Elements Of Chemical Reaction Engineering

Transcription

ELEMENTS OFCHEMICAL REACTIONENGINEERINGFIFTH EDITION1-1. SCOTT FOGLERINTERNITIONAL SERIEPHYSICAL AND CHEMICAL ENGINEERING SCIENCESFREE SAMPLE CHAPTERSHARE WITH OTHERS:t rm:

Elementsof ChemicalReactionEngineeringFifth Edition

Elementsof ChemicalReactionEngineeringFifth EditionH. SCOTT FOGLERAme and Catherine Vennema Professor of Chemical Engineeringand the Arthur F. Thurnau ProfessorThe University of Michigan, Ann ArborBoston Columbus Indianapolis New York San Francisco Amsterdam Cape TownDubai London Madrid Milan Munich Paris Montreal Toronto Delhi Mexico CitySão Paulo Sidney Hong Kong Seoul Singapore Taipei Tokyo

Many of the designations used by manufacturers and sellers to distinguish their products are claimed astrademarks. Where those designations appear in this book, and the publisher was aware of a trademark claim,the designations have been printed with initial capital letters or in all capitals.The author and publisher have taken care in the preparation of this book, but make no expressed or impliedwarranty of any kind and assume no responsibility for errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of the use of the information or programscontained herein.For information about buying this title in bulk quantities, or for special sales opportunities (which may includeelectronic versions; custom cover designs; and content particular to your business, training goals, marketingfocus, or branding interests), please contact our corporate sales department at corpsales@pearsoned.com or(800) 382-3419.For government sales inquiries, please contact governmentsales@pearsoned.com.For questions about sales outside the United States, please contact international@pearsoned.com.Visit us on the Web: informit.comLibrary of Congress Cataloging-in-Publication DataFogler, H. Scott, author.Elements of chemical reaction engineering / H. Scott Fogler.—Fifth edition.pages cmIncludes index.ISBN 978-0-13-388751-8 (hardcover : alk. paper)1. Chemical reactors. I. Title.TP157.F65 2016660'.2832—dc232015032892Copyright 2016 Pearson Education, Inc.All rights reserved. Printed in the United States of America. This publication is protected by copyright, andpermission must be obtained from the publisher prior to any prohibited reproduction, storage in a retrievalsystem, or transmission in any form or by any means, electronic, mechanical, photocopying, recording, orlikewise. For information regarding permissions, request forms and the appropriate contacts within the Pearson Education Global Rights & Permissions Department, please visit www.pearsoned.com/permissions/.ISBN-13: 978-0-13-388751-8ISBN-10: 0-13-388751-0Text printed in the United States on recycled paper at RR Donnelley in Kendallville, Indiana.First printing, January 2016

Dedicated toJanet Meadors FoglerFor her companionship, encouragement,sense of humor, love, and support throughout the years

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ContentsPREFACExviiABOUT THE AUTHORCHAPTER 11.11.21.31.41.5CHAPTER 22.12.22.32.42.5xxxiiiMOLE BALANCES1The Rate of Reaction, –rA4The General Mole Balance Equation8Batch Reactors (BRs)10Continuous-Flow Reactors121.4.1Continuous-Stirred Tank Reactor (CSTR)1.4.2Tubular Reactor141.4.3Packed-Bed Reactor (PBR)18Industrial Reactors2212CONVERSION AND REACTOR SIZINGDefinition of Conversion32Batch Reactor Design Equations32Design Equations for Flow Reactors352.3.1CSTR (Also Known as a Backmix Reactor or a Vat)362.3.2Tubular Flow Reactor (PFR)362.3.3Packed-Bed Reactor (PBR)37Sizing Continuous-Flow Reactors38Reactors in Series472.5.1CSTRs in Series482.5.2PFRs in Series522.5.3Combinations of CSTRs and PFRs in Series532.5.4Comparing the CSTR and PFR Reactor Volumes and ReactorSequencing57vii31

