FUNDAMENTALS OF INDUSTRIAL CATALmlC PROCESSES FUNDAMENTALS OF INDUSTRIAL CATALYTIC PROCESSES Second Edition Calvin H. Bartholomew Brigham Young University Provo, Utah Robert J. Farrauto Engelhard Corporation Iselin, New Jersey WILEY- INTERSCIENCE Δ I f"* h F° A JOHN WILEY & SONS, INC., PUBLICATION Copyright 0 2006 by John Wiley & Sons, Inc. All rights reserved. Published by John Wiley & Sons, Inc., Hoboken, New Jersey. Published simultaneously in Canada. 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For general information on our other products and services please contact our Customer Care Department within the U.S. at 877-762-2974, outside the U.S. at 317-572-3993 or fax 3 17-572-4002, Wiley also publishes its books in a variety of electronic formats. Some content that appears in print, however, may not be available in electronic format. Library of Congress Cataloging-in-Publication Data: Farrauto, Robert J., 1941- Fundamentals of industrial catalytic processes / Robert J. Farrauto, Calvin H. Bartholomew. - 2nd ed. p. cm. Includes bibliographical references and index. ISBN-I 3 978-0-471 -45713-8 ISBN-I0 0-471 -4571 3-2 1. Catalysis. 2. Catalysts-Industrial applications. I. Bartholomew, Calvin H. 11. Title. QD505.F37 2005 660'.2995--dc22 2004026800 Printed in the United States ofAmerica 10 9 8 7 6 5 4 To my family and especially my wife Karen, for patience, love, and support. C.H.B. To my Italian-American heritage and all my family members, past, present, and future, who have provided me with an understanding of what is important in life. R.J.F. CONTENTS Preface xiv Acknowledgements xiv Nomenclature xvii Part One: Introduction and Fundamentals 1 1 Catalysis: Introduction and Fundamental Catalytic Phenomena 3 1.1 Emergence of Catalyst Technology, A Brief History 4 I .1.1 Basic Variables for Control of Chemical Reactions 4 I. 1.2 A Brief History of Catalyst Technology Development 4 1.2 Importance of Catalysis and Catalyst Technology 6 I .2.1 Impact on Society and Life Forms 6 1.2.2 Economic Importance of Catalyst Technology 8 1.2.3 Catalyst Technology of the Present 8 1.2.4 Catalysis in Your Future 10 1.3 Fundamental Catalytic Phenomena and Principles 12 1.3.1 Definitions 12 1.3.2 The Structure of a Supported Catalyst: Model and Reality 16 1.3.3 Steps in a Heterogeneous Catalytic Reaction 17 I .3.4 Adsorption and Desorption 18 1.3.5 Reaction and Diffusional Resistances for a Catalytic Reaction 24 1.3.6 Kinetics of Catalytic Surface Reactions 33 1.3.7 Effects of Surface Structure and Support on Catalytic Activity 41 1.4 Summary of Important Principles 51 I .5 Recommended Sources for Further Study 54 1.6 Exercises 54 I .7 References 57 2 Catalyst Materials, Properties and Preparation 60 2.1 Introduction 61 2.2 Catalyst Materials 61 2.2.1 Make-up of a Typical Heterogeneous Catalyst 62 2.2.2 Active Phases, Carriers, Promoters 62 2.2.3 Molecular Sieves and Zeolites 68 2 3 Catalyst Properties 78 2.3.1 Catalyst Engineering 78 2.3.2 Physical, Mechanical, and Chemical Properties 80 2.3.3 Dynamic (Catalytic) Properties of Catalysts 89 2.4 Catalyst Preparation and