HETEROGENEOUS CATALYSIS IN |NDUSTRIAL PRACTICE SECOND EDITION Charles N. Satterfield Professor Emeritus of Chemical Engineering Massachusetts Institute of Technology Cambridge, Massachusetts & KRIEGER PUBLISHING COMPANY Malabar, FloridaOriginal Edition 1980 Second Edition 1991 Reprint Edition 1996 with corrections Printed and Published by KRIEGER PUBLISHING COMPANY KRIEGER DRIVE MALABAR, FLORIDA 32950 Copyright © 1980, 1991 by McGraw-Hill, Inc. Transferred to author, 1996 Reprinted by arrangement All rights reserved. No part of this book may be reproduced in any form or by any means, electronic or mechanical, including information storage and retrieval systems without permission in writing from the publisher. No liability is assumed with respect to the use of the information contained herein. Printed in the United States of America. FROM A DECLARATION OF PRINCIPLES JOINTLY ADOPTED BY A COMMITTEE OF THE AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS: This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold with the understanding that the publisher is not engaged in rendering legal, accounting, or other professional service. If legal advice or other expert assistance is required, the services of a competent professional person should be sought. Library of Congress Cataloging-In-Publication Data Satterfield, Charles N. Heterogeneous catalysis in industrial practice / Charles N. Satterfield. -- 2nd ed. Pp. oom. Reprint. Originally published: 2nd ed. New York : McGraw-Hill, c1991. Includes bibliographical references and index. ISBN 1-57524-002-5 (cloth : alk. paper). 1. Heterogeneous catalysis. 1. Title [TP156.C35S27 1996] 660' .2995--de20 96-16571 cIP 10 9 8 7 6 5 4 3Preface xili Preface to the First Edition xv Chapter 1. Introduction and Basic Concepts Ww 1.2 1.3 1.4 15 1.6 Introduction Industrial Heterogeneous Catalysts Definitions 1.3.4 Catalyst 1.3.2 Catalyst Activity 1.3.3 Catalyst Selectivity and Functionality 1.3.4 Negative Catalyst 1.3.5 Heterohomogeneous Catalysis 1.3.6 Sites 1.3.7 Turnover Number 1.3.8 Naming of Catalysts and Catalyst Structures 1.3.9 Catalyst Deactivation Thermodynamics and Energetics 1.4.1 Reaction Pathways Classification and Selection of Catalysts Homogeneous Catalysis References Chapter 2. Adsorption 24 Characterization of Type of Sorption 2.1.1 Heat Effect 2.1.2 Rate of Adsorption 2.1.3 Effect of Temperature on Amount Adsorbed 2.1.4 Extent of Adsorption 2.1.5 Reversibility 2.1.6 Specificity Contents SSeeReeesvi Contents 2.2 Physical Adsorption Isotherms 2.3 Heat of Adsorption 2.4 Models for Adsorption Isotherms 2.4.1, Langmulr Isotherm 2.4.2 Freundlich Isotherm 2.4.3 Temkin (Slygin-Frumkin) Isotherm 2.8 Chemisorption References Chapter 3. Rates and Kinetic Models of Catalytic Reactions 3.1 Introduction 3.2. Empirical Correlations 3.3. Formal Kinetic Models 3.3.1 Langmulr-Hinshelwood Mode! 3.3.2 Apparent Activation Energies 3.3.3 Maximum in Rate with Increased Temperature 3.3.4 Rideal Model 3.3.5 Two-Step Kinetic Models 3.3.6 Reversible Reaction 3.4 Some Uses and Limitations of Kinetic Models 3.5. Mixtures of Reactants 3.6 Polsoning and Induction Periods 3.6.1 Rate of Deactivation 3.7. Compensation 3.7.1 False Compensation References Chapter 4. Catalyst Preparation and Manufacture 4.1 General Methods of Manufacture 4.2 Precipitation Method 4.2.1 Precipitation 4.2.2 Forming Operations 4.2.3 Calcination 4.2.4 Reduction to the Metal 4.3. Impregnation 4.3.1 Distribution through Pellet 4.4 Special Preparative Methods 4.4.1 Massive Metal Catalysts 4.4.2 Thermal Fusion 4.4.3 Leaching Processes 4.4.4 Miscellaneous Catalyst Supports 4.5.1 Alumina 45.2 Sillea 4.5.3 Activated Carbon 4. a 39 a aa 46 a7 a7 SSIISSRRRSSRAS 84 87 93 95 97 101 103 107 108 110 110 110 10 112 12 114 120 12246 Contents 4.5.4 Titania 4.5.5 Other Supports Promoters 4.6.1 Textural Promoters 4.6.2 Structural Promoters References Chapter 5. Physical Characterization and Examination 5.1 5.2 5.3 5.4 5.5 5.6 Measurement of Surface Area 5.1.1 Physical Adsorption tsotherms 5.1.2 