Elements of Chemical Reaction Engineering,

Description

The Definitive Guide to Chemical Reaction Engineering Problem-Solving -- With Updated Content and More Active Learning For decades, H. Scott Fogler's Elements of Chemical Reaction Engineering has been the world's dominant chemical reaction engineering text. This Sixth Edition and integrated Web site deliver a more compelling active learning experience than ever before. Using sliders and interactive examples in Wolfram, Python, POLYMATH, and MATLAB, students can explore reactions and reactors by running realistic simulation experiments. Writing for today's students, Fogler provides instant access to information, avoids extraneous details, and presents novel problems linking theory to practice. Faculty can flexibly define their courses, drawing on updated chapters, problems, and extensive Professional Reference Shelf web content at diverse levels of difficulty. The book thoroughly prepares undergraduates to apply chemical reaction kinetics and physics to the design of chemical reactors. And four advanced chapters address graduate-level topics, including effectiveness factors. To support the field's growing emphasis on chemical reactor safety, each chapter now ends with a practical safety lesson. Updates throughout the book reflect current theory and practice and emphasize safetyNew discussions of molecular simulations and stochastic modelingIncreased emphasis on alternative energy sources such as solar and biofuelsThorough reworking of three chapters on heat effects Full chapters on nonideal reactors, diffusion limitations, and residence time distribution About the Companion Web Site (umich.edu/~elements/6e/index.html) Complete PowerPoint slides for lecture notes for chemical reaction engineering classesLinks to additional software, including POLYMATH™, MATLAB™, Wolfram Mathematica™, AspenTech™, and COMSOL™Interactive learning resources linked to each chapter, including Learning Objectives, Summary Notes, Web Modules, Interactive Computer Games, Solved Problems, FAQs, additional homework problems, and links to LearnchemeLiving Example Problems -- unique to this book -- that provide more than 80 interactive simulations, allowing students to explore the examples and ask "what-if" questionsProfessional Reference Shelf, which includes advanced content on reactors, weighted least squares, experimental planning, laboratory reactors, pharmacokinetics, wire gauze reactors, trickle bed reactors, fluidized bed reactors, CVD boat reactors, detailed explanations of key derivations, and moreProblem-solving strategies and insights on creative and critical thinking Register your book for convenient access to downloads, updates, and/or corrections as they become available. See inside book for details. Cover Half Title Title Page Copyright Dedication Contents Introduction About the Author Chapter 1. Mole Balances 1.1 The Rate of Reaction, –rA 1.2 The General Mole Balance Equation (GMBE) 1.3 Batch Reactors (BRs) 1.4 Continuous-Flow Reactors 1.4.1 Continuous-Stirred Tank Reactor (CSTR) 1.4.2 Tubular Reactor 1.4.3 Packed-Bed Reactor (PBR) 1.4.4 Well-Mixed “Fluidized” Catalytic Bed Reactor 1.5 Industrial Reactors 1.6 And Now… A Word from Our Sponsor—Safety 1 (AWFOS–S1 Safety) 1.6.1 What Is Chemical Process Safety? 