Forming 90 2.4.1 Making the Finished Catalyst 91 2.4.2 Catalyst Forming 102 2.5 The Future 107 2.5.1 Multidisciplinary, Mission-Oriented, Fundamental Research Aimed at Development of 107 New Concepts of Catalysis Design 2.5.2 Design of New Molecular Sieves 107 2.5.3 Design of Sophisticated Composite Catalysts Based on Nanostructures 108 2.5.4 Biocatalysts: The Development of Stabilized andlor Supported Enzymes 109 and Organometallic Enzyme Mimics 2.5.5 Novel Catalyst Preparation Methods: The Preparation of Amorphous Metal Powders, 109 Supported Catalysts and Nanocolloids by a Sonochemical Technique 2.5.6 Combinatorial Design of Catalysts 110 2.5.7 Computational Methods for Design of Catalysts 111 2.6 Summary I l l -7.7 Recommended Sources for Further Study 112 2.8 Exercises 1 I3 2.9 References 1 I4 viii CONTENTS 3 Catalyst Characterization and Selection 118 3.1 Principles and Objectives of Catalyst Characterization 1 I9 3.1.1 Definition of Catalyst Characterization 119 3.1.2 Objectives of Catalyst Characterization 121 3.1.3 Some Perspectives and Principles of Characterization 123 3.2 Determining Physical Properties of Catalysts 124 3.2.1 Surface Area, Pore Size, and Pore Volume 124 3.2.2 Particle Size and Size Distribution 135 3.2.3 Mechanical Strength 136 3.2.4 Density 137 3.3 Determining Chemical Properties of Catalysts 138 3.3.1 Chemical Composition 139 3.3.2 Chemical Structure and Morphology 139 3.3.3 Dispersion or Crystallite Size of Catalytic Species 135 3.3.4 Surface Acidity 152 3.3.5 Surface Reactivity 153 3.3.6 Surface Chemistry, Structure, and Composition 160 3.4 Catalyst Selection 179 3.5 The Future 181 3.5.1 Future Directions 181 3.5.2 Future Needs for Catalyst Characterization 184 3.6 Summary 184 3.7 Recommended Sources for Further Study 186 3.8 Exercises 187 3.9 References 191 4 Reactors, Reactor Design, and Activity Testing 197 4.1 Introduction 198 4.2 Definition and Classification of Reactors 198 4.2. i Definition 198 4.2.2 Classification 199 4.3 Fundamentals of Reactor Design 200 4.3.1 Basic Approach to Reactor Design 200 4.3.2 Material Balances for Ideal Reactors 202 4.3.3 Temperature Effects and Energy Balances 208 4.3.4 Examples of Reactor Design 216 4.4 Collecting, Analyzing and Reporting Data from Laboratory Reactors 224 4.4.1 Collection of Data: Integral and Differential Reactors 224 4.4.2 Analyzing and Reporting Data from Laboratory Reactors 227 4.4.3 Examples of Rate Data Analysis 230 4.5 Choosing Reactors in the Laboratory and Plant 237 4.5.1 Choosing Reactors for the Laboratory 237 4.5.2 Selection of Plant Reactors 242 4.6 The Future 247 4.6.1 Future Trends in Reactor Design and Kinetics 247 4.6.2 Kinetic Models for Reactor and Process Design 248 4.6.3 Process Plant Simulation and Corporate Modeling: A New Paradigm 249 4.7 Summary 250 4.8 Recommended Sources for Further Study 25 I 4.9 Exercises 252 4.10 References 258 5 Catalyst Deactivation: Causes, Mechanisms, and Treatment 260 5.1 Introduction 26 1 5.2 Causes and Mechanisms of Deactivation 26 I 5.2.1 Poisoning 262 5.2.2 Fouling, Coking, and Carbon Deposition 267 5.2.3 Thermal Degradation