Chemical Reactor Analysis and Design, 2nd Edition

by Gilbert F. Froment (Rijksuniversiteit Gent, Belgium); Kenneth B. Bischoff (Univ. of Delaware)

• ISBN13: 9780471510444
• ISBN10: 0471510440
• Edition: 2nd
• Format: Paperback
• Copyright: 1990-01-01
• Publisher: Wiley

Summary

This is the Second Edition of the standard text on chemical reaction engineering, beginning with basic definitions and fundamental principles and continuing all the way to practical applications, emphasizing real-world aspects of industrial practice. The two main sections cover applied or engineering kinetics, reactor analysis and design. Includes updated coverage of computer modeling methods and many new worked examples. Most of the examples use real kinetic data from processes of industrial importance.

Table of Contents

Notation	xxi
Greek Symbols	xxx
Subscripts	xxxiii
Superscripts	xxxiv
PART ONE CHEMICAL ENGINEERING KINETICS	1	(290)
Elements of Reaction Kinetics	3	(58)
Reaction Rate	3	(1)
Conversion and Extent of Reaction	4	(2)
Order of Reaction	6	(8)
The Rate of an Autocatalytic Reaction	11	(3)
Complex Reactions	14	(21)
Complex Reaction Networks	16	(4)
Catalytic Cracking of Gasoil	20	(3)
Rate Determining Step and Steady State Approximation	23	(2)
Classical Unimolecular Rate Theory	25	(4)
Thermal Cracking of Ethane	29	(3)
Free Radical Addition Polymerization Kinetics	32	(3)
Influence of Temperature	35	(3)
Determination of the Activation Energy	36	(1)
Activation Energy for Complex Reactions	36	(2)
Thermodynamically Nonideal Conditions	38	(4)
Reactions of Dilute Strong Electrolytes	40	(1)
Pressure Effects in Gas-Phase Reactions	41	(1)
Determination of Kinetic Parameters	42	(19)
Simple Reactions	42	(1)
Complex Reactions	43	(3)
Rate Constant Determination by the Himmelblau-Jones-Bischoff method	46	(2)
Thermal Cracking of Propane	48	(13)
Kinetics of Heterogeneous Catalytic Reactions	61	(64)
Introduction	61	(6)
Adsorption on Solid Catalysts	67	(3)
Rate Equations	70	(14)
Single Reactions	71	(3)
Competitive Hydrogenation Reactions	74	(4)
Complex Reactions	78	(4)
Some Further Thoughts on the Hougen-Watson Rate Equations	82	(2)
Model Discrimination and Parameter Estimation	84	(41)
Experimental Reactors	84	(3)
The Differential Method of Kinetic Analysis	87	(5)
The Integral Method of Kinetic Analysis	92	(2)
Parameter Estimation and Statistical Testing of Models and Parameters in Single Reactions	94	(1)
Models that are Linear in the Parameters	94	(4)
Models that are Nonlinear in the Parameters	98	(1)
Parameter Estimation and Statistical Testing of Models and Parameters in Simultaneous Reactions	99	(2)
Benzothiophene Hydrogenolysis	101	(2)
Sequential Design of Experiments	103	(1)
Sequential Design	104	(1)
Single Response Case	104	(2)
Model Discrimination in the Dehydrogenation of 1-Butene into butadiene	106	(3)
Ethanol Dehydrogenation : Sequential Discrimination using the Integral Method of Kinetic Analysis	109	(3)
Multiresponse Case	112	(1)
Sequential Design for Optimal Estimation	113	(1)
Single Response Models	113	(1)
Multiresponse Models	113	(1)
Sequential Design for Optimal Parameter Estimation in Benzothiophene Hydrogenolysis	114	(1)
Expert Systems in Kinetic Studies	114	(3)