1.6.2 Why Study Process Safety? Chapter 2. Conversion And Reactor Sizing 2.1 Definition of Conversion 2.2 Batch Reactor Design Equations 2.3 Design Equations for Flow Reactors 2.3.1 CSTR (Also Known as a Backmix Reactor or a Vat) 2.3.2 Tubular Flow Reactor (PFR) 2.3.3 Packed-Bed Reactor (PBR) 2.4 Sizing Continuous-Flow Reactors 2.5 Reactors in Series 2.5.1 CSTRs in Series 2.5.2 PFRs in Series 2.5.3 Combinations of CSTRs and PFRs in Series 2.5.4 Comparing the CSTR and PFR Volumes and Reactor Sequencing 2.6 Some Further Definitions 2.6.1 Space Time 2.6.2 Space Velocity 2.7 And Now… A Word from Our Sponsor—Safety 2 (AWFOS–S2 The NFPA Diamond) Chapter 3. Rate Laws 3.1 Basic Definitions 3.1.1 Relative Rates of Reaction 3.2 The Rate Law 3.2.1 Power Law Models and Elementary Rate Laws 3.2.2 Nonelementary Rate Laws 3.2.3 Reversible Reactions 3.3 The Reaction-Rate Constant 3.3.1 The Rate Constantkand Its Temperature Dependence 3.3.2 Interpretation of the Activation Energy 3.3.3 The Arrhenius Plot 3.4 Molecular Simulations 3.4.1 Historical Perspective 3.4.2 Stochastic Modeling of Reactions 3.5 Present Status of Our Approach to Reactor Sizing and Design 3.6 And Now… A Word from Our Sponsor—Safety 3 (AWFOS–S3 The GHS Diamond) Chapter 4. Stoichiometry 4.1 Batch Reactors (BRs) 4.1.1 Batch Concentrations for the Generic Reaction, Equation (2-2) 4.2 Flow Systems 4.2.1 Equations for Concentrations in Flow Systems 4.2.2 Liquid-Phase Concentrations 4.2.3 Gas-Phase Concentrations 4.3 Reversible Reactions and Equilibrium Conversion 4.4 And Now… A Word from Our Sponsor—Safety 4 (AWFOS–S4 The Swiss Cheese Model) Chapter 5. Isothermal Reactor Design: Conversion 5.1 Design Structure for Isothermal Reactors 5.2 Batch Reactors (BRs) 5.2.1 Batch Reaction Times 5.3 Continuous-Stirred Tank Reactors (CSTRs) 5.3.1 A Single CSTR 5.3.2 CSTRs in Series 5.4 Tubular Reactors 5.4.1 Liquid-Phase Reactions in a PFR υ=υ0 5.4.2 Gas-Phase Reactions in a PFR [υ=υ0(1 +εX) (T/T0)(P0/P)] 5.4.3 Effect ofεon Conversion 5.5 Pressure Drop in Reactors 5.5.1 Pressure Drop and the Rate Law 5.5.2 Flow Through a Packed Bed 5.5.3 Pressure Drop in Pipes 5.5.4 Analytical Solution for Reaction with Pressure Drop 5.5.5 Robert the Worrier Wonders:What If… 5.6 Synthesizing the Design of a Chemical Plant 5.7 And Now… A Word from Our Sponsor—Safety 5 (AWFOS–S5 A Safety Analysis of the Incident Algorithm) Chapter 6. Isothermal Reactor Design: Moles And Molar Flow Rates 6.1 The Moles and Molar Flow Rate Balance Algorithms 6.2 Mole Balances on CSTRs, PFRs, PBRs, and Batch Reactors 6.2.1 Liquid Phase 6.2.2 Gas Phase 6.3 Application of the PFR Molar Flow Rate Algorithm to a Microreactor 6.4 Membrane Reactors 6.5 Unsteady-State Operation of Stirred Reactors 6.6 Semibatch Reactors 6.6.1 Motivation for Using a Semibatch Reactor 6.6.2 Semibatch Reactor Mole Balances 6.6.3 Equilibrium Conversion 6.7 And Now… A Word from Our Sponsor—Safety 6 (AWFOS–S6 The BowTie Diagram) Chapter 7. Collection And Analysis Of Rate Data 7.1 The Algorithm for Data Analysis 7.2 Determining the Reaction Order for Each of Two Reactants Using the Method of Excess 7.3 Integral Method 7.4 Differential Method of Analysis 7.4.1 Graphical Differentiation Method 7.4.2 Numerical Method 7.4.3 Finding the Rate-Law