Elements of Chemical Reaction Engineering

H. Scott Fogler is the Ame and Catherine Vennema Professor of Chemical Engineering and the Arthur F. Thurnau Professor at the University of Michigan. He has been research advisor to forty-five Ph.D. students, and has more than two hundred thirty-five refereed publications. He was 2009 President of the American Institute of Chemical Engineers. Fogler has chaired ASEE’s Chemical Engineering Division, served as director of the American Institute of Chemical Engineers, and earned the Warren K. Lewis Award from AIChE for contributions to chemical engineering education. He has received the Chemical Manufacturers Association’s National Catalyst Award and the 2010 Malcom E. Pruitt Award from the Council for Chemical Research.

Preface xvii

About the Author xxxiii

 

Chapter 1: Mole Balances 1

1.1 The Rate of Reaction, –rA 4

1.2 The General Mole Balance Equation 8

1.3 Batch Reactors (BRs) 10

1.4 Continuous-Flow Reactors 12

1.5 Industrial Reactors 22

 

Chapter 2: Conversion and Reactor Sizing 31

2.1 Definition of Conversion 32

2.2 Batch Reactor Design Equations 32

2.3 Design Equations for Flow Reactors 35

2.4 Sizing Continuous-Flow Reactors 38

2.5 Reactors in Series 47

2.6 Some Further Definitions 58

 

Chapter 3: Rate Laws 69

3.1 Basic Definitions 70

3.2 The Reaction Order and the Rate Law 72

3.3 Rates and the Reaction Rate Constant 83

3.4 Present Status of Our Approach to Reactor Sizing and Design 93

 

Chapter 4: Stoichiometry 105

4.1 Batch Systems 107

4.2 Flow Systems 113

4.3 Reversible Reactions and Equilibrium Conversion 126

 

Chapter 5: Isothermal Reactor Design: Conversion 139

5.1 Design Structure for Isothermal Reactors 140

5.2 Batch Reactors (BRs) 144

5.3 Continuous-Stirred Tank Reactors (CSTRs) 152

5.4 Tubular Reactors 162

5.5 Pressure Drop in Reactors 169

5.6 Synthesizing the Design of a Chemical Plant 190

 

Chapter 6: Isothermal Reactor Design: Moles and Molar Flow Rates 207

6.1 The Molar Flow Rate Balance Algorithm 208

6.2 Mole Balances on CSTRs, PFRs, PBRs, and Batch Reactors 208

6.3 Application of the PFR Molar Flow Rate Algorithm to a Microreactor 212

6.4 Membrane Reactors 217

6.5 Unsteady-State Operation of Stirred Reactors 225

6.6 Semibatch Reactors 227

 

Chapter 7: Collection and Analysis of Rate Data 243

7.1 The Algorithm for Data Analysis 244

7.2 Determining the Reaction Order for Each of Two Reactants Using the Method of Excess 246

7.3 Integral Method 247

7.4 Differential Method of Analysis 251

7.5 Nonlinear Regression 258

7.6 Reaction-Rate Data from Differential Reactors 264

7.7 Experimental Planning 271

 

Chapter 8: Multiple Reactions 279

8.1 Definitions 280

8.2 Algorithm for Multiple Reactions 282

8.3 Parallel Reactions 285

8.4 Reactions in Series 294

8.5 Complex Reactions 304

8.6 Membrane Reactors to Improve Selectivity in Multiple Reactions 312

8.7 Sorting It All Out 317

8.8 The Fun Part 317

 

Chapter 9: Reaction Mechanisms, Pathways, Bioreactions, and Bioreactors 333

9.1 Active Intermediates and Nonelementary Rate Laws 334

9.2 Enzymatic Reaction Fundamentals 343

9.3 Inhibition of Enzyme Reactions 356

9.4 Bioreactors and Biosynthesis 364

 

Chapter 10: Catalysis and Catalytic Reactors 399

10.1 Catalysts 399

10.2 Steps in a Catalytic Reaction 405

10.3 Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step 421

10.4 Heterogeneous Data Analysis for Reactor Design 436

10.5 Reaction Engineering in Microelectronic Fabrication 446

10.6 Model Discrimination 451

10.7 Catalyst Deactivation 454

 

Chapter 11: Nonisothermal Reactor Design—The Steady-State Energy Balance and Adiabatic PFR Applications 493

11.1 Rationale 494

11.2 The Energy Balance 495

11.3 The User-Friendly Energy Balance Equations 502

11.4 Adiabatic Operation 508

11.5 Adiabatic Equilibrium Conversion 518

11.6 Reactor Staging 522

11.7 Optimum Feed Temperature 526

 

Chapter 12: Steady-State Nonisothermal Reactor Design—Flow Reactors with Heat Exchange 539