Physicochemical Tests	117	(8)
Transport Processes with Reactions Catalyzed By Solids	125	(73)
Interfacial Gradient Effects	125	(1)
Reaction of a Component of a Fluid at the Surface of a Solid	125	(2)
Mass and Heat Transfer Resistances	127	(5)
Mass Transfer Coefficients	127	(1)
Heat Transfer Coefficients	128	(2)
Multicomponent Diffusion in a Fluid	130	(2)
Use of Mean Effective Binary Diffusivity	132	(1)
Concentration or Partial Pressure and Temperature Differences between Bulk Fluid and Surface of a Catalyst Particle	132	(7)
Intefacial Gradients in Ethanol Dehydrogenation Experiments	133	(6)
Intraparticle Gradient Effects	139	(1)
Catalyst Internal Structure	139	(3)
Pore Diffusion	142	(15)
Definitions and Experimental Observations	142	(1)
Effect of Pore Diffusion in the Cracking of Alkanes on Zeolites	143	(2)
General Quantitative Description of Diffusion in a Porous Catalyst	145	(3)
The Random Pore Model	148	(1)
The Parallel Cross-Linked Pore Model	149	(2)
The Pore Network Model of Beeckman and Froment	151	(2)
Experimental Determination of the Effective Diffusivity of a Component Inside a Particle or of the Tortuosity Factor	153	(1)
Pore Diffusion with Adsorption; Surface Diffusion; Configurational Diffusion	154	(1)
Surface Diffusion in Liquid-Filled Pores	155	(2)
Diffusion and Reaction Inside Catalyst Particles	157	(18)
The Concept of Effectiveness Factor	157	(3)
Generalized Modulus	160	(2)
Generalized Modulus for Simple Rate Equations	162	(1)
Diffusional Falsification of Rate Coefficients and Activation Energy	163	(2)
Effectiveness Factors for Sucrose Inversion in Ion Exchange Resins	165	(1)
Criteria for Importance of Diffusional Limitations	166	(1)
Minimum Distance Between Bifunctional Catalyst Sites for Absence of Diffusional Limitations	167	(3)
Use of Extended Weisz-Prater Criterion	170	(1)
Combination of External and Internal Diffusion Resistance	171	(2)
On Diagnostic Experimental Criteria for the Absence of Mass Transfer Limitations	173	(1)
Multiplicity of Steady States in Catalyst Particles	174	(1)
Complex Reactions in the Presence of Diffusional Limitations	175	(5)
Accounting for the Structure of the Pore Network	180	(3)
Catalytic Demetallization and Desulfurization of Residuum Petroleum Fractions	181	(2)
Nonisothermal Particles	183	(15)
Thermal Gradients Inside Catalyst Particles	183	(3)
External and Internal Temperature Gradients	186	(2)
Temperature Gradients Inside the Catalyst Particles in Butene Hydrogenation	188	(10)
Noncatalytic Gas--Solid Reactions	198	(21)
A Qualitative Discussion of Gas-Solid Reactions	198	(3)
General Model with Interfacial and Intraparticle Gradients	201	(6)
Heterogeneous Model with Shrinking Unreacted Core	207	(5)
Combustion of Coke within Porous Catalyst Particles	209	(3)
Models Accounting Explicitly for the Structure of the Solid	212	(4)
On the Use of More Complex Kinetic Equations	216	(3)
Catalyst Deactivation	219	(37)
Types of Catalyst Deactivation	219	(1)
Solid-State Transformations	219	(1)
Poisoning	219	(1)
Coking	220	(1)
Kinetics of Catalyst Poisoning	220	(10)
Introduction	220	(1)
Kinetics of Uniform Poisoning	221	(2)
Shell-Progressive Poisoning	223	(4)
Effect of Shell-Progressive Poisoning on the Selectivity of Complex Reactions	227	(3)