Parameters 7.5 Nonlinear Regression 7.5.1 Concentration–Time Data 7.5.2 Model Discrimination 7.6 Reaction-Rate Data from Differential Reactors 7.7 Experimental Planning 7.8 And Now… A Word from Our Sponsor—Safety 7 (AWFOS–S7 Laboratory Safety) Chapter 8. Multiple Reactions 8.1 Definitions 8.1.1 Types of Reactions 8.1.2 Selectivity 8.1.3 Yield 8.1.4 Conversion 8.2 Algorithm for Multiple Reactions 8.2.1 Modifications to the Chapter 6 CRE Algorithm for Multiple Reactions 8.3 Parallel Reactions 8.3.1 Selectivity 8.3.2 Maximizing the Desired Product for One Reactant 8.3.3 Reactor Selection and Operating Conditions 8.4 Reactions in Series 8.5 Complex Reactions 8.5.1 Complex Gas-Phase Reactions in a PBR 8.5.2 Complex Liquid-Phase Reactions in a CSTR 8.5.3 Complex Liquid-Phase Reactions in a Semibatch Reactor 8.6 Membrane Reactors to Improve Selectivity in Multiple Reactions 8.7 Sorting It All Out 8.8 The Fun Part 8.9 And Now… A Word from Our Sponsor—Safety 8 (AWFOS–S8 The Fire Triangle) 8.9.1 The Fire Triangle 8.9.2 Defining Some Important Terms 8.9.3 Ways to Prevent Fires 8.9.4 Ways to Protect from Fires Chapter 9. Reaction Mechanisms, Pathways, Bioreactions, And Bioreactors 9.1 Active Intermediates and Nonelementary Rate Laws 9.1.1 Pseudo-Steady-State Hypothesis (PSSH) 9.1.2 If Two Molecules Must Collide, How Can the Rate Law Be First Order? 9.1.3 Searching for a Mechanism 9.1.4 Chain Reactions 9.2 Enzymatic Reaction Fundamentals 9.2.1 Enzyme–Substrate Complex 9.2.2 Mechanisms 9.2.3 Michaelis–Menten Equation 9.2.4 Batch Reactor Calculations for Enzyme Reactions 9.3 Inhibition of Enzyme Reactions 9.3.1 Competitive Inhibition 9.3.2 Uncompetitive Inhibition 9.3.3 Noncompetitive Inhibition (Mixed Inhibition) 9.3.4 Substrate Inhibition 9.4 Bioreactors and Biosynthesis 9.4.1 Cell Growth 9.4.2 Rate Laws 9.4.3 Stoichiometry 9.4.4 Mass Balances 9.4.5 Chemostats 9.4.6 CSTR Bioreactor Operation 9.4.7 Washout 9.5 And Now… A Word from Our Sponsor—Safety 9 (AWFOS–S9 Process Safety Triangle) 9.5.1 Levels of the Process Safety Triangle 9.5.2 Application to Process Safety 9.5.3 Examples of Process Safety Triangle Chapter 10. Catalysis And Catalytic Reactors 10.1 Catalysts 10.1.1 Definitions 10.1.2 Catalyst Properties 10.1.3 Catalytic Gas–Solid Interactions 10.1.4 Classification of Catalysts 10.2 Steps in a Catalytic Reaction 10.2.1 Mass Transfer Step 1: Diffusion from the Bulk to the External Surface of the Catalyst—An Overview 10.2.2 Mass Transfer Step 2: Internal Diffusion—An Overview 10.2.3 Adsorption Isotherms 10.2.4 Surface Reaction 10.2.5 Desorption 10.2.6 The Rate-Limiting Step 10.3 Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step 10.3.1 Is the Adsorption of Cumene Rate-Limiting? 10.3.2 Is the Surface Reaction Rate-Limiting? 10.3.3 Is the Desorption of Benzene the Rate-Limiting Step (RLS)? 