12.1 Steady-State Tubular Reactor with Heat Exchange 540

12.2 Balance on the Heat-Transfer Fluid 543

12.3 Algorithm for PFR/PBR Design with Heat Effects 545

12.4 CSTR with Heat Effects 564

12.5 Multiple Steady States (MSS) 574

12.6 Nonisothermal Multiple Chemical Reactions 581

12.7 Radial and Axial Variations in a Tubular Reactor 595

12.8 Safety 603

 

Chapter 13: Unsteady-State Nonisothermal Reactor Design 629

13.1 Unsteady-State Energy Balance 630

13.2 Energy Balance on Batch Reactors 632

13.3 Semibatch Reactors with a Heat Exchanger 646

13.4 Unsteady Operation of a CSTR 651

13.5 Nonisothermal Multiple Reactions 656

 

Chapter 14: Mass Transfer Limitations in Reacting Systems 679

14.1 Diffusion Fundamentals 680

14.2 Binary Diffusion 684

14.3 Diffusion Through a Stagnant Film 688

14.4 The Mass Transfer Coefficient 690

14.5 What If . . . ? (Parameter Sensitivity) 705

 

Chapter 15: Diffusion and Reaction 719

15.1 Diffusion and Reactions in Homogeneous Systems 720

15.2 Diffusion and Reactions in Spherical Catalyst Pellets 720

15.3 The Internal Effectiveness Factor 730

15.4 Falsified Kinetics 737

15.5 Overall Effectiveness Factor 739

15.6 Estimation of Diffusion- and Reaction-Limited Regimes 743

15.7 Mass Transfer and Reaction in a Packed Bed 744

15.8 Determination of Limiting Situations from Reaction-Rate Data 750

15.9 Multiphase Reactors in the Professional Reference Shelf 751

15.10 Fluidized Bed Reactors 753

15.11 Chemical Vapor Deposition (CVD) 753

 

Chapter 16: Residence Time Distributions of Chemical Reactors 767

16.1 General Considerations 767

16.2 Measurement of the RTD 770

16.3 Characteristics of the RTD 777

16.4 RTD in Ideal Reactors 784

16.5 PFR/CSTR Series RTD 789

16.6 Diagnostics and Troubleshooting 793

 

Chapter 17: Predicting Conversion Directly from the Residence Time Distribution 807

17.1 Modeling Nonideal Reactors Using the RTD 808

17.2 Zero-Adjustable-Parameter Models 810

17.3 Using Software Packages 827

17.4 RTD and Multiple Reactions 830

 

Chapter 18: Models for Nonideal Reactors 845

18.1 Some Guidelines for Developing Models 846

18.2 The Tanks-in-Series (T-I-S) One-Parameter Model 848

18.3 Dispersion One-Parameter Model 852

18.4 Flow, Reaction, and Dispersion 854

18.5 Tanks-in-Series Model versus Dispersion Model 869

18.6 Numerical Solutions to Flows with Dispersion and Reaction 870

18.7 Two-Parameter Models—Modeling Real Reactors with Combinations of Ideal Reactors 871

18.8 Use of Software Packages to Determine the Model Parameters 880

18.9 Other Models of Nonideal Reactors Using CSTRs and PFRs 882

18.10 Applications to Pharmacokinetic Modeling 883

 

Appendix A: Numerical Techniques 897

A.1 Useful Integrals in Reactor Design 897

A.2 Equal-Area Graphical Differentiation 898

A.3 Solutions to Differential Equations 900

A.4 Numerical Evaluation of Integrals 901

A.5 Semilog Graphs 903

A.6 Software Packages 903

 

Appendix B: Ideal Gas Constant and Conversion Factors 905

 

Appendix C: Thermodynamic Relationships Involving the Equilibrium Constant 909

 

Appendix D: Software Packages 915

D.1 Polymath 915

D.2 MATLAB 916

D.3 Aspen 916

D.4 COMSOL Multiphysics 917

 

Appendix E: Rate Law Data 919

 

Appendix F: Nomenclature 921

 

Appendix G: Open-Ended Problems 925

G.1 Design of Reaction Engineering Experiment 925

G.2 Effective Lubricant Design 925

G.3 Peach Bottom Nuclear Reactor 925

G.4 Underground Wet Oxidation 926

G.5 Hydrodesulfurization Reactor Design 926

G.6 Continuous Bioprocessing 926

G.7 Methanol Synthesis 926

G.8 Cajun Seafood Gumbo 926

G.9 Alcohol Metabolism 927

G.10 Methanol Poisoning 928

 

Appendix H: Use of Computational Chemistry Software Packages 929

 

Appendix I: How to Use the CRE Web Resources 931

I.1 CRE Web Resources Components 931

I.2 How the Web Can Help Your Learning Style 933

I.3 Navigation 934

 

Index 937