Kinetics of Catalyst Deactivation by Coking	230	(26)
Introduction	230	(2)
Kinetics of Coking	232	(1)
Deactivation Functions	232	(1)
Catalyst Deactivation by Site Coverage Only	232	(5)
Catalyst Deactivation by Site Coverage and Pore Blockage	237	(2)
Deactivation by Site Coverage and Pore Blockage in the Presence of Diffusional Limitations	239	(4)
Deactivation by Site Coverage, Growth of Coke, and Blockage in Networks of Pores	243	(1)
Influence of Coking on the Selectivity	243	(2)
Kinetic Analysis of Deactivation by Coke Formation	245	(2)
Coking in the Dehydrogenation of 1-Butene into Butadiene	247	(3)
Rigorous Kinetic Equations for the Catalyst Deactivation by Coke Deposition in the Dehydrogenation of 1-Butene into Butadiene	250	(6)
Gas--Liquid Reactions	256	(35)
Introduction	256	(1)
Models for Transfer at a Gas--Liquid Interface	256	(3)
Two-Film Theory	259	(16)
Single Irreversible Reaction with General Kinetics	259	(1)
First-Order and Pseudo-First-Order Irreversible Reactions	260	(3)
Single, Instantaneous, and Irreversible Reactions	263	(4)
Some Remarks on Boundary Conditions and on Utilization and Enhancement Factors	267	(3)
Extension to Reactions with Higher Orders	270	(1)
Complex Reactions	271	(4)
Surface Renewal Theory	275	(7)
Single Instantaneous Reactions	276	(2)
Single Irreversible (Pseudo)-First-Order Reactions	278	(3)
Surface Renewal Models with Surface Elements of Limited Thickness	281	(1)
Experimental Determination of the Kinetics of Gas--Liquid Reactions	282	(9)
Introduction	282	(1)
Determination of kL and Av	283	(1)
Determination of kG and Av	284	(1)
Specific Equipment	284	(7)
PART TWO ANALYSIS AND DESIGN OF CHEMICAL REACTORS	291	(351)
The Fundamental Mass, Energy, and Momentum Balance Equations	293	(12)
Introduction	293	(2)
The Continuity Equations	293	(1)
The Energy Equation	294	(1)
The Momentum Equation	295	(1)
The Fundamental Equations	295	(10)
The Continuity Equations	295	(3)
Simplified Forms of the ``General'' Continuity Equation	298	(3)
The Energy Equation	301	(1)
Simplified Forms of the ``General'' Energy Equation	302	(3)
The Batch and Semibatch Reactors	305	(29)
The Isothermal Batch Reactor	305	(4)
Example of Derivation of a Kinetic Equation by Means of Batch Data	307	(2)
The Nonisothermal Batch Reactor	309	(5)
Decomposition of Acetylated Castor Oil Ester	312	(2)
Models for a Semibatch Reactor	314	(3)
Key Simulation of Semibatch Reactor Operation	315	(2)
Optimal Operation Policies and Control Strategies	317	(17)
Optimal Batch Operation Time	319	(2)
Optimum Conversion and Maximum Profit for a First-Order Reaction	321	(1)
Optimal Temperature Policies	321	(1)
Optimal Temperature Trajectories for First-Order Reversible Reactions	322	(5)
Optimum Temperature Policies for Consecutive and Parallel Reactions	327	(7)
The Plug Flow Reactor	334	(24)
The Continuity, Energy, and Momentum Equations	334	(6)
Derivation of a Kinetic Equation from Experiments in an Isothermal Tubular Reactor with Plug Flow. Thermal Cracking of Propane	338	(2)
Kinetic Analysis of Nonisothermal Data	340	(7)
Derivation of a Rate Equation for the Thermal Cracking of Acetone from Nonisothermal Data	343	(4)
Design of Tubular Reactors with Plug Flow	347	(11)