10.3.4 Summary of the Cumene Decomposition 10.3.5 Reforming Catalysts 10.3.6 Rate Laws Derived from the Pseudo-Steady-State Hypothesis (PSSH) 10.3.7 Temperature Dependence of the Rate Law 10.4 Heterogeneous Data Analysis for Reactor Design 10.4.1 Deducing a Rate Law from the Experimental Data 10.4.2 Finding a Mechanism Consistent with Experimental Observations 10.4.3 Evaluation of the Rate-Law Parameters 10.4.4 Reactor Design 10.5 Reaction Engineering in Microelectronic Fabrication 10.5.1 Overview 10.5.2 Chemical Vapor Deposition (CVD) 10.6 Model Discrimination 10.7 Catalyst Deactivation 10.7.1 Types of Catalyst Deactivation 10.7.2 Decay in Packed-Bed Reactors 10.8 Reactors That Can Be Used to Help Offset Catalyst Decay 10.8.1 Temperature–Time Trajectories 10.8.2 Moving-Bed Reactors 10.8.3 Straight-Through Transport Reactors (STTR) 10.9 And Now… A Word from Our Sponsor—Safety 10 (AWFOS–S10 Exxon Mobil Torrance Refinery Explosion Involving a Straight–Through Transport Reactor [STTR]) Chapter 11. Nonisothermal Reactor Design: The Steady-state Energy Balance And Adiabatic Pfr Applications 11.1 Rationale 11.2 The Energy Balance 11.2.1 First Law of Thermodynamics 11.2.2 Evaluating the Work Term 11.2.3 Overview of Energy Balances 11.3 The User-Friendly Energy Balance Equations 11.3.1 Dissecting the Steady-State Molar Flow Rates to Obtain the Heat of Reaction 11.3.2 Dissecting the Enthalpies 11.3.3 Relating ˜HRx(T), ˜H˚Rx (TR), and ˜CP 11.4 Adiabatic Operation Q=O 11.4.1 Adiabatic Energy Balance 11.4.2 Adiabatic Tubular Reactor 11.5 Adiabatic Equilibrium Conversion 11.5.1 Equilibrium Conversion 11.6 Reactor Staging with Interstage Cooling or Heating 11.6.1 Exothermic Reactions 11.6.2 Endothermic Reactions 11.7 Optimum Feed Temperature 11.8 And Now… A Word from Our Sponsor—Safety 11 (AWFOS–S11 Acronyms) Chapter 12. Steady-State Nonisothermal Reactor Design: Flow Reactors With Heat Exchange 12.1 Steady-State Tubular Reactor with Heat Exchange 12.1.1 Deriving the Energy Balance for a PFR 12.1.2 Applying the Algorithm to Flow Reactors with Heat Exchange 12.2 Balance on the Heat-Transfer Fluid 12.2.1 Co-Current Flow 12.2.2 Countercurrent Flow 12.3 Examples of the Algorithm for PFR/PBR Design with Heat Effects 12.3.1 Applying the Algorithm to an Exothermic Reaction 12.3.2 Applying the Algorithm to an Endothermic Reaction 12.4 CSTR with Heat Effects 12.4.1 Heat Added to the Reactor, Q 12.5 Multiple Steady States (MSS) 12.5.1 Heat-Removed Term, R(T) 12.5.2 Heat-Generated Term, G(T) 12.5.3 Ignition–Extinction Curve 12.6 Nonisothermal Multiple Chemical Reactions 12.6.1 Energy Balance for Multiple Reactions in Plug-Flow Reactors 12.6.2 Energy Balance for Multiple Reactions in a CSTR 12.6.3 Series Reactions in a CSTR 12.6.4 Complex Reactions in a PFR 12.7 Radial and Axial Temperature Variations in a Tubular Reactor 12.8 And Now… A Word from Our Sponsor—Safety 12 (AWFOS–S12 Safety Statistics) 12.8.1 The Process Safety Across the Chemical Engineering Curriculum Web site 12.8.2 Safety Statistics 12.8.3 Additional Resources CCPS and SAChE Chapter 13. Unsteady-State Nonisothermal Reactor Design 13.1 The Unsteady-State Energy Balance 13.2 Energy Balance on Batch Reactors (BRs) 13.2.1 Adiabatic Operation of a Batch Reactor 13.2.2 Case History of a Batch Reactor with Interrupted Isothermal Operation Causing a Runaway Reaction 13.3 Batch and Semibatch Reactors with a Heat Exchanger 13.3.1 Startup of a CSTR 13.3.2 Semibatch Operation 13.4 Nonisothermal Multiple Reactions 13.5 And Now… A Word from Our Sponsor—Safety 13 (AWFOS–S13 Safety Analysis of the T2 Laboratories Incident) Chapter 14. Mass Transfer Limitations In Reacting Systems 14.1 Diffusion Fundamentals 14.1.1 Definitions 14.1.2 Molar