JOHANN STICHLMAIR PHD, is the Emeritus of the Institute of Plant and Process Technology, Technical University of Munich. He is the winner of the Arnold Eucken Award 1978, the Emil Kirschbaum Medal 2003 and the Arnold Eucken Medal 2008 of the German Association of Chemical Engineers. He was also honored in a special session at the AIChE National Meeting in 2004. HARALD KLEIN PHD, is the current head of the Institute of Plant and Process Technology at the Technical University of Munich. His research is based on modeling and simulation of chemical processes, equipment design as well as thermodynamic property data. SEBASTIAN REHFELDT PHD, is a senior lecturer for equipment design and process design at the Technical University of Munich. His research concentrates on gas-liquid contact apparatus and heat exchangers.

• 1 Introduction 11.1 Principle of Distillation Separation 11.2 Historical 32 Vapor-Liquid Equilibrium 72.1 Basic Thermodynamic Correlations 72.1.1 Measures of Concentration 72.1.2 Equations of State (EOS) 82.1.3 Molar Mixing and Partial Molar State Variables 122.1.4 Saturation Vapor Pressure and Boiling Temperature of Pure Components 132.1.5 Fundamental Equation and the Chemical Potential 142.1.6 Gibbs-Duhem Equation and Gibbs-Helmholtz Equation 172.2 Calculation of Vapor-Liquid Equilibrium in Mixtures 182.2.1 Basic Equilibrium Conditions 182.2.2 Gibbs Phase Rule 192.2.3 Correlations for the Chemical Potential 192.2.4 Calculating Activity Coefficients with the Molar Excess Free Energy 232.2.5 Thermodynamic Consistency Check of Molar Excess Free Energy and Activity Coefficients 282.2.6 Iso-fugacity Condition 302.2.7 Fugacity of the Liquid Phase 302.2.8 Fugacity of the Vapor Phase 312.2.9 Vapor-Liquid Equilibrium Using an Equation of State 322.2.10 Fugacity of Pure Liquid as Standard Fugacity: Raoult’s Law 472.2.11 Fugacity of Infinitely Diluted Component as Standard Fugacity: Henry’s Law 482.2.12 Correlations describing the Molar Excess Free Energy and Activity Coefficients 492.2.13 Using Experimental Data of Binary Mixtures for Correlations Describing the MolarExcess Free Energy and Activity Coefficients .552.2.14 Vapor-Liquid Equilibrium Ratio of Mixtures 592.2.15 Relative Volatility of Mixtures 592.2.16 Boiling Condition of Liquid Mixtures 612.2.17 Condensation (Dew Point) Condition of Vapor Mixtures .622.3 Binary Mixtures and Phase Diagrams 812.3.1 Boiling Curve Correlation 812.3.2 Condensation (Dew Point) Curve Correlation 832.3.3 (p, x, y)-Diagram.842.3.4 (T, x, y)-Diagram 842.3.5 McCabe-Thiele Diagram 862.3.6 Boiling and Condensation Behavior of Binary Mixtures 862.3.7 General Aspects of Azeotropic Mixtures 902.3.8 Limiting Cases of Binary Mixtures 1042.4 Ternary Mixtures 1142.4.1 Boiling and Condensation Conditions of Ternary Mixtures 1142.4.2 Triangular Diagrams 1162.4.3 Boiling Surfaces 1162.4.4 Condensation Surfaces 1222.4.5 Derivation of Distillation Lines .1232.4.6 Examples for Distillation Lines 1283 Single Stage Distillation and Condensation 1373.1 Continuous Closed Distillation and Condensation 1373.1.1 Closed Distillation of Binary Mixtures 1373.1.2 Closed Distillation of Multicomponent Mixtures 1403.2 Batchwise Open Distillation and Open Condensation 1523.2.1 Binary Mixtures .1523.2.2 Ternary Mixtures 1573.2.3 Multicomponent Mixtures 1673.3 Semi-continuous Single Stage Distillation 1693.3.1 Semi-continuous Single Stage Distillation of Binary Mixtures 1694 Multistage Continuous Distillation (Rectification) 1734.1 Principles 1734.1.1 Equilibrium-Stage Concept 1764.1.2 Transfer-Unit Concept 1774.1.3 Comparison of Equilibrium-Stage and Transfer-Unit Concepts 1804.2 Multistage Distillation of Binary Mixtures 1814.2.1 Calculations Based on Material Balances 1824.2.2 Calculation Based on Material and Enthalpy Balances 1894.2.3 Distillation of Binary Mixtures at Total Reflux and Reboil .1924.2.4 Distillation of Binary Mixtures at Minimum Reflux and Reboil 1984.2.5 Energy Requirement for Distillation of Binary Mixtures.2044.3 Multistage Distillation of Ternary Mixtures 2064.3.1 Calculations Based on Material Balances 2084.3.2 Distillation of Ternary Mixtures at Total Reflux and Reboil 2154.3.3 Distillation of Ternary Mixtures at Minimum Reflux and Reboil 2244.3.4 Energy Requirement of Ternary Distillation 2484.4 Multistage Distillation of Multicomponent Mixtures 2554.4.1 Rigorous Column Simulation 2565 Reactive Distillation, Catalytic Distillation 2835.1 Fundamentals 2845.1.1 Chemical Equilibrium 2845.1.2 Stoichiometric Lines 2845.1.3 Non-Reactive and Reactive Distillation Lines .2875.1.4 Reactive Azeotropes 2895.2 Topology of Reactive Distillation Lines 2935.2.1 Reactions in Ternary Systems 2935.2.2 Reactions in Ternary Systems with Inert Components 2955.2.3 Reactions with Side Products 2975.2.4 Reactions in Quaternary Systems.2985.3 