Elements of Chemical Reaction Engineering

<p>Introduction xix<br>About the Author xxxiii</p> <p><strong>Chapter 1: Mole Balances 1</strong><br>1.1 The Rate of Reaction, –r_A 4<br>1.2 The General Mole Balance Equation (GMBE) 8<br>1.3 Batch Reactors (BRs) 10<br>1.4 Continuous-Flow Reactors 12<br>1.5 Industrial Reactors 24<br>1.6 And Now . . . A Word from Our Sponsor -- Safety 1 (AWFOS - S1 Safety) 25</p> <p><strong>Chapter 2: Conversion and Reactor Sizing 35</strong><br>2.1 Definition of Conversion 36<br>2.2 Batch Reactor Design Equations 36<br>2.3 Design Equations for Flow Reactors 39<br>2.4 Sizing Continuous-Flow Reactors 42<br>2.5 Reactors in Series 51<br>2.6 Some Further Definitions 62<br>2.7 And Now . . . A Word from Our Sponsor -- Safety 2 (AWFOS - S2 The NFPA Diamond) 66</p> <p><strong>Chapter 3: Rate Laws 75</strong><br>3.1 Basic Definitions 76<br>3.2 The Rate Law 78<br>3.3 The Reaction-Rate Constant 89<br>3.4 Molecular Simulations 100<br>3.5 Present Status of Our Approach to Reactor Sizing and Design 103<br>3.6 And Now . . . A Word from Our Sponsor -- Safety 3 (AWFOS - S3 The GHS Diamond) 104</p> <p><strong>Chapter 4: Stoichiometry 117</strong><br>4.1 Batch Reactors (BRs) 119<br>4.2 Flow Systems 125<br>4.3 Reversible Reactions and Equilibrium Conversion 138<br>4.4 And Now . . . A Word from Our Sponsor -- Safety 4 (AWFOS - S4 The Swiss Cheese Model) 143</p> <p><strong>Chapter 5: Isothermal Reactor Design: Conversion 155</strong><br>5.1 Design Structure for Isothermal Reactors 156<br>5.2 Batch Reactors (BRs) 160<br>5.3 Continuous-Stirred Tank Reactors (CSTRs) 168<br>5.4 Tubular Reactors 178<br>5.5 Pressure Drop in Reactors 185<br>5.6 Synthesizing the Design of a Chemical Plant 208<br>5.7 And Now . . . A Word from Our Sponsor -- Safety 5 (AWFOS - S5 A Safety Analysis of the Incident Algorithm) 210</p> <p><strong>Chapter 6: Isothermal Reactor Design: Moles and Molar Flow Rates 229</strong><br>6.1 The Moles and Molar Flow Rate Balance Algorithms 230<br>6.2 Mole Balances on CSTRs, PFRs, PBRs, and Batch Reactors 230<br>6.3 Application of the PFR Molar Flow Rate Algorithm to a Microreactor 234<br>6.4 Membrane Reactors 239<br>6.5 Unsteady-State Operation of Stirred Reactors 248<br>6.6 Semibatch Reactors 249<br>6.7 And Now . . . A Word from Our Sponsor -- Safety 6 (AWFOS - S6 The BowTie Diagram) 256</p> <p><strong>Chapter 7: Collection and Analysis of Rate Data 269</strong><br>7.1 The Algorithm for Data Analysis 270<br>7.2 Determining the Reaction Order for Each of Two Reactants Using the Method of Excess 272<br>7.3 Integral Method 273<br>7.4 Differential Method of Analysis 277<br>7.5 Nonlinear Regression 284<br>7.6 Reaction-Rate Data from Differential Reactors 290<br>7.7 Experimental Planning 297<br>7.8 And Now . . . A Word from Our Sponsor -- Safety 7 (AWFOS - S7 Laboratory Safety) 297</p> <p><strong>Chapter 8: Multiple Reactions 309</strong><br>8.1 Definitions 310<br>8.2 Algorithm for Multiple Reactions 313<br>8.3 Parallel Reactions 316<br>8.4 Reactions in Series 325<br>8.5 Complex Reactions 335<br>8.6 Membrane Reactors to Improve Selectivity in Multiple Reactions 343<br>8.7 Sorting It All Out 348<br>8.8 The Fun Part 348<br>8.9 And Now . . . A Word from Our Sponsor -- Safety 8 (AWFOS - S8 The Fire Triangle) 349</p> <p><strong>Chapter 9: Reaction Mechanisms, Pathways, Bioreactions, and Bioreactors 367</strong><br>9.1 Active Intermediates and Nonelementary Rate Laws 368<br>9.2 Enzymatic Reaction Fundamentals 377<br>9.3 Inhibition of Enzyme Reactions 391<br>9.4 