Brunauer-Emmett-Teller (BET) Method 5.1.3 Specific Area by Selective Chemisorption Pore Volume Pore Size Distribution 5.3.1 Nitrogen Adsorption 5.3.2 Microporosity and Surface Area by the tplot Method 5.3.3 Mercury Intrusion Porosimetry 5.3.4 Examples of Pore Size Distributions Mechanical Properties 5.4.1 Crush Tests, Abrasion and Attribution Resistance 5.4.2 Particle Size Distribution Selected Instrumental Methods 5.5.1 Microscopy 5.5.2 Auger Electron Spectroscopy (AES) 5.5.3 X-ray Photoelectron Spectroscopy (XPS, ESCA) 5.5.4 Electron Microprobe Analysis 5.5.5 X-ray Diffraction (XRD) Crystallography 5.5.6 Calorimetry 5.5.7 Gravimetric Methods Reference Catalysts References Chapter 6. Supported Metal Catalysts 6.1 6.2 63 6.4 65 6.6 Metal Activity 6.1.1 Structure Sensitivity Metal Dispersion (Percentage Exposed) Alloy Catalysts 6.3.1 Surface Composition 6.3.2 Reactions on Alloys 6.3.3 Site-Number Requirements (Geometrical Ettects) Sintering, Mobility, and Redispersion 6.4.1 Metal-Support Interactions 6.4.2 Spillover 6.4.3 Solution of Metals as Metal Oxides Carbon Formation Poisoning of Metal Catalysts vil 123 124 127 128 129 157 175 198vit Contents 6.7 Hydrogenation Reactions 201 6.7.1 Edible Oils 202 6.7.2 Selective Hydrogenation of Unsaturated Aliphatics 203 6.7.3 Cyclohexane 205 6.7.4 Solvent Purification 206 References 207 Chapter 7. Acid and Zeolite Catalysts 209 7.1 Source of Acidity 209 7.2 Determination of Acid Strength 212 7.2.1 Indicator Methods 212 7.2.2 Other Physical Methods 214 7.2.3 Use of Model Reactions 216 7.3. Acid Properties of Representative Sollds 216 7.4 Correlations between Acidity and Catalytic Activity 220 7.5 Mechanism of Catalytic Cracking 222 7.6 Base and Acid-Base Catalysts 225 7.7 Zeolites 226 7.7.1 Pore Structure 230 7.7.2 Synthesis 236 7.7.3 Effective Pore Size 239 7.7.4 Diffusion In Zeolites 240 7.7.5 Shape-Selective Catalysis 244 7.7.6 Activity 250 7.7.7 Catalytic Cracking with Zeolites 252 7.7.8 Coke Formation 254 7.7.9 Methanol to Gasoline 258 7.7.10 Literature on Zeolites 258 7.8 Other Solid Acids 259 7.9 Methyl-Tert-Butyl Ether (MTBE) 260 References (262 Chapter 8. Catalytic Oxidation 267 8.1 Redox Mechanism 269 8.2 Oxidation and Ammoxidation of Propylene 273 8.2.1 Acrylonitrile 273 8.2.2 Acrolein and Acrylic Acid 278 8.2.3 Other Ammoxidation Processes 279 8.3 Ethylene to Ethylene Oxide 279 8.4 Methanol to Formaldehyde 285 8.4.1 Methanol-Rich System (Silver Catalyst) 286 8.4.2 Methanol-Lean System (Iron-Molybdate Catalyst) 288 8.5 Butylenes to Butadiene 230 8.6 Maleic Anhydride and Phthalic Anhydride 291 8.6.1 Maleic Anhydride 29287 8.8 8.9 8.10 8.11 8.12 8.13 8.14 Contents 8.6.2 Phthalic Anhydride Vinyl Acetate Oxychlorination Sulturie Acid Ammonia Oxidation ‘Synthesis of Hydrogen Cyanide Control of Vehicle Engine Emissions 8.12.1 Simultaneous Removal of CO, Hydrocarbons and NO, 8.12.2 Diesel Particulate Emissions Reduction of NO, from Stationary Sources Literature References Chapter 9. Processing of Petroleum and Hydrocarbons 9.1 9.2 9.3 9.4 9.5 9.6 9.7 98 9.9 9.10 9.11 9.12 9.13 9.14 9.15 9.16 917 9.18 9.19 Composition of Petroleum Fractionation Motor Fuels Catalytic Cracking Catalytic Reforming 9.5.1 Catalyst Dual Functionality 9.5.2 Reactor Configurations 9.5.3 Catalyst Compositions 9.5.4 Literature Cyclization 9.6.1 From C,-C, Parattins 9.8.2 From C,-C, Paraffins Isomerization 9.7.1 Parattin Isomerization 9.7.2 Xylene Isomerization Molybdenum Sulfide Catalysts Hydrodesulfurization (HDS) Hydrodenitrogenation (HON) Hydrodeoxygenation (HDO) Hydrodemetallation (HDM) Hydrocracking Interaction Effects Conversion of Residua and Heavy Oils Hydrotreating Dehydrogenation 9.17.1. Dehydrogenation of Butane and Butene 9.17.2 Styrene from Ethylbenzene Hydrodealkylation Regeneration of Coked Catalysts by Combustion 9.19.1 Intrinsic Kinetics: Nature of Coke Deposits 9.19.2 Carbon Gasification Kinetics 9.19.3 Regeneration of Coked Catalysts In Practice References 298 301 304 306 312 320 324 328 330 331 333 334 339 340 342 344 352 358 360 364 366 369 370 370 