Flux: WA 14.1.3 Fick’s First Law 14.2 Binary Diffusion 14.2.1 Evaluating the Molar Flux 14.2.2 Diffusion and Convective Transport 14.2.3 Boundary Conditions 14.2.4 Temperature and Pressure Dependence of DAB 14.3 Modeling Diffusion with Chemical Reaction 14.3.1 Diffusion through a Stagnant Film to a Particle 14.4 The Mass Transfer Coefficient 14.5 Mass Transfer to a Single Particle 14.5.1 First-Order Rate Laws 14.5.2 Limiting Regimes 14.6 The Shrinking Core Model 14.6.1 Dust Explosions, Particle Dissolution, and Catalyst Regeneration 14.7 Mass Transfer–Limited Reactions in Packed Beds 14.8 Robert the Worrier 14.9 What If . . . ? (Parameter Sensitivity) 14.10 And Now… A Word from Our Sponsor—Safety 14 (AWFOS–S14 Sugar Dust Explosion) Chapter 15. Diffusion And Reaction 15.1 Diffusion and Reactions in Homogeneous Systems 15.2 Diffusion and Reactions in Spherical Catalyst Pellets 15.2.1 Effective Diffusivity 15.2.2 Derivation of the Differential Equation Describing Diffusion and Reaction in a Single Spherical Catalyst Pellet 15.2.3 Writing the Diffusion with the Catalytic Reaction Equation in Dimensionless Form 15.2.4 Solution to the Differential Equation for a First-Order Reaction 15.3 The Internal Effectiveness Factor 15.3.1 Isothermal First-Order Catalytic Reactions 15.3.2 Effectiveness Factors with Volume Change with Reaction 15.3.3 Internal-Diffusion-Limited Reactions Other Than First Order 15.3.4 Weisz–Prater Criterion for Internal Diffusion Limitations 15.4 Falsified Kinetics 15.5 Overall Effectiveness Factor 15.6 Estimation of Diffusion- and Reaction-Limited Regimes 15.6.1 Mears Criterion for External Diffusion Limitations 15.7 Mass Transfer and Reaction in a Packed Bed 15.8 Determination of Limiting Situations from Reaction-Rate Data 15.9 Multiphase Reactors in the Professional Reference Shelf 15.9.1 Slurry Reactors 15.9.2 Trickle Bed Reactors 15.10 Fluidized Bed Reactors 15.11 Chemical Vapor Deposition (CVD) 15.12 And Now… A Word from Our Sponsor—Safety 15 (AWFOS–S15 Critical Thinking Questions Applied to Safety) Chapter 16. Residence Time Distributions Of Chemical Reactors 16.1 General Considerations 16.1.1 Residence Time Distribution (RTD) Function 16.2 Measurement of the RTD 16.2.1 Pulse Input Experiment 16.2.2 Step Tracer Experiment 16.3 Characteristics of the RTD 16.3.1 Integral Relationships 16.3.2 Mean Residence Time 16.3.3 Other Moments of the RTD 16.3.4 Normalized RTD Function, E 16.3.5 Internal-Age Distribution, I 16.4 RTD in Ideal Reactors 16.4.1 RTDs in Batch and Plug-Flow Reactors 16.4.2 Single-CSTR RTD 16.4.3 Laminar-Flow Reactor (LFR) 16.5 PFR/CSTR Series RTD 16.6 Diagnostics and Troubleshooting 16.6.1 General Comments 16.6.2 Simple Diagnostics and Troubleshooting Using the RTD for Ideal Reactors 16.7 And Now… A Word from Our Sponsor—Safety 16 (AWFOS–S16 Critical Thinking Actions) Chapter 17. Predicting Conversion Directly From The Residence Time Distribution 17.1 Modeling Nonideal Reactors Using the RTD 17.1.1 Modeling and Mixing Overview 17.1.2 Mixing 17.2 Zero Adjustable Parameter Models 17.2.1 Segregation Model 17.2.2 Maximum Mixedness Model 17.3 Using Software Packages Such as Polymath to Find Maximum Mixedness Conversion 17.3.1 Comparing Segregation and Maximum Mixedness Predictions 17.4 Tanks-in-Series