An Adiabatic Reactor with Plug Flow Conditions	348	(1)
Design of a Nonisothermal Reactor for Thermal Cracking of Ethane	349	(9)
The Perfectly Mixed Flow Reactor	358	(34)
Introduction	358	(1)
Mass and Energy Balances	358	(7)
Basic Equations	358	(1)
Steady-State Reactor Design	359	(6)
Design for Optimum Selectivity in Complex Reactions	365	(11)
General Considerations	365	(6)
Polymerization Reactions	371	(5)
Stability of Operation and Transient Behavior	376	(16)
Stability of Operation	376	(5)
Transient Behavior	381	(2)
Temperature Oscillations in a Mixed Reactor for the Vapor-Phase Chlorination of Methyl Chloride	383	(9)
Fixed Bed Catalytic Reactors	392	(117)
Introduction	392	(1)
The Importance and Scale of Fixed Bed Catalytic Processes	392	(1)
Factors of Progress: Technological Innovations and Increased Fundamental Insight	393	(1)
Factors Involved in the Preliminary Design of Fixed Bed Reactors	394	(7)
Modeling of Fixed Bed Reactors	401	(2)
Pseudohomogeneous Models	403	(1)
The Basic One-Dimensional Model	403	(43)
Model Equations	403	(3)
Calculation of Pressure Drop in Packed Beds	406	(1)
Design of a Fixed Bed Reactor According to the One-Dimensional Pseudohomogeneous Model	407	(2)
Runaway Criteria	409	(5)
Application of the First Runaway Criterion of Van Welsenaere and Froment	414	(2)
The Multibed Adiabatic Reactor	416	(7)
Fixed Bed Reactors with Heat Exchange between the Feed and Effluent or between the Feed and Reacting Gas. ``Autothermal Operation''	423	(14)
Nonsteady-State Behavior of Fixed Bed Catalytic Reactors Due to Catalyst Deactivation	437	(9)
One-Dimensional Model with Axial Mixing	446	(5)
Two-Dimensional Pseudohomogeneous Models	451	(16)
The Effective Transport Concept	451	(3)
The Static Contribution	454	(2)
The Dynamic Contribution	456	(1)
Continuity and Energy Equations	456	(1)
Design or Simulation of a Fixed Bed Reactor for Catalytic Hydrocarbon Oxidation	457	(5)
An Equivalent One-Dimensional Model	462	(1)
A Two-Dimensional Model Accounting for Radial Variations in Bed Structure	463	(3)
Two-Dimensional Cell Models	466	(1)
Heterogeneous Models	467	(1)
One-Dimensional Model Accounting for Interfacial Gradients	467	(10)
Model Equations	467	(4)
Simulation of the Transient Behavior of a Reactor	471	(1)
A Gas-Solid Reaction in a Fixed Bed Reactor	472	(5)
One-Dimensional Model Accounting for Interfacial and Intraparticle Gradients	477	(19)
Model Equations	477	(5)
Simulation of a Primary Steam Reformer	482	(9)
Simulation of an Industrial Reactor for 1-Butene Dehydrogenation into Butadiene	491	(5)
Two-Dimensional Heterogeneous Models	496	(13)
Nonideal Flow Patterns and Population Balance Models	509	(57)
Introduction	509	(1)
Age Distribution Functions	509	(8)
RTD of a Perfectly Mixed Vessel	511	(1)
Determination of RTD from Experimental Tracer Curve	512	(2)
Calculation of Age Distribution Fuctions from Experimental Data	514	(3)
Flow Patterns from the Interpretation of Age Distribution Functions	517	(3)
Measures of the Spectrum of Fluid Residence Times	517	(1)
Age Distribution Functions for a Series of n Stirred Tanks	517	(2)
RTD for Combinations of Noninteracting Regions	519	(1)
Detection of Regions of Fluid Stagnancy from Characteristics of Age Distributions	520	(1)