and Sintering 274 5.2.4 Loss of Catalytic Phases by Vapor Transport 279 CONTENTS ix 5.2.5 Mechanical Failure: Attrition and Crushing of Catalysts 281 5.3 Prevention and Regenerative Treatment of Catalyst Decay 283 5.3.1 Prevention of Catalyst Decay 283 5.3.2 Regeneration of Deactivated Catalysts 287 5.4 Treatment of Catalyst Decay in Reactor and Process Design and Operation 293 5.4.1 Modeling and Design of Deactivation Processes 293 5.4.2 Experimental Assessment of Deactivation Kinetics 3 00 5.4.3 Reactor and Process Design and Operation with Deactivating Catalyst 312 5.5 The Future 321 5.5.1 Projected Trends 321 5.5.2 Future Needs 322 5.6 Summary 322 5.7 Recommended Sources for Further Study 323 5.8 Exercises 324 5.9 References 33 1 Part Two: Industrial Practice 337 6 Hydrogen Production and Synthesis Gas Reactions 339 6.1 Introduction 340 6.2 Production of Hydrogen and Synthesis Gas via Steam Reforming 342 6.2.1 Overall Process 342 6.2.2 Purification of Hydrocarbons 344 6.2.3 Primary Steam Reforming 345 6.2.4 Secondary Steam Reforming 367 6.2.5 High-Temperature Water-Gas-Shift 367 6.2.6 Low-Temperature Water-Gas-Shift 369 6.2.7 Final CO/C02R emoval/Methanation 3 70 6.3 Ammonia Synthesis 371 6.3.1 Introduction and Background 371 6.3.2 Reaction Chemistry, Thermodynamics, Kinetics, and Mechanism 372 6.3.3 Catalyst Design 3 76 6.3.4 Catalyst Deactivation 3 79 3 80 6.3.5 Reactor and Process Design 382 6.4 Methanol Synthesis 6.4.1 Introduction 382 6.4.2 Reaction Chemistry and Equilibrium Thermodynamics 382 6.4.3 Reaction Mechanism, Active Sites, and Kinetics 385 390 6.4.4 Methanol Synthesis Catalysts 3 92 6.4.5 Catalyst Deactivation 393 6.4.6 Methanol Synthesis Process 397 6.4.7 Methanol Synthesis Literature 398 6.4.8 Higher Alcohol Synthesis 398 6.5 Fischer-Tropsch Synthesis 398 6.5.1 Introduction 398 6.5.2 History 402 6.5.3 Chemistry and Thermodynamics 405 6.5.4 Mechanisms, Kinetics, and Models 6.5.6 Co Product Distributions in and Selectivity Models of FTS 429 450 6.5.7 Catalyst Deactivation and Regeneration 457 6.5.8 Reactor Design 46 1 6.5.9 Process Technology 464 6.6 The Future 464 6.6.1 General Trends 6.6.2 Hydrogen and Synthesis Gas Production 46 5 465 6.6.3 Ammonia Synthesis 465 6.6.4 Methanol Synthesis 466 6.6.5 Fischer-Tropsch Synthesis 466 6.7 Summary 467 6.8 Recommended Readings for Further Study 4 70 6.9 Exercises X CONTENTS 6. I0 References 472 7 Hydrogenation and Dehydrogenation of Organic Compounds 487 7.1 Introduction 488 7.2 Hydrogenation Catalyst and Reactor Technologies 488 7.2.1 Hydrogenation Catalysts 488 7.2.2 Hydrogenation Reactor Design, Reactor Technology, and Process Conditions 496 7.3 Hydrogenation Reactions and Processes 513 7.3.1 Hydrogenation of Alkenes to Alkanes and Alkadienes or Alkynes to Alkenes 513 7.3.2 Hydrogenation of Aromatics and Nitroaromatics 518 7.3.3 Hydrogenation of Nitriles to Amines 523 7.3.4 Hydrogenation of Fats and Oils 524 7.3.5 Hydrogenation of Carbonyl Groups 53 1 7.3.6 Miscellaneous Hydrogenation Reactions 532 7.4 Dehydrogenation: Reaction Chemistry; Catalyst and Reactor Technologies 533 7.4.1 Dehydrogenation