Organic Synthesis Engineering

by Doraiswamy, L. K.

• ISBN13: 9780195096897
• ISBN10: 0195096894
• Format: Hardcover
• Copyright: 2001-02-15
• Publisher: Oxford University Press

Summary

This book will formally launch "organic synthesis engineering" as a distinctive field in the armory of the reaction engineer. Its main theme revolves around two developments: catalysis and the role of process intensification in enhancing overall productivity. Each of these two subjects are becoming increasingly useful in organic synthesis engineering, especially in the production of medium and small volume chemicals and enhancing reaction rates by extending laboratory techniques, such as ultrasound, phase transfer catalysts, membrane reactor, and microwaves, to industrial scale production. This volume describes the applications of catalysis in organic synthesis and outlines different techniques of reaction rate and/or selectivity enhancement against a background of reaction engineering principles for both homogeneous and heterogeneous systems.

Table of Contents

Introduction and Structure of the Book	3	(14)
Why Organic Synthesis Engineering	3	(1)
The Organic Chemicals Ladder and the Role of Catalysis	4	(4)
Process Intensification	8	(1)
Structure of the Book	9	(4)
Internal Organization of Chapters	13	(4)
PART I REACTIONS AND REACTORS IN ORGANIC SYNTHESIS: BASIC CONCEPTS
Rates and Equilibria in Organic Reactions: The Thermodynamic and Extrathermodynamic Approaches	17	(19)
Basic Thermodynamic Relationships and Properties	17	(9)
Thermodynamics of Reactions in Solution	26	(2)
The Extrathermodynamic Approach	28	(2)
Extrathermodynamic Relationships between Rate and Equilibrium Parameters	30	(6)
Estimation of Properties of Organic Compounds	36	(16)
Correlation Strategy	37	(1)
Basic Properties	37	(1)
Thermodynamic and Equilibrium Properties	38	(5)
Reaction Properties	43	(3)
Transport Properties	46	(5)
Surface Tension and Ultrasonic Velocity	51	(1)
Reactions and Reactors: Basic Concepts	52	(33)
Reaction Rates	52	(4)
Stoichiometry of the Rate Equation	56	(2)
Reactors	58	(19)
Transport between Phases	77	(4)
Laboratory Reactors	81	(4)
Complex Reactions	85	(40)
Reduction of Complex Reactions	86	(6)
Rate Equations	92	(3)
Selectivity and Yield	95	(15)
Simultaneous Homogeneous and Catalytic (or Autocatalytic) Reactions	110	(15)
Notation to Part I	113	(5)
References to Part I	118	(7)
PART II CATALYSIS IN ORGANIC SYNTHESIS AND TECHNOLOGY
Catalysis by Solids, I: Organic Intermediates and Fine Chemicals	125	(46)
Modified Forms of the More Common Catalysts	127	(2)
Zeolites	129	(14)
Heteropolyacid Catalysts	143	(2)
Clays in Catalysis: A Class of Supported Reagents	145	(4)
Solid Superacids	149	(1)
Solid Base Catalysts	149	(1)
Metallic Glass Catalysts	150	(2)
Ion-Exchange Resins	152	(2)
Catalysis by Inclusion: Cyclodextrins	154	(1)
Titanates	155	(1)
Catalysts for Selected Classes of Reactions	156	(7)
``Heterogenized'' Homogeneous Catalysts	163	(5)
Role of Solvent in Catalysis by Solids	168	(3)
Catalysis by Solids, 2: The Catalyst and Its Microenvironment	171	(42)
Modeling of Solid Catalyzed Reactions	171	(12)
Role of Diffusion in Pellets: Catalyst Effectiveness	183	(18)