371 371 371 373 375 378 383 388 390 390 393 395 400 402 402 403 405 406 408 409 ant 413x Contents Chapter 10. Synthesis Gas and Associated Processes 10.1 10.2 10.3 10.4 10.5 10.6 Steam Retorming 10.1.1 Formation and Reactions of Carbon 10.1.2 Applications of Steam Reforming 10.1.3 Reforming Catalysts 10.1.4 Retorming Processes Fischer-Tropsch Synthesis 10.2.1 Mechanism 10.2.2 Catalysts 10.2.3 Reaction Network 10.2.4 The Literature Water-Gas Shift Reaction 10.3.1 High-Temperature Shift Catalyst 10.3.2 Low-Temperature Shift Catalyst Methanol Synthesis 10.4.1 High-Pressure Process 10.4.2 Low-Pressure Process 10.4.3 Kinetics 10.4.4 Higher Alcohols Ammonia Synthesis 10.5.1 Reactors 10.5.2 Kinetics Methanation References Chapter 11. Experimental Methods Wd 11.2 11.3 W4 11.5 Commercial Reactors 11.1.1 Adlabatic Reactor 11.1.2 Multitube Reactor with Heat Exchange 11.1.3 Fluidized-Bed Reactor 11.1.4 Slurry Reactor 11.1.5 Contact Time Reaction Regimes 11.2.1 Examples Theoretical Criterla 11.3.1 Intraparticle 11.3.2 Interphase Transport 11.3.3 Reactor Gradients 11.3.4 Axial Dispersion Effective Diffusivity 11.4.1 Bulk Diffusion 11.4.2 Bulk Diffusion in Porous Catalysts 11.4.3 Knudsen Diffusion 11.4.4 The Transition Region 11.4.5 Recommended Procedures Thermal Conductivity of Porous CatalystsContents 11.6 Bulk-Mass Transfer 11.6.1 Heat Transfer 11.6.2 Temperature Difference between Solid and Fluld 11.7. Examples of Use of Criteria 11,8 Experimental Laboratory Reactors 11.8.1 A Scouting Laboratory Reactor 11.8.2 A Catalyst-Optimization Reactor 11.8.3 The Prototype Reactor 11.8.4 Gradientless Reactors 11.9 Reactor Modeling: An Example References Index 541 xt 516 518 518Preface Since publication of the first edition in 1980, the underlying purpose of this book remains unchanged, but its contents have been brought up to date in a variety of ways to respond to the developments of the past decade. All the chapters have undergone scrutiny and revision, but the major changes are found in Chapter 5 on physical character- ization, in Chapter 7 on acid and zeolite catalysts, in Chapter 8 on cat- alytic oxidation, in Chapter 9 on processing of petroleum and hydro- carbons, and in Chapter 10 on synthesis gas and associated processes. Some theoretical concepts of lesser significance have been condensed or discarded, and newer theories and possible mechanisms supported by evidence have been introduced. The resulting volume is a useful current reference for professionals with a variety of backgrounds who are concerned with some aspect of catalysis and heterogeneous cata- lysts. Since 1980, applications of solid catalysts have continued to expand, spurred especially by growing concerns for the environment, by the continuing evolution of fossil fuel processing, and by the ever present goal of new and improved processes for chemical manufacture. Mod- ern instrumental techniques have undergone rapid gains in providing an understanding of catalyst surface structure and interactions of adsorbed species with surfaces. The improved characterization of the complex structures of practical catalysts and correlation with perfor- mance has proceeded apace. This has been aided by major advances in analytical techniques, the use of automated experimental equipment, and data reduction by sophisticated computer methods. The goal of practical catalyst design on a rational and an a priori basis continues to beckon and is steadily being approached. An author is indebted to countless individuals in ways that are fre- quently difficult to recognize and to acknowledge explicitly. The first edition was the outgrowth of class notes that I wrote for use in a sub- ject in catalysis, directed primarily to seniors and first-year graduate students in chemical engineering, and further tested in intensive courses in industry. Since then I have continued to learn from the op- portunity to engage in a wide variety of problems involving catalysts, both in the plant and in the laboratory. As with the first edition, I amxiv Pretace indebted