REACTIVE DISTILLATION
CONTENTS PART I INDUSTRIAL APPLICATIONS 1 INDUSTRIAL APPLICATIONS OF REACTIVE DISTILLATION 3 11 INTRODUCTION 3 12 ETHERIFICATION: MTBE, ETBE, AND TAME 14 13 DIMERIZATION, OLIGOMERIZATION, AND CONDENSATION 15 14 ESTERIFICATION: METHYL ACETATE AND OTHER ESTERS 16 15 HYDROLYSIS OF ESTERS 18 16 HYDRATION 20 17 HYDROGENATION/HYDRODESULFURIZATION/HYDROCRACKING 20 171 BENZENE TO CYCLOHEXANE 21 172 SELECTIVE HYDROGENATION OF C STREAM 21 173 HYDROGENATION OF PENTADIENE 21 174 C ACETYLENE CONVERSION 22 175 HYDRODESULFURIZATION, HYDRODENITROGENATION, AND HYDROCRACKING 22 18 CHLORINATION 23 176 MISCELLANEOUS HYDROGENATIONS 22 19 ACETALIZATION/KETALIZATION 23 441 OUTLINE 74 110 RECOVERY AND PURIFICATION OF CHEMICALS 24 111 DIFFICULT SEPARATIONS 25 112 CHEMICAL HEAT PUMPS 26 113 RD WITH SUPERCRITICAL FLUIDS 26 114 CONCLUSIONS 26 2 REACTIVE DISTILLATION PROCESS DEVELOPMENT IN THE CHEMICAL PROCESS INDUSTRIES 30 21 INTRODUCTION 30 22 PROCESS SYNTHESIS 32 23 PROCESS DESIGN AND OPTIMIZATION 35 LIMITATIONS OF THE METHODS FOR SYNTHESIS AND DESIGN: 24 THE SCALE-UP PROBLEM 37 25 CHOICE OF EQUIPMENT 38 26 SOME REMARKS ON THE ROLE OF CATALYSIS 46 27 CONCLUSIONS 46 28 ACKNOWLEDGMENTS 47 29 NOTATION 47 APPLICATION OF REACTIVE DISTILLATION AND STRATEGIES IN PROCESS DESIGN 49 3 INTRODUCTION 49 31 32 CHALLENGES IN PROCESS DESIGN FOR REACTIVE DISTILLATION 51 321 FEASIBILITY ANALYSIS 51 322 CATALYST AND HARDWARE SELECTION 51 323 COLUMN SCALE-UP 51 33 MTBE DECOMPOSITION VIA REACTIVE DISTILLATION 52 331 CONCEPTUAL DESIGN 52 3321 CATALYST SELECTION AND REACTION KINETICS 55 332 MODEL DEVELOPMENT 54 3322 PHASE EQUILIBRIUM MODEL 55 3323 STEADY-STATE SIMULATION 56 333 LAB-SCALE EXPERIMENTS 57 334 PILOT-PLANT EXPERIMENTS 58 34 CONCLUSIONS 61 PART II PHYSICOCHEMICAL FUNDAMENTALS 4 THERMODYNAMICS OF REACTIVE SEPARATIONS 65 41 INTRODUCTION 65 42 PROCESS MODELS FOR REACTIVE DISTILLATION 66 421 OUTLINE 66 422 CASE STUDY: METHYL ACETATE 66 43 EQUILIBRIUM THERMODYNAMICS OF REACTING MULTIPHASE MIXTURES 70 44 FLUID PROPERTY MODELS FOR REACTIVE DISTILLATION 74 442 EXAMPLES 75 4421 HEXYL ACETATE: SENSITIVITY ANALYSIS 75 4422 METHYL ACETATE: PREDICTION OF POLYNARY VAPOR-LIQUID EQUILIBRIA 77 4423 BUTYL ACETATE: THERMODYNAMIC CONSISTENCY 81 4424 ETHYL ACETATE: CONSEQUENCES OF INCONSISTENCY 82 4425 FORMALDEHYDE + WATER + METHANOL: INTRINSICALLY REACTIVE COMPLEX MIXTURE 83 45 EXPERIMENTAL STUDIES OF PHASE EQUILIBRIA IN REACTING SYSTEMS 88 451 OUTLINE 88 452 REACTIVE VAPOR-LIQUID EQUILIBRIA 90 4521 BATCH EXPERIMENTS 90 4522 FLOW EXPERIMENTS 91 ACTIVA 4523 RECIRCULATION EXPERIMENTS 92 46 CONCLUSIONS 92 47 ACKNOWLEDGMENTS 93 48 NOTATION 93 5 IMPORTANCE OF REACTION KINETICS FOR CATALYTIC DISTILLATION PROCESSES 97 51 INTRODUCTION 97 52 REACTIVE IDEAL BINARY MIXTURES 98 521 REACTION-DISTILLATION PROCESS WITH EXTERNAL RECYCLING 100 5211 (00,00)-ANALYSIS 101 