viiiContents2.6CHAPTER 33.13.23.33.4CHAPTER 44.14.24.3CHAPTER 55.15.25.35.45.55.6Some Further Definitions582.6.1Space Time582.6.2Space Velocity60RATE LAWS69Basic Definitions703.1.1Relative Rates of Reaction71The Reaction Order and the Rate Law723.2.1Power Law Models and Elementary Rate Laws723.2.2Nonelementary Rate Laws763.2.3Reversible Reactions80Rates and the Reaction Rate Constant833.3.1The Rate Constant k833.3.2The Arrhenius Plot90Present Status of Our Approach to Reactor Sizing and Design93STOICHIOMETRYBatch Systems1074.1.1Batch Concentrations for the Generic Reaction,Equation (2-2)109Flow Systems1134.2.1Equations for Concentrations in Flow Systems4.2.2Liquid-Phase Concentrations1144.2.3Gas-Phase Concentrations115Reversible Reactions and Equilibrium Conversion126105114ISOTHERMAL REACTOR DESIGN: CONVERSIONDesign Structure for Isothermal Reactors140Batch Reactors (BRs)1445.2.1Batch Reaction Times145Continuous-Stirred Tank Reactors (CSTRs)1525.3.1A Single CSTR1525.3.2CSTRs in Series155Tubular Reactors162Pressure Drop in Reactors1695.5.1Pressure Drop and the Rate Law1695.5.2Flow Through a Packed Bed1705.5.3Pressure Drop in Pipes1745.5.4Analytical Solution for Reaction with Pressure Drop5.5.5Robert the Worrier Wonders: What If 181Synthesizing the Design of a Chemical Plant190139177

ixContentsCHAPTER 6ISOTHERMAL REACTOR DESIGN:MOLES AND MOLAR FLOW RATES6.16.26.36.46.56.6CHAPTER 77.17.27.37.47.57.67.7CHAPTER 88.18.28.38.4The Molar Flow Rate Balance Algorithm208Mole Balances on CSTRs, PFRs, PBRs, and Batch Reactors6.2.1Liquid Phase2086.2.2Gas Phase210Application of the PFR Molar Flow Rate Algorithm to aMicroreactor212Membrane Reactors217Unsteady-State Operation of Stirred Reactors225Semibatch Reactors2276.6.1Motivation for Using a Semibatch Reactor2276.6.2Semibatch Reactor Mole Balances227207208COLLECTION AND ANALYSIS OF RATE DATA243The Algorithm for Data Analysis244Determining the Reaction Order for Each of Two Reactants Using theMethod of Excess246Integral Method247Differential Method of Analysis2517.4.1Graphical Differentiation Method2527.4.2Numerical Method2527.4.3Finding the Rate-Law Parameters253Nonlinear Regression258Reaction-Rate Data from Differential Reactors264Experimental Planning271MULTIPLE REACTIONSDefinitions2808.1.1Types of thm for Multiple Reactions2828.2.1Modifications to the Chapter 6 CRE Algorithm for MultipleReactions284Parallel Reactions2858.3.1Selectivity2858.3.2Maximizing the Desired Product for One Reactant2858.3.3Reactor Selection and Operating Conditions291Reactions in Series294279

xContents8.58.68.78.8CHAPTER 9Complex Reactions3048.5.1Complex Gas-Phase Reactions in a PBR3048.5.2Complex Liquid-Phase Reactions in a CSTR3078.5.3Complex Liquid-Phase Reactions in a SemibatchReactor310Membrane Reactors to Improve Selectivityin Multiple Reactions312Sorting It All Out317The Fun Part317REACTION MECHANISMS, PATHWAYS, BIOREACTIONS,AND BIOREACTORS9.19.29.39.4CHAPTER 1010.110.2333Active Intermediates and Nonelementary Rate Laws3349.1.1Pseudo-Steady-State Hypothesis (PSSH)3359.1.2Why Is the Rate Law First Order?3389.1.3Searching for a Mechanism3399.1.4Chain Reactions343Enzymatic Reaction Fundamentals3439.2.1Enzyme–Substrate n Equation3489.2.4Batch-Reactor Calculations for Enzyme Reactions354Inhibition of Enzyme Reactions3569.3.1Competitive Inhibition3579.3.2Uncompetitive Inhibition3599.3.3Noncompetitive Inhibition (Mixed Inhibition)3619.3.4Substrate Inhibition363Bioreactors and Biosynthesis3649.4.1Cell Growth3689.4.2Rate Laws3699.4.3Stoichiometry3719.4.4Mass Balances3779.4.5Chemostats3819.4.6CSTR Bioreactor Operation3819.4.7Wash-Out383CATALYSIS AND CATALYTIC REACTORSCatalysts39910.1.1 Definitions40010.1.2 Catalyst Properties40110.1.3 Catalytic Gas-Solid Interactions40310.1.4 Classification of Catalysts404Steps in a Catalytic Reaction40510.2.1 Step 1 Overview: Diffusion from the Bulk to the ExternalSurface of the Catalyst40810.2.2 Step 2 Overview: Internal Diffusion409399