Reaction Chemistry 534 7.4.2 Dehydrogenation Catalysts 535 7.4.3 Dehydrogenation Reactor Technology 536 7.5 Important Dehydrogenation Reactions and Processes 536 7.5.1 Alkanes to Alkenes 536 7.5.2 Dehydrogenation of Ethylbenzene to Styrene 543 7.6 The Future 545 7.6.1 Hydrogenation Catalysis 545 7.6.2 Dehydrogenation Catalysis 548 7.7 Summary 549 7.8 Recommended Sources for Further Study 5 50 7.9 Exercises 55 1 7.10 References 554 8 Catalytic Oxidations of Inorganic and Organic Compounds 560 8.1 Catalytic Oxidation Reactions 56 1 8. I. 1 Introduction, Background, and Perspective 56 1 8.1.2 Classification of Oxidation Reactions 56 I 8.2 Oxidation of Inorganic Compounds 562 8.2.1 Introduction 562 8.2.2 Sulfuric Acid Production 562 8.2.3 Nitric Acid Production 570 8.3 Hydrogen Cyanide Production (Ammoxidation of Methane) 575 8.3.1 Reaction Chemistry 575 8.3.2 Catalyst 576 8.3.3 Processes 5 76 8.3.4 Catalyst Deactivation 578 8.4 Selective (Partial) Oxidation of Organic Compounds 578 8.4.1 Introduction, Background and Chemistry 578 8.4.2 Methanol to Formaldehyde 584 8.4.3 Ethylene to Ethylene Oxide 597 8.4.4 Ammoxidation of Propylene to Acrylonitrile and Related Processes 604 8.4.5 n-Butane to Maleic Anhydride 610 8.5 Future of Catalytic Oxidation 618 8.5.1 Short-Term Trends 619 8.5.2 Long-Term Future 62 1 8.6 Summary 624 8.7 Recommended Sources for Further Study 626 8.8 Exercises 627 8.9 References 629 9 Petroleum Refining and Processing 635 9.1 Petroleum Refining 636 9.1.1 Introduction 636 9.1.2 Fractionation of Petroleum 637 CONTENTS xi 9.1.3 Major Catalytic Applications for Upgrading Distilled Crude Oil 639 9.2 Hydrotreating 639 9.2.1 Reaction Chemistry and Kinetics 639 9.2.2 Hydrotreating Catalyst Design 645 9.2.3 Reactor Design 647 9.2.4 Hydrotreating Process 648 9.2.5 Catalyst Deactivation and Regeneration 649 9.2.6 Ultra Low Sulfur Diesel 652 9.3 Catalytic Cracking 653 9.3.1 Reaction Chemistry of Fluidized Catalytic Cracking 653 9.3.2 Mechanisms and Kinetics 655 9.3.3 Cracking Catalysts 662 9.3.4 Catalytic Cracking Process 669 9.3.5 Deactivation 670 9.4 Hydrocracking 67 1 9.4.1 Chemistry 67 I 9.4.2 Catalysts 672 9.4.3 Process 673 9.4.4 Catalyst Deactivation 673 9.5 Naphtha Reforming 674 9.5. I Chemistry 675 9.5.2 Catalysts 678 9.5.3 Process 679 9.5.4 Catalyst Deactivation and Regeneration 68 1 9.6 Isomerization 682 9.6. I Hydroisomerization of Normal Butane, Pentane and Hexane 682 9.6.2 Isomerization of Xylenes 684 9.7 Alkylation 685 9.7.1 Catalysts 685 9.7.2 Liquid Acid Process 686 9.7.3 Ethylbenzene Synthesis 687 9.8 Reformulated Gasoline and Methyl-f-Butyl Ether 687 9.8.1 Reformulated Gasoline (RFG) 687 9.8.2 MTBE Production 688 9.9 The Future 689 9.9.1 Near-Term and Process-Specific Trends 689 9.9.2 The Long Term Future of Refining (the next 10-25 years) 692 695 9.10 Summary 9.1 1 Recommended Sources for Further Study 696 696 9.12 Exercises 699 9.13 References 10 Environmental Catalysis: Mobile Sources 705 706 10.1 introduction 707 10.2 Automotive Gasoline Catalytic Converters 707 10.2.1 Introduction and Background 708 10.2.2 Early Oxidation Converters (1 