5212 (00, N) ANALYSIS 102 522 DISTILLATION COLUMN WITH REACTIVE REBOILER 103 FULLY REACTIVE DISTILLATION COLUMN 106 523 KINETIC EFFECTS ON ATTAINABLE PRODUCTS 109 53 SINGULAR POINT ANALYSIS 110 531 532 IDEAL TEMARY MIXTURES 112 5321 CASE A: DC = 02, C= 30 112 5322 CASE B: AAC 50, ASC= 30 112 533 NON-IDEAL MIXTURES 115 5331 SYNTHESIS OF MTBE 115 5332 SYNTHESIS OF TAME 117 534 SYSTEMS WITH LIQUID-PHASE SPLITTING 121 535 SYSTEMS WITH INTERFACIAL MASS-TRANSFER RESISTANCES 126 54 DETERMINATION AND ANALYSIS OF REACTION KINETICS 129 541 PHYSICOCHEMICAL TRANSPORT PHENOMENA 129 542 PROCESS EVALUATION BY DIMENSIONLESS NUMBERS 131 543 FORMULATION OF REACTION RATE EXPRESSIONS 133 544 IMPORTANCE OF TRANSPORT RESISTANCES FOR COLUMN OPERATION 135 55 CONCLUSIONS 138 56 ACKNOWLEDGMENTS 139 57 NOTATION 140 PART III PROCESS DESIGN WITH INTEGRATED SEPARATION 210 6 FEASIBILITY AND PROCESS ALTERNATIVES FOR REACTIVE DISTILLATION 145 61 INTRODUCTION 145 62 MOTIVATION 147 63 FLASH CASCADE MODEL 153 64 FEASIBILITY HYPOTHESIS 156 65 BIFURCATION ANALYSIS OF THE FLASH CASCADE MODEL 160 66 CONCLUSIONS 165 67 NOTATION 165 7 HARDWARE SELECTION AND DESIGN ASPECTS FOR REACTIVE DISTILLATION COLUMNS 169 71 INTRODUCTION 169 72 HARDWARE FOR HOMOGENEOUS REACTIVE DISTILLATION 169 721 CASE STUDY FOR METHYL ACETATE PRODUCTION 173 73 HARDWARE FOR HETEROGENEOUS REACTIVE DISTILLATION 177 731 DIFFERENT HARDWARE CONFIGURATIONS 177 732 HARDWARE SELECTION ASPECTS 183 74 THE SIDE-REACTOR CONCEPT 185 75 CONCLUSIONS 187 76 ACKNOWLEDGMENTS 188 8 DEVELOPMENT OF UNSTRUCTURED CATALYTIC PACKING FOR REACTIVE DISTILLATION PROCESSES 190 81 INTRODUCTION 190 82 REQUIREMENTS FOR RD CATALYTIC PACKING 190 83 STATE OF THE ART: CATALYTIC PACKING FOR RD PROCESSES 191 831 COMMERCIAL PACKING 191 832 ALTERNATIVE CONCEPTS 193 8321 CATALYSTS MADE OF PURE CATALYTIC MATERIAL 193 8322 CATALYSTS SUPPORTED ON CARRIER MATERIALS 194 84 NEW CATALYST CONCEPT: POROUS POLYMER/CARRIER COMPOSITE 195 841 REQUIREMENTS FOR THE CARRIER MATERIALS 198 842 REQUIREMENTS FOR THE POLYMERIZATION PROCESS 199 85 PREPARATION OF SULFONATED LON-EXCHANGE POLYMER/CARRIER CATALYSTS 200 86 PERFORMANCE OF POLYMER/CARRIER CATALYSTS 203 861 INFLUENCE OF POLYMER CONTENT AND REACTANT CONCENTRATION 204 862 INFLUENCE OF REACTION TEMPERATURE 205 863 INFLUENCE OF CROSS-LINKING 207 864 INFLUENCE OF CROSS-LINKING AT LOW POLYMER CONTENT 207 865 INFLUENCE OF CROSS-LINKING AT HIGH POLYMER CONTENT 209 87 OUTLOOK: EXTENSION TO OTHER SYNTHETIC PROCESSES 871 REACTIVE STRIPPING 210 872 REACTIVE CHROMATOGRAPHY 211 873 POLYMER-ASSISTED SOLUTION-PHASE ORGANIC SYNTHESIS 212 88 CONCLUSIONS 212 PART IV MODELING AND PROCESS CONTROL 9 MODELING OF HOMOGENEOUS AND HETEROGENEOUS REACTIVE DISTILLATION PROCESSES 217 91 INTRODUCTION 217 92 EQUILIBRIUM STAGE MODELS 217 93 NON-EQUILIBRIUM STAGE MODELING 220 931 THE CONVENTIONAL NEQ MODEL 220 ACTIVATE GO TO SETT