Effect of External Mass and Heat Transfer	201	(3)
Combined Effects of Internal and External Diffusion	204	(1)
Relative Roles of Mass and Heat Transfer in Internal and External Diffusion	205	(1)
Regimes of Control	206	(1)
Eliminating or Accounting for Transport Disguises	207	(3)
Experimental Reactors	210	(3)
Homogeneous Catalysis	213	(30)
Homogeneous versus Heterogeneous Catalysis	214	(1)
Formalisms in Transition-Metal Catalysis	214	(8)
The Operational Scheme of Homogeneous Catalysis	222	(1)
The Basic Reactions of Homogeneous Catalysis	223	(3)
Main Features of Transition-Metal Catalysis in Organic Synthesis: A Summary	226	(2)
Important Classes of Reactions with Industrial Examples	228	(10)
General Kinetic Analysis	238	(5)
Asymmetric Synthesis	243	(62)
Basic Definitions/Concepts	244	(4)
Methods of Preparing Pure Enantiomers	248	(10)
Asymmetric Synthesis	258	(2)
Homogenous Asymmetric Catalysis	260	(16)
Heterogeneous Asymmetric Catalysis	276	(29)
Notation to Part II	280	(5)
References to Part II	285	(20)
PART III REACTOR DESIGN FOR HOMOGENEOUS AND FLUID-SOLID (CATALYTIC) REACTIONS
Reactor Design for Simple Reactions	305	(28)
Plug-Flow Reactors with Recycle	305	(4)
Mixed-Flow Reactors in Series	309	(6)
Semibatch Reactors	315	(11)
Varying Volume Reactors	326	(4)
Measures of Mixing: Comparison of the Series, Recycle, and Variable Volume Reactors	330	(1)
Comments	331	(2)
Reactor Design for Complex Reactions	333	(24)
Batch Reactor	334	(5)
Plug-Flow Reactor	339	(1)
Continuous Stirred Tank Reactor	340	(3)
Reactor Choice for Maximizing Yields and Selectivities	343	(5)
Optimum Temperatures or Temperature Profiles for Maximizing Yields and Selectivities	348	(9)
Reactor Design for Solid-Catalyzed Fluid Phase Reactions	357	(39)
Fixed-Bed Reactor	357	(20)
Fluidized-Bed Reactor	377	(13)
Reactor Choice for a Deactivating Catalyst	390	(6)
Mixing, Multiple Solutions, and Forced Unsteady-State Operation	396	(35)
Role of Mixing	396	(13)
Multiple Solutions	409	(22)
Notation to Part III	417	(6)
References to Part III	423	(8)
PART IV FLUID-FLUID AND FLUID-FLUID-SOLID REACTIONS AND REACTORS
Gas-Liquid Reactions	431	(37)
The Basis	431	(2)
Diffusion Accompanied by an Irreversible Reaction of General Order	433	(8)
Effect of Temperature	441	(2)
Discerning the Controlling Regime in Simple Reactions	443	(1)
Diffusion Accompanied by a Complex Reaction	443	(5)
Simultaneous Absorption and Reaction of Two Gases	448	(9)
Absorption of a Gas Followed by Reaction with Two Liquid-Phase Components	457	(1)
Extension to Complex Rate Models: Homogeneous Catalysis	458	(6)
Measurement of Mass Transfer Coefficients	464	(1)
Examples of Gas-Liquid Reactions	465	(3)
Liquid-Liquid and Solid-Liquid Reactions	468	(22)
Liquid-Liquid Reactions	468	(9)
Solid-Liquid Reactions	477	(13)
Gas-Liquid and Liquid-Liquid Reactor Design	490	(27)
A Generalized Form of Equation for All Regimes	490	(3)
Classification of Gas-Liquid Contactors	493	(2)
Reactor Design for Gas-Liquid Reactions	495	(9)
Reactor Choice for Gas-Liquid Reactions	504	(6)
Liquid-Liquid Contactors	510	(5)
Stirred Tank Reactor: Some Practical Considerations	515	(2)
Multiphase Reactions and Reactors	517	(58)