One Parameter Model, n 17.4.1 Find the Number of T-I-S to Model the Real Reactor 17.4.2 Calculating Conversion for the T-I-S Model 17.4.3 Tanks-in-Series versus Segregation for a First-Order Reaction 17.5 RTD and Multiple Reactions 17.5.1 Segregation Model 17.5.2 Maximum Mixedness 17.6 And Now… A Word from Our Sponsor—Safety 17 (AWFOS–S17 Brief Case History on an Air Preheater) Chapter 18. Models For Nonideal Reactors 18.1 Some Guidelines for Developing Models 18.1.1 One-Parameter Models 18.1.2 Two-Parameter Models 18.2 Flow and Axial Dispersion of Inert Tracers in Isothermal Reactors 18.2.1 Balances on Inert Tracers 18.2.2 Boundary Conditions for Flow and Reaction 18.3 Flow, Reaction, and Axial Dispersion 18.3.1 Balance Equations 18.3.2 Solution for a Closed-Closed System 18.4 Flow, Reaction, and Axial Dispersion in Isothermal Laminar-Flow Reactors and Finding Meno 18.4.1 Determine the Dispersion Coefficient (Da) and the Péclet Number (Per) 18.4.2 Correlations for Da 18.4.3 Dispersion in Packed Beds 18.4.4 Experimental Determination of Da 18.5 Tanks-in-Series Model versus Dispersion Model 18.6 Numerical Solutions to Flows with Dispersion and Reaction 18.7 Nonisothermal Flow with Radial and Axial Variations in a Tubular Reactor 18.7.1 Molar Flux 18.7.2 Energy Flux 18.7.3 Energy Balance 18.8 Two-Parameter Models—Modeling Real Reactors with Combinations of Ideal Reactors 18.8.1 Real CSTR Modeled Using Bypassing and Dead Space 18.8.2 Real CSTR Modeled as Two CSTRs with Interchange 18.8.3 Other Models of Nonideal Reactors Using CSTRs and PFRs 18.8.4 Applications to Pharmacokinetic Modeling 18.9 And Now… A Word from Our Sponsor—Safety 18 (AWFOS–S18 An Algorithm for Management of Change (MoC)) Appendix A. Numerical Techniques A.1 Useful Integrals in Chemical Reactor Design A.2 Equal-Area Graphical Differentiation A.3 Solutions to Differential Equations A.3.A First-Order Ordinary Differential Equations A.3.B Coupled Differential Equations A.3.C Second-Order Ordinary Differential Equations A.4 Numerical Evaluation of Integrals A.5 Semi-Log Graphs A.6 Software Packages Appendix B. Ideal Gas Constant And Conversion Factors Appendix C. Thermodynamic Relationships Involving The Equilibrium Constant Appendix D. Software Packages D.1 Polymath D.1.A About Polymath (http://www.umich.edu/~elements/6e/software/polymath.html) D.1.B Polymath Tutorials (http://www.umich.edu/~elements/6e/software/polymath-tutorial.html) D.1.C Living Example Problems (LEPs) D.2 Wolfram D.3 Python D.4 MATLAB D.5 Excel D.6 COMSOL (http://www.umich.edu/~elements/6e/12chap/comsol.html) D.7 Aspen D.8 Visual Encyclopedia of Equipment—Reactors Section D.9 Reactor Lab Appendix E. Rate-Law Data Appendix F. Nomenclature Appendix G. Open-Ended Problems G.1 ChemE Car G.2 Effective Lubricant Design G.3 Peach Bottom Nuclear Reactor G.4 Underground Wet Oxidation G.5 Hydrodesulfurization Reactor Design G.6 Continuous Bioprocessing G.7 Methanol Synthesis G.8 Cajun Seafood Gumbo G.9 Alcohol Metabolism G.10 Methanol Poisoning G.11 Safety Appendix H. Use Of Computational Chemistry Software Packages H.1 Computational Chemical Reaction Engineering Appendix I. How To Use The Cre Web Resources I.1 CRE Web Resources Components Index A B C D E F G H I J K L M N O P Q R S T U V W Y Z Credits