsofchemicalreactionengineering/MarkE.Davis,RobertJ.Davis.- 1sted.


    p. em.- (McGraw-Hilichemicalengineeringseries)


    Includesindex.


    ISBN0-07-245007-X(acid-freepaper)- ISBN0-07-119260-3(acid-freepaper:ISE)


    I. Chemicalprocesses. I. Davis,RobertJ. II. Title. III. Series.


    TP155.7 .D38 2003


    660'.28-dc21 2002025525


    CIP


    INTERNATIONALEDITION ISBN0-07-119260-3


    Copyright©2003.ExclusiverightsbyTheMcGraw-HillCompanies,Inc.,formanufactureandexport.


    Thisbookcannot bere-exportedfrom thecountrytowhichitissoldbyMcGraw-HilI.TheInternational


    EditionisnotavailableinNorthAmerica.


    www.mhhe.com McGraw.Hili Chemical Engineering Series


    Editorial Advisory Board


    Eduardo D. Glandt, Dean, SchoolofEngineeringandAppliedScience, UniversityofPennsylvania


    Michael T. Klein, Dean, SchoolofEngineering, Rutgers University


    Thomas F. Edgar, ProfessorofChemicalEngineering, UniversityofTexasatAustin


    BaileyandOllis Marlin


    BiochemicalEngineeringFundamentals ProcessControl: DesigningProcessesandControl


    SystemsforDynamicPerformance


    Bennettand Myers


    Momentum,HeatandMassTransfer McCabe,Smith,and Harriott


    UnitOperationsofChemicalEngineering


    Coughanowr


    ProcessSystemsAnalysisand Control Middlemanand Hochberg


    ProcessEngineeringAnalysisinSemiconductor


    deNevers


    DeviceFabrication


    AirPollutionControlEngineering


    PerryandGreen


    de Nevers


    Perry'sChemicalEngineers'Handbook


    FluidMechanicsfor ChemicalEngineers


    PetersandTimmerhaus


    Douglas


    PlantDesignandEconomicsforChemicalEngineers


    ConceptualDesignofChemicalProcesses


    Reid,Prausnitz,andPoling


    Edgarand Himmelblau


    PropertiesofGasesandLiquids


    OptimizationofChemicalProcesses


    Smith,Van Ness,andAbbott


    Gates,Katzer,and Schuit


    Introductionto ChemicalEngineeringThermodynamics


    ChemistryofCatalyticProcesses


    Treybal


    King


    MassTransferOperations


    SeparationProcesses


    Luyben


    ProcessModeling,Simulation,andControlfor


    ChemicalEngineers To Mary, Kathleen, and our parents Ruth and Ted. _________________C.Ott:rEHl:S


    Preface xi Chapter 4


    Nomenclature xii


    The Steady-State Approximation:


    Catalysis 100


    Chapter 1


    4.1 Single Reactions 100


    The Basics of Reaction Kinetics


    4.2 The Steady-StateApproximation 105


    for Chemical Reaction


    4.3 Relaxation Methods 124


    Engineering 1


    1.1 The Scope ofChemical Reaction


    Chapter 5


    Engineering I


    Heterogeneous Catalysis 133


    1.2 The Extent ofReaction 8


    1.3 The Rate ofReaction 16 5.1 Introduction 133


    1.4 General Properties ofthe Rate Function for a 5.2 Kinetics ofElementary Steps: Adsorption,


    Single Reaction 19 Desorption, and Surface Reaction 140


    1.5 Examples ofReaction Rates 24 5.3 Kinetics ofOverall Reactions 157


    5.4 Evaluation ofKinetic Parameters 171


    Chapter 2


    Rate Constants of Elementary Chapter 6


    Reactions 53 Effects of Transport Limitations


    on Rates of Solid-Catalyzed


    2.1 Elementary Reactions 53


    Reactions 184


    2.2 Arrhenius Temperature Dependence ofthe


    Rate Constant 54 6.1 Introduction 184


    2.3 Transition-State Theory 56 6.2 External Transport Effects 185


    6.3 Internal Transport Effects 190


    Chapter 3 6.4 Combined Internal and External Transport


    Effects 218


    Reactors for Measuring Reaction


    Rates 64 6.5 Analysis ofRate Data 228


    3.1 Ideal Reactors 64


    Chapter 7


    3.2 Batch and Semibatch Reactors 65


    Microkinetic Analysis of Catalytic


    3.3 Stirred-Flow Reactors 70


    Reactions 240


    3.4 Ideal Tubular Reactors 76


    3.5 Measurement ofReaction Rates 82 7.1 Introduction 240


    3.5.1 Batch Reactors 84 7.2 Asymmetric Hydrogenation ofProchiral


    Olefins 240


    3.5.2FlowReactors 87


    ix x Contents


    7.3 Ammonia Synthesis on Transition Metal 10.2 One-Dimensional Models for Fixed-Bed


    Catalysts 246 Reactors 317


    7.4 Ethylene Hydrogenation on Transition 10.3 Two-Dimensional Models for Fixed-Bed


    Metals 252 Reactors 325


    7.5 Concluding Remarks 257 lOA Reactor Configurations 328


    10.5 FluidizedBedswithRecirculatingSolids 331


    Chapter 8


    Nonideal Flow in Reactors 260 Appendix A


    Review of Chemical Equilibria 339


    8.1 Introduction 260


    8.2 Residence Time Distribution (RTD) 262 A.1 Basic Criteria for Chemical Equilibrium of


    8.3 Application ofRTD Functions to the Reacting Systems 339


    Prediction ofReactor Conversion 269 A.2 Determination ofEquilibrium


    804 Dispersion Models for Nonideal Compositions 341


    Reactors 272


    8.5 Prediction ofConversion with an Axially Appendix B


    Dispersed PFR 277 Regression Analysis 343


    8.6 Radial Dispersion 282


    B.1 Method ofLeast Squares 343


    8.7 Dispersion Models for Nonideal Flow


    B.2 Linear Correlation Coefficient 344


    in Reactors 282


    B.3 Correlation Probability with a Zero


    Y-Intercept 345


    Chapter 9


    BA NonlinearRegression 347


    Nonisothermal Reactors 286


    9.1 The Nature ofthe Problem 286 Appendix C


    9.2 Energy Balances 286 Transport in Porous Media 349


    9.3 Nonisothermal Batch Reactor 288


    C.1 Derivation ofFlux Relationships in


    9.4 Nonisothermal Plug Flow Reactor 297


    One-Dimension 349


    9.5 Temperature Effects in a CSTR 303


    C.2 Flux Relationships in Porous Media 351


    9.6 Stability and Sensitivity ofReactors


    Accomplishing Exothermic Reactions 305


    Index 355


    Chapter 10


    Reactors Accomplishing


    Heterogeneous Reactions 315


    10.1 Homogeneous Versus Heterogeneous


    Reactions in TubularReactors 315


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