Analysis of Three-Phase Catalytic Reactions	518	(8)
Design of Three-Phase Catalytic Reactors	526	(7)
Types of Three-Phase Reactors	533	(14)
Collection and Interpretation of Laboratory Data for Three-Phase Catalytic Reactions	547	(1)
Examples of Three-Phase Catalytic Reactions in Organic Synthesis and Technology	548	(1)
Three-Phase Noncatalytic Reactions	549	(26)
Notation to Part IV	559	(6)
References to Part IV	565	(10)
PART V STRATEGIES FOR ENHANCING THE RATES OF ORGANIC REACTIONS
Biphasic Reaction Engineering	575	(31)
Equilibria in Biphasic Reactions	576	(9)
Solvent Selection	585	(2)
Role of Aqueous Phase Volume	587	(1)
Matching the pH Optima for Reaction Equilibrium and Catalyst Activity	588	(1)
Modeling of Biphasic Biocatalytic Systems	589	(6)
Use of Biphasing in Organic Synthesis	595	(6)
Examples of Biphasing	601	(5)
Phase-Transfer Reaction Engineering	606	(41)
General Features	607	(5)
Kinetics and Modeling of Soluble PTC	612	(13)
Immobilized PTC	625	(16)
Industrial Applications of PTC	641	(6)
Bioorganic Synthesis Engineering	647	(35)
Microbes and Enzymes	648	(5)
Kinetics and Modeling of Bioreactions	653	(9)
Bioreactors	662	(12)
Examples of the Use of Biocatalysts in Organic Synthesis	674	(8)
Electroorganic Synthesis Engineering	682	(29)
Basic Concepts and Definitions	683	(10)
Modeling of Electroorganic Reactions and Reactors	693	(1)
Reaction Modeling	693	(2)
Reactor Modeling	695	(9)
Scale-Up of Electrochemical Reactors	704	(2)
Industrial Electrochemical Cell Components and Configurations	706	(1)
Selected Examples of Industrial Electroorganic Synthesis	707	(4)
Sonoorganic Synthesis Engineering	711	(33)
Devices for Producing Ultrasound	712	(2)
Homogeneous Reactions	714	(8)
Heterogeneous Reactions	722	(4)
Ultrasound in Organic Synthesis	726	(7)
Scale-Up of Sonochemical Reactors	733	(4)
Design of Cavitation Reactors	737	(2)
Sonochemical Effect without Ultrasound: Hydrodynamic Cavitation	739	(5)
Microphase-Assisted Reaction Engineering	744	(21)
Classification of Microphases	744	(2)
Analysis of Microphase Action	746	(3)
Microphase as a Chemical (Catalytic) or Physical Sink	749	(8)
Microphase as a Physical Carrier	757	(1)
Microphase as a Source---Reactant as Microphase	758	(1)
Solid Product as a Microphase---Microphase-Assisted Autocatalysis	759	(6)
Membrane-Assisted Reactor Engineering	765	(27)
General Considerations	766	(7)
Modeling of Membrane Reactors	773	(10)
Operational Features	783	(5)
Comparison of Reactors	788	(1)
Examples of the Use of Membrane Reactors in Organic Technology and Synthesis	789	(3)
Multifunctional Reactor Engineering	792	(23)
Reaction-Extraction	793	(9)
Distillation-Reaction	802	(13)
Other Important (and Some Lesser Known) Strategies of Rate Enhancement	815	(84)
Photochemical Enhancement	815	(12)
Enhancement by Micelles	827	(4)
Microwave-Assisted Organic Synthesis	831	(8)
Organic Syntheis in Supercritical Fluids	839	(4)
Use of Hydrotropes (Hydrotropic Solubilization)	843	(4)
Combinatorial Strategies	847	(8)
Use of Micromixing and Forced Unsteady-State Operation	855	(44)
Notation to Part V	856	(18)
References to Part V	874	(25)
A Process Overview	899	(4)
Epilogue	903	(2)
Acknowledgments for Figures and Tables	905	(4)
Index	909