xiContents10.310.410.510.610.7CHAPTER 1111.111.211.311.410.2.3 Adsorption Isotherms41010.2.4 Surface Reaction41610.2.5 Desorption41810.2.6 The Rate-Limiting Step419Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step42110.3.1 Is the Adsorption of Cumene Rate-Limiting?42410.3.2 Is the Surface Reaction Rate-Limiting?42710.3.3 Is the Desorption of Benzene Rate-Limiting?42910.3.4 Summary of the Cumene Decomposition43010.3.5 Reforming Catalysts43110.3.6 Rate Laws Derived from the Pseudo-SteadyState Hypothesis (PSSH)43510.3.7 Temperature Dependence of the Rate Law436Heterogeneous Data Analysis for Reactor Design43610.4.1 Deducing a Rate Law from the Experimental Data43810.4.2 Finding a Mechanism Consistent with ExperimentalObservations43910.4.3 Evaluation of the Rate-Law Parameters44010.4.4 Reactor Design443Reaction Engineering in Microelectronic Fabrication44610.5.1 Overview44610.5.2 Chemical Vapor Deposition448Model Discrimination451Catalyst Deactivation45410.7.1 Types of Catalyst Deactivation45610.7.2 Reactors That Can Be Used to Help Offset CatalystDecay46510.7.3 Temperature–Time Trajectories46510.7.4 Moving-Bed Reactors46710.7.5 Straight-Through Transport Reactors (STTR)472NONISOTHERMAL REACTOR DESIGN–THE STEADYSTATE ENERGY BALANCE AND ADIABATICPFR APPLICATIONSRationale494The Energy Balance49511.2.1 First Law of Thermodynamics49511.2.2 Evaluating the Work Term49611.2.3 Overview of Energy Balances498The User-Friendly Energy Balance Equations50211.3.1 Dissecting the Steady-State Molar Flow Ratesto Obtain the Heat of Reaction50211.3.2 Dissecting the Enthalpies50411.3.3 Relating H Rx (T), H Rx (T R), and C P505Adiabatic Operation50811.4.1 Adiabatic Energy Balance50811.4.2 Adiabatic Tubular Reactor509493

xiiContents11.511.611.7CHAPTER 12Adiabatic Equilibrium Conversion51811.5.1 Equilibrium Conversion518Reactor Staging52211.6.1 Reactor Staging with Interstage Cooling or Heating11.6.2 Exothermic Reactions52311.6.3 Endothermic Reactions523Optimum Feed Temperature526522STEADY-STATE NONISOTHERMAL REACTORDESIGN—FLOW REACTORS WITH HEAT EXCHANGE12.112.212.312.412.512.612.712.8CHAPTER 1313.113.2539Steady-State Tubular Reactor with Heat Exchange54012.1.1 Deriving the Energy Balance for a PFR54012.1.2 Applying the Algorithm to Flow Reactors with HeatExchange542Balance on the Heat-Transfer Fluid54312.2.1 Co-current Flow54312.2.2 Countercurrent Flow544Algorithm for PFR/PBR Design with Heat Effects54512.3.1 Applying the Algorithm to an Exothermic Reaction54812.3.2 Applying the Algorithm to an Endothermic Reaction555CSTR with Heat Effects56412.4.1 Heat Added to the Reactor, Q̇564Multiple Steady States (MSS)57412.5.1 Heat-Removed Term, R(T )57512.5.2 Heat-Generated Term, G(T )57612.5.3 Ignition-Extinction Curve578Nonisothermal Multiple Chemical Reactions58112.6.1 Energy Balance for Multiple Reactions in Plug-FlowReactors58112.6.2 Parallel Reactions in a PFR58212.6.3 Energy Balance for Multiple Reactions in a CSTR58512.6.4 Series Reactions in a CSTR58512.6.5 Complex Reactions in a PFR588Radial and Axial Variations in a Tubular Reactor59512.7.1 Molar Flux59612.7.2 Energy Flux59712.7.3 Energy Balance598Safety603UNSTEADY-STATE NONISOTHERMAL REACTOR DESIGNUnsteady-State Energy Balance630Energy Balance on Batch Reactors63213.2.1 Adiabatic Operation of a Batch Reactor63313.2.2 Case History of a Batch Reactor with Interrupted IsothermalOperation Causing a Runaway Reaction640629