to Craig Abernethy for his careful typing and editing of the manuscript and to Claire Chanenchuk, one of my current doctoral the- sis students, for providing a meticulous perspective on the contents. Again I wish to express my special gratitude to my wife Anne, for help in a variety of ways. Charles N. SatterfieldPreface to the First Edition Studies of solid catalysts and reactions catalyzed by solids have bur- geoned in recent years, stimulated by an increasing number and va- riety of applications in industry. Significant contributions have come from individuals or groups whose formal academic education was in one or more of a wide variety of disciplines: these have ranged over the entire field of chemistry (including organic chemistry, inorganic chemistry, physical chemistry, chemical kinetics, and surface chemis- try) to solid-state and surface physics, ceramics, physical metallurgy, and chemical reaction engineering. One's first impression, which may be reinforced by further study, is apt to be that it is a vast and confusing field replete with an enormous quantity of perhaps significant but empirical facts intermixed with perhaps useful theories. The situation is not surprising when one re- flects that heterogeneous catalysis in practice is concerned with con- trolling the rate and direction of a chemical reaction or group of reac- tions, whose basic mechanism is frequently understood only in broad outline; by means of a complex solid substance, typically rather poorly characterized, selected from one or more of the many elements of the periodic table. In such a situation there is the need for an overview of the land- scape to identify features that provide orientation. This book has been written for chemists, chemical engineers, and others who seek such an overview, and especially for those who have had little previous expo- sure to heterogeneous catalysis and would like an introduction to the subject. The term “industrial practice” in the title is to warn the reader that attention is devoted primarily to catalysts and reactions that are of industrial significance for large-scale operations and uti- lized under practicable conditions of pressure, temperature, and con- tact time, often processing impure reactants or mixtures. At present, theoretical concepts are the most successful in interpretation of the re- actions of small molecules such as hydrogen, carbon monoxide, oxy- gen, and nitrogen on well-characterized surfaces. In the present vol- ume, theory has not been neglected, but the attention devoted to xvxvi Preface to the First Edition various theoretical concepts is in some proportion to those that have stood the test of time and also seem to be of present practical impor- tance or of some value for prediction for those reactions of industrial interest. Properly applied and with appreciation for their limitations, these various correlations, hypotheses, and theories can be a useful guide for effectively employing knowledge, past experience, and intu- ition. This book is intended to provide a comprehensive introduction to the kinds of information that one needs to know in order to work with solid catalysts in the laboratory, pilot plant, or commercial installa- tions. For those concerned with chemical reaction engineering it may provide some perspective on the chemical aspects that must be consid- ered in reactor design in addition to the mathematical aspects treated in numerous texts. In this respect the present volume can be useful as a text or reference. To some degree, the value of an introductory treatment such as this may be inversely proportional to its size, and therefore it has been at- tempted, at the risk of oversimplification, to reduce each topic to its essentials. It is hoped that readers may find the balance appropriate and useful for their needs, Because of their rather specialized nature, polymerization reactions, photochemical and electrochemical cataly- sis, and electrocatalysis have not been considered. Experience has shown that many laboratory