976-1 979) 713 10.2.3 Three-way Catalysts (I 979-2000) 717 10.2.4 Modern Three Way Catalytic Converters (Post-2000) 724 10.2.5 Lean Burn Engines and Emissions Abatement Catalysts 725 10.2.6 Converter Design 73 1 10.3 Catalytic Abatement of Emissions from Diesel Engines 10.3. I Diesel Emissions 73 1 733 10.3.2 Diesel Oxidation Catalyst 736 10.3.3 Engine Testing of Catalysts 736 10.3.4 Catalyst Deactivation 73 7 10.3.5 Catalytic Treatment of Soot from Diesel Emission 738 10.3.6 Future of Diesel Emission Abatement 742 10.4 Ozone Abatement in High-Flying Commercial Aircraft 743 10.5 Summary xii CONTENTS 10.5.1 Development, Technological Significance and Status of Catalytic Emissions Controls for 743 Gasoline-Powered Vehicles 10.5.2 Development and Status of Catalytic Emissions Control Technology for Diesel-Powered Vehicles 744 10.5.3 Future Trends in Catalytic Emissions Control for Mobile Sources 745 10.6 Recommended Sources for Further Study 745 10.7 Exercises 746 10.8 References 747 11 Environmental Catalysis: Stationary Sources 753 1 I. 1 Introduction 754 1 1.2 Catalytic Reduction of NO, 755 1 1.2.1 Non-Selective Catalytic Reduction of NO, 755 1 1.2.2 Selective Catalytic Reduction of NO, 756 11.2.3 N20 Decomposition 777 I 1.3 Catalytic Oxidation of Hydrocarbon (VOC) Emissions 778 1 1.4 Catalytic Oxidation of CO Emissions 783 I 1.5 Kinetics of and Reactor Design for CO and VOC Oxidations 784 1 1.5.1 Kinetics and Reactor Design for Oxidation of CO 785 1 I S.2 Kinetics and Reactor Design for Oxidation of Hydrocarbons 789 1 1.5.3 Representative, Relevant Modeling Studies 794 1 1.6 Catalytic Abatement of Emissions from Wood Stoves 785 1 1.7 The Future 796 1 1.7.1 Introduction 796 1 1.7.2 Advanced/Novel Catalytic Materials 796 1 1.7.3 Catalytically Supported Thermal Combustion 797 I 1.7.4 Management of Hazardous and Toxic Materials, Wastes and CFCs 800 1 1.7.5 Catalytic Clean-up for Specialty Applications 800 1 1.7.6 Green Engineering/Chemistry and Renewable Processes 802 1 1.7.7 Future Needs 805 11.8 Summary 80 5 1 1.9 Recommendations for Further Study 806 1 1 .I0 Exercises 807 I 1.1 1 References 810 12 Homogeneous, Enzyme, And Polymerization Catalysis 820 12.1 Homogeneous Catalysis 82 1 12. I. 1 Introduction and Definitions 82 1 12.1.2 Fundamentals of Homogeneous Catalysis 822 12.1.3 Industrial Homogeneous Catalytic Processes 837 12.1.4 Examples of Important Processes 840 12. I .5 The Future of Homogeneous Catalysis 844 12.2 Enzyme Catalysis 846 12.2.1 Introduction 846 12.2.2 Chemistry, Kinetics, and Mechanisms 847 12.2.3 Industrial Enzymatic Processes and Biotechnology 852 12.2.4 Examples of Important Processes 859 12.2.5 The Future of Enzyme Catalysis 862 12.3 Polymerization Catalysis 864 12.3.1 Introduction and Definitions 864 12.3.2 Fundamentals of Polymerization Synthesis/Catalysis 871 12.3.3 Industrial Polymerization Catalysts and Catalytic Processes 879 12.3.4 Examples of Important Polymerization Processes 887 12.3.5 The Future of Polymerization Catalysis 895 12.4 Summary 897 12.5 Recommended Sources for Further Study 899 12.6 Exercises 90 1 12.7 References 903