Bioreactors and Biosynthesis 399<br>9.5 And Now . . . A Word from Our Sponsor -- Safety 9 (AWFOS - S9 Process Safety Triangle) 422</p> <p><strong>Chapter 10: Catalysis and Catalytic Reactors 441</strong><br>10.1 Catalysts 441<br>10.2 Steps in a Catalytic Reaction 447<br>10.3 Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step 463<br>10.4 Heterogeneous Data Analysis for Reactor Design 479<br>10.5 Reaction Engineering in Microelectronic Fabrication 490<br>10.6 Model Discrimination 493<br>10.7 Catalyst Deactivation 496<br>10.8 Reactors That Can Be Used to Help Offset Catalyst Decay 507<br>10.9 And Now . . . A Word from Our Sponsor -- Safety 10 (AWFOS - S10 Exxon Mobil Torrance Refinery Explosion Involving<br>a Straight-Through Transport Reactor [STTR]) 519</p> <p><strong>Chapter 11: Nonisothermal Reactor Design: The Steady-State Energy Balance and Adiabatic PFR Applications 541</strong><br>11.1 Rationale 542<br>11.2 The Energy Balance 543<br>11.3 The User-Friendly Energy Balance Equations 551<br>11.4 Adiabatic Operation 557<br>11.5 Adiabatic Equilibrium Conversion 566<br>11.6 Reactor Staging with Interstage Cooling or Heating 571<br>11.7 Optimum Feed Temperature 575<br>11.8 And Now . . . A Word from Our Sponsor -- Safety 11 (AWFOS - S11 Acronyms) 579</p> <p><strong>Chapter 12: Steady-State Nonisothermal Reactor Design: Flow Reactors with Heat Exchange 591</strong><br>12.1 Steady-State Tubular Reactor with Heat Exchange 592<br>12.2 Balance on the Heat-Transfer Fluid 595<br>12.3 Examples of the Algorithm for PFR/PBR Design with Heat Effects 598<br>12.4 CSTR with Heat Effects 619<br>12.5 Multiple Steady States (MSS) 630<br>12.6 Nonisothermal Multiple Chemical Reactions 637<br>12.7 Radial and Axial Temperature Variations in a Tubular Reactor 652<br>12.8 And Now . . . A Word from Our Sponsor -- Safety 12 (AWFOS - S12 Safety Statistics) 652</p> <p><strong>Chapter 13: Unsteady-State Nonisothermal Reactor Design 681</strong><br>13.1 The Unsteady-State Energy Balance 682<br>13.2 Energy Balance on Batch Reactors (BRs) 684<br>13.3 Batch and Semibatch Reactors with a Heat Exchanger 700<br>13.4 Nonisothermal Multiple Reactions 711<br>13.5 And Now . . . A Word from Our Sponsor -- Safety 13 (AWFOS - S13 Safety Analysis of the T2 Laboratories Incident) 723</p> <p><strong>Chapter 14: Mass Transfer Limitations in Reacting Systems 739</strong><br>14.1 Diffusion Fundamentals 740<br>14.2 Binary Diffusion 744<br>14.3 Modeling Diffusion with Chemical Reaction 748<br>14.4 The Mass Transfer Coefficient 750<br>14.5 Mass Transfer to a Single Particle 752<br>14.6 The Shrinking Core Model 758<br>14.7 Mass Transfer-Limited Reactions in Packed Beds 763<br>14.8 Robert the Worrier 766<br>14.9 What If . . . ? (Parameter Sensitivity) 770<br>14.10 And Now . . . A Word from Our Sponsor -- Safety 14 (AWFOS - S14 Sugar Dust Explosion) 778</p> <p><strong>Chapter 15: Diffusion and Reaction 791</strong><br>15.1 Diffusion and Reactions in Homogeneous Systems 792<br>15.2 Diffusion and Reactions in Spherical Catalyst Pellets 793<br>15.3 The Internal Effectiveness Factor 802<br>15.4 Falsified Kinetics 809<br>15.5 Overall Effectiveness Factor 811<br>15.6 Estimation of Diffusion- and Reaction-Limited Regimes 816<br>15.7 Mass Transfer and Reaction in a Packed Bed 817<br>15.8 Determination of Limiting Situations from Reaction-Rate Data 823<br>15.9 Multiphase Reactors in the Professional Reference Shelf 824<br>15.10 Fluidized Bed Reactors 826<br>15.11 Chemical Vapor Deposition (CVD) 826<br>15.12 And Now . . . A Word from Our Sponsor -- Safety 15 (AWFOS - S15 Critical Thinking Questions Applied to Safety) 826</p> <p><strong>Chapter 16: Residence Time Distributions of Chemical Reactors 843</strong><br>16.1 General Considerations 844<br>16.2 Measurement of the RTD 846<br>16.3 Characteristics of the RTD 853<br>16.4 RTD in Ideal Reactors 860<br>16.5 PFR/CSTR Series RTD 866<br>16.6 Diagnostics and Troubleshooting 869<br>16.7 And Now . . . A Word from Our Sponsor -- Safety 16 (AWFOS - S16 Critical Thinking Actions) 876</p> <p><strong>Chapter 17: Predicting Conversion Directly from the Residence Time Distribution 887</strong><br>17.1 Modeling Nonideal Reactors Using the RTD 888<br>17.2 Zero Adjustable Parameter Models 890<br>17.3 Using Software Packages Such as Polymath to Find Maximum Mixedness Conversion 907<br>17.4 Tanks-in-Series One Parameter Model, n 910<br>17.5 RTD and Multiple Reactions 912<br>17.6 And Now . . . A Word from Our Sponsor -- Safety 17 (AWFOS - S17 Brief Case History on an Air Preheater) 917</p> <p><strong>Chapter 18: Models for Nonideal Reactors 929</strong><br>18.1 Some Guidelines for Developing Models 930<br>18.2 Flow and Axial Dispersion of Inert Tracers in Isothermal Reactors 933<br>18.3 Flow, Reaction, and Axial Dispersion 937<br>18.4 Flow, Reaction, and Axial Dispersion in Isothermal Laminar-Flow Reactors and Finding Meno 941<br>18.5 Tanks-in-Series Model versus Dispersion Model 951<br>18.6 Numerical Solutions to Flows with Dispersion and Reaction 952<br>18.7 Nonisothermal Flow with Radial and Axial Variations in a Tubular Reactor 956<br>18.8 Two-Parameter Models -- Modeling Real Reactors with Combinations of Ideal Reactors 964<br>18.9 And Now . . . A Word from Our Sponsor -- Safety 18 (AWFOS - S18 An Algorithm for Management of Change (MoC)) 974</p> <p><strong>Appendix A: Numerical Techniques 991</strong><br>A.1 Useful Integrals in Chemical Reactor Design 991<br>A.2 Equal-Area Graphical Differentiation 992<br>A.3 Solutions to Differential Equations 994<br>A.4 Numerical Evaluation of Integrals 995<br>A.5 Semi-Log Graphs 997<br>A.6 Software Packages 997</p> <p><strong>Appendix B: Ideal Gas Constant and Conversion Factors 999</strong></p> <p><strong>Appendix C: Thermodynamic Relationships Involving the Equilibrium Constant 1003</strong></p> <p><strong>Appendix D: Software Packages 1009</strong><br>D.1 Polymath 1009<br>D.2 Wolfram 1010<br>D.3 Python 1011<br>D.4 MATLAB 1011<br>D.5 Excel 1011<br>D.6 COMSOL (<a href="http://www.umich.edu/~elements/6e/12chap/comsol.html">http://www.umich.edu/~elements/6e/12chap/comsol.html</a>) 1012<br>D.7 Aspen 1013<br>D.8 Visual Encyclopedia of Equipment -- Reactors Section 1013<br>D.9 Reactor Lab 1013</p> <p><strong>Appendix E: Rate-Law Data 1015</strong></p> <p><strong>Appendix F: Nomenclature 1017</strong></p> <p><strong>Appendix G: Open-Ended Problems 1021</strong><br>G.1 Chem-E-Car 1021<br>G.2 Effective Lubricant Design 1021<br>G.3 Peach Bottom Nuclear Reactor 1021<br>G.4 Underground Wet Oxidation 1022<br>G.5 Hydrodesulfurization Reactor Design 1022<br>G.6 Continuous Bioprocessing 1022<br>G.7 Methanol Synthesis 1022<br>G.8 Cajun Seafood Gumbo 1022<br>G.9 Alcohol Metabolism 1023<br>G.10 Methanol Poisoning 1024<br>G.11 Safety 1024</p> <p><strong>Appendix H: Use of Computational Chemistry Software Packages 1025</strong><br>H.1 Computational Chemical Reaction Engineering 1025</p> <p><strong>Appendix I: How to Use the CRE Web Resources 1027</strong><br>I.1 CRE Web Resources Components 1027</p> <p>Index 1029</p>