Topology of Reactive Distillation Processes 2985.3.1 Single Product Reactions 3005.3.2 Decomposition Reactions.3025.3.3 Side Reactions 3065.4 Arrangement of Catalysts in Columns 3075.4.1 Homogeneous Catalyst.3075.4.2 Heterogeneous Catalyst 3086 Multistage Batch Distillation 3136.1 Batch Distillation of Binary Mixtures 3146.1.1 Operation with Constant Reflux 3156.1.2 Operation with Constant Distillate Composition 3186.1.3 Operation with Minimum Energy Input 3236.1.4 Comparison of Energy Requirement for Different Modes of Distillation.3276.2 Batch Distillation of Ternary Mixtures 3276.2.1 Zeotropic Mixtures 3286.2.2 Azeotropic Mixtures 3326.3 Batch Distillation of Multicomponent Mixtures 3366.4 Influence of Column Liquid Hold-up on Batch Distillation 3376.5 Processes for Separating Zeotropic Mixtures by Batch Distillation 3406.6 Processes for Separating Azeotropic Mixtures by Batch Distillation 3416.6.1 Processes in One Distillation Field 3426.6.2 Processes in Two Distillation Fields 3436.6.3 Process Simplifications 3486.6.4 Hybrid Processes 3487 Energy Economization in Distillation 3577.1 Energy Requirement of Single Columns 3587.1.1 Reduction of Energy Requirement 3587.1.2 Reduction of Exergy Losses 3597.2 Optimal Separation Sequences of Ternary Distillation 3637.2.1 Process and Energy Requirement of the a-Path 3637.2.2 Process and Energy Requirement of the c-Path.3657.2.3 Process and Energy Requirement of the Preferred a/c-Path 3667.3 Modifications of the Basic Processes 3687.3.1 Material (Direct) Coupling of Columns.3687.3.2 Processes with Side Columns 3707.3.3 Thermal (Indirect) Coupling of Columns 3867.4 Design of Heat Exchanger Networks 3907.4.1 Optimum Heat Exchanger Networks 3927.4.2 Modifying the Optimum Heat Exchanger Network 3977.4.3 Dual Flow Heat Exchangers Networks 4017.4.4 Process Modifications 4018 Industrial Distillation Processes 4078.1 Constraints for Industrial Distillation Processes 4078.2 Fractionation of Binary Mixtures 4128.2.1 Recycling of Diluted Sulfuric Acid 4128.2.2 Ammonia Recovery from Waste Water 4148.2.3 Hydrogen Chloride Recovery from Inert Gases .4168.2.4 Linde Process for Air Separation 4188.2.5 Process Water Purification 4218.2.6 Steam Distillation 4258.3 Fractionation of Multicomponent Zeotropic Mixtures 4298.3.1 Separation Paths 4298.3.2 Processes with Side Columns 4318.4 Fractionation of Heterogeneous Azeotropic Mixtures 4358.5 Fractionation of Azeotropic Mixtures by Pressure Swing Processes 4368.6 Fractionation of Azeotropic Mixtures by Addition of an Entrainer 4398.6.1 Processes for Systems without Distillation Boundary 4408.6.2 Processes for Systems with Distillation Boundary 4438.6.3 Hybrid Processes.4558.7 Industrial Processes of Reactive Distillation 4698.7.1 Synthesis of MTBE 4698.7.2 Synthesis of Mono-Ethylene Glycol 4718.7.3 Synthesis of TAME 4738.7.4 Synthesis of Methyl-Acetate 4749 Design of Mass Transfer Equipment 4819.1 Types of Design 4829.1.1 Tray Columns.4829.1.2 Packed Columns 4849.1.3 Criteria for Use of Tray or Packed Columns 4869.2 Design of Tray Columns 4879.2.1 Design Parameters of Tray Columns 4879.2.2 Operating Region of Tray Columns 4899.2.3 Two-Phase Flow on Trays 4979.2.4 Mass Transfer in the Two-Phase Layer on Column Trays 5189.3 Design of Packed Columns 5339.3.1 Design Parameters of Packed Columns 5349.3.2 Operating Region of Packed Columns 5459.3.3 Two-Phase Flow in Packed Columns .5489.3.4 Mass Transfer in Packed Columns 5689.4 Appendix to Chapter 9: Pressure Drop in Packed Beds 58710 Control of Distillation Processes 60110.1 Control Loops 60210.1.1 Single Control Loop 60210.1.2 Ratio Control Loop 60410.1.3 Disturbance Feed Forward Control Loop 60410.1.4 Cascade Control Loop 60510.2 Single Control Tasks for Distillation Columns 60510.2.1 Liquid Level Control 60510.2.2 Split Stream Control 60610.2.3 Pressure Control 61110.2.4 Product Concentration Control 61310.3 Basic Control Configurations of Distillation Columns 61310.3.1 Basic Control Systems without Composition Control 61710.3.2 One-Point Composition Control Configurations 62310.3.3 Two-Point Composition Control Configurations 62610.4 Application Ranges of the Basic Control Configurations 62910.4.1 Impact of Split Parameters according to Split Rule 2.62910.4.2 Sharp Separations of Ideal Mixtures with Constant Relative Volatility at MinimumReflux and Boilup Ratio 63910.4.3 Extended Application Ranges of the Basic Control Configurations 64310.5 Examples for Control Configurations of Distillation Processes 64610.5.1 Azeotropic Distillation Process by Pressure Change.64610.5.2 Distillation Process for Air Separation 64710.5.3 Distillation Process with a Main and a Side Column 64910.5.4 Azeotropic Distillation Process by Using an Entrainer 65010.6 Control Configurations for Batch Distillation Processes 651Index 655

Select Guide Rating