The Direct Application of Age Distribution Functions	520	(4)
Mean Value of the Rate Constant in a Well-Mixed Reactor	522	(2)
Macro- and Micromixing	524	(5)
Models Accounting for Flow Patterns	529	(22)
Axial Dispersion Model and Tanks-in-Series Model	529	(2)
Axial Dispersion Model for Laminar Flow in Round Tubes	531	(6)
Multizone Models	537	(3)
Transient Mass Transfer in a Packed Column	540	(3)
Recycle Model for Large-Scale Mixing Effects	543	(4)
Parameter Estimation in Models Accounting for Flow Patterns	547	(4)
Population Balance Models	551	(15)
Population Balance Model for Micromixing	552	(6)
Surface Reaction-Induced Changes in Pore Size Distribution	558	(8)
Fluidized Bed and Transport Reactors	566	(37)
Introduction	566	(1)
Catalytic Cracking of Gasoil	567	(2)
Fluidized Bed Catalytic Cracking	567	(1)
Transport or Riser Catalytic Cracking	568	(1)
Some Features of the Fluidization and Transport of Solids	569	(5)
Heat Transfer in Fluidized Beds	574	(2)
Modeling of Fluidized Bed Reactors	576	(9)
Basic Two-Phase Model	576	(3)
Bubble Velocity, Size, and Growth	579	(1)
A Hydrodynamic Interpretation of the Interchange Coefficient, kI	579	(5)
One-Phase Model	584	(1)
Modeling of a Transport or Riser Reactor	585	(1)
The Catalytic Cracking of Gasoil	586	(17)
Modeling of the Catalytic Cracking of Gasoil in a Fluidized Bed Reactor	588	(1)
Simulation of Fluidized Bed Catalytic Cracking of Gasoil	589	(3)
Modeling of the Cracking of Gasoil in a Riser Reactor	592	(1)
Simulation of Riser Catalytic Cracking of Gasoil	593	(3)
Kinetics of the Regeneration of a Coked Cracking Catalyst	596	(1)
Modeling of the Regenerator	596	(1)
Simulation of the Regenerator of a Catalytic Cracking Unit	597	(1)
Simultaneous Simulation of a Fluidized Bed Catalytic Cracker and Regenerator	597	(6)
Multiphase Flow Reactors	603	(39)
Types of Multiphase Flow Reactors	603	(3)
Packed Columns	603	(2)
Plate Columns	605	(1)
Empty Columns	605	(1)
Stirred Vessel Reactors	606	(1)
Miscellaneous Reactors	606	(1)
Design Models for Multiphase Flow Reactors	606	(4)
Gas and Liquid Phase Completely Mixed	607	(1)
Gas and Liquid Phase in Plug Flow	607	(1)
Gas Phase in Plug Flow. Liquid Phase Completely Mixed	608	(1)
An Effective Diffusion Model	608	(1)
A Two-Zone Model	609	(1)
An Alternate Approach	610	(1)
Specific Design Aspects	610	(32)
Packed Absorbers	610	(3)
The Simulation or Design of a Packed Bed Absorption Tower	613	(3)
The Absorption of CO2 in a Monoethanolamine (MEA) Solution	616	(3)
Two-Phase Fixed Bed Catalytic Reactors with Cocurrent Downflow. ``Trickle'' Bed Reactors and Downflow Packed Bubble Reactors	619	(7)
Two-Phase Fixed Bed Catalytic Reactors with Cocurrent Upflow. Upflow Packed Bubble Reactors	626	(1)
Plate Columns	627	(2)
The Simulation or Design of a Plate Column for Absorption and Reaction	629	(3)
The Absorption of CO2 in an Aqueous Solution of Mono- and Diethanolamine (MEA and DEA)	632	(4)
Spray Towers	636	(1)
Bubble Reactors	637	(1)
Stirred Vessel Reactors	638	(4)
Design of a Liquid-Phase o-Xylene Oxidation Reactor	642	(1)
A. Stirred Tank Reactor	642	(3)
B. Bubble Reactor	645	(6)
Acknowledgments	651	(2)
Author Index	653	(6)
Subject Index	659