xiiiContents13.313.413.5CHAPTER 1414.114.214.314.414.5CHAPTER 1515.115.215.315.415.515.6Semibatch Reactors with a Heat ExchangerUnsteady Operation of a CSTR65113.4.1 Startup651Nonisothermal Multiple Reactions656646MASS TRANSFER LIMITATIONS IN REACTING SYSTEMS679Diffusion Fundamentals68014.1.1 Definitions68114.1.2 Molar Flux68214.1.3 Fick’s First Law683Binary Diffusion68414.2.1 Evaluating the Molar Flux68414.2.2 Diffusion and Convective Transport68514.2.3 Boundary Conditions68514.2.4 Temperature and Pressure Dependence of DAB68614.2.5 Steps in Modeling Diffusion without Reaction68714.2.6 Modeling Diffusion with Chemical Reaction687Diffusion Through a Stagnant Film688The Mass Transfer Coefficient69014.4.1 Correlations for the Mass Transfer Coefficient69014.4.2 Mass Transfer to a Single Particle69314.4.3 Mass Transfer–Limited Reactions in Packed Beds69714.4.4 Robert the Worrier700What If . . . ? (Parameter Sensitivity)705DIFFUSION AND REACTIONDiffusion and Reactions in Homogeneous Systems720Diffusion and Reactions in Spherical Catalyst Pellets72015.2.1 Effective Diffusivity72115.2.2 Derivation of the Differential Equation Describing Diffusionand Reaction in a Single Catalyst Pellet72315.2.3 Writing the Diffusion with the Catalytic Reaction Equation inDimensionless Form72615.2.4 Solution to the Differential Equation for a First-OrderReaction729The Internal Effectiveness Factor73015.3.1 Isothermal First-Order Catalytic Reactions73015.3.2 Effectiveness Factors with Volume Change withReaction73315.3.3 Isothermal Reactors Other Than First Order73315.3.4 Weisz–Prater Criterion for Internal Diffusion734Falsified Kinetics737Overall Effectiveness Factor739Estimation of Diffusion- and Reaction-Limited Regimes74315.6.1 Mears Criterion for External Diffusion Limitations743719

xivContents15.715.815.9Mass Transfer and Reaction in a Packed Bed744Determination of Limiting Situations from Reaction-Rate DataMultiphase Reactors in the Professional Reference Shelf75115.9.1 Slurry Reactors75215.9.2 Trickle Bed Reactors75215.10 Fluidized Bed Reactors75315.11 Chemical Vapor Deposition (CVD)753CHAPTER 16RESIDENCE TIME DISTRIBUTIONS OFCHEMICAL REACTORS16.116.216.316.416.516.6CHAPTER 17750General Considerations76716.1.1 Residence Time Distribution (RTD) Function769Measurement of the RTD77016.2.1 Pulse Input Experiment77016.2.2 Step Tracer Experiment775Characteristics of the RTD77716.3.1 Integral Relationships77716.3.2 Mean Residence Time77816.3.3 Other Moments of the RTD77816.3.4 Normalized RTD Function, E( )78216.3.5 Internal-Age Distribution, I( )783RTD in Ideal Reactors78416.4.1 RTDs in Batch and Plug-Flow Reactors784

Elements of Chemical Reaction Engineering Fifth Edition H. SCOTT FOGLER Ame and Catherine Vennema Professor of Chemical Engineering and the Arthur F. Thurnau Professor The University of Michigan, Ann Arbor Boston Columbus Indianapolis New York San Francisco Amsterdam Cape Town