studies of practical catalysts are vitiated by inadequate experimental procedures, and especially by lack of rec- ognition of the possible effects of mass- and heat-transfer gradients. Some suggestions on design of experiments and warning signals to look for in analyzing data are made in the last chapter.Chapter Introduction and Basic Concepts 1.1. Introduction ‘The concept of catalysis as a method of controlling the rate and direc- tion of a chemical reaction has captured the imagination of scientists and technologists since Berzelius in 1835 coordinated a number of dis- parate observations on chemical transformations by attributing them to a “catalytic force” and coined the term catalysis to refer to the “de- composition of bodies” by this force. At about the same time Mitscherlich introduced the term contact action for a similar group of phenomena. Ideas of what constitutes a catalyst and the mechanism of catalytic activity have since undergone continuous refinement, spurred by the enormous industrial importance of catalysts as illus- trated by the variety of catalytic processes characteristic of modern petroleum refineries and of the chemical industries. Most of these pro- cesses involve solid catalysts, and an understanding of catalysis from both the theoretical and practical point of view is essential to chemists and chemical engine In practice catalysis is primarily a technology that draws on many fields such as organic chemistry, surface chemistry, chemical kinetics, thermodynamics, solid-state physics, ceramics, and physical metal- -. No unified theory of catalysis exists, and there are frequently several alternative, and not necessarily mutually exclusive, theoreti- cal explanations for any given set of facts. A basic concept is that a catalyzed reaction involves the transitory adsorption (almost always chemisorption) of one or more of the reac- tants onto the surface of the catalyst, rearrangement of the bonding, and desorption of the products. This leads to three groups of theories of catalysis:2 Chapter One 1. The geometrical theories emphasize the importance of the corre- spondence between the geometrical configuration of the active atoms at the surface of the catalyst and the arrangement of atoms in the por- tion of the reacting molecule that adsorbs on the catalyst, this portion sometimes being called the index group. In one sense the usefulness of this approach is limited in that seldom can one change the geometri- cal arrangement of atoms in the catalyst surface without changing something else. Studies of reaction rates on different crystal faces of a metal have shown that the rates may indeed change with geometry. The introduc- tion of defects by cold rolling a sheet of metal, by grinding, or by ra- dioactive bombardment may substantially change the rate of a reac- tion if the reaction temperature is sufficiently low that either the defects do not rapidly anneal or the structure does not assume a more stable configuration. An aspect of the geometrical approach of great usefulness is the ob- servation that reaction selectivity may be markedly altered by the number and arrangement of sites required for competing reactions, which leads to the concepts of the importance of “ensembles” or spe- cific grouping of atoms at the catalyst surface and structure sensitivity as affected by particle size, alloying, and other variables (Chap. 6). 2. The electronic theories proceed from the fact that chemisorption involves the distortion or displacement of electron clouds, and they at- tempt to relate activity to the electronic properties of the catalyst. ‘This theory may be in terms of the electronic structure of the solid as a whole, or in terms of the orbitals around individual atoms. In the charge-transfer theory of catalysis (see, e.g., Volkenstein 1963), the reaction rate is postulated to be controlled by the availability of charge carriers, electrons or holes in the catalyst. These are visual- ized as being nonlocalized; i-e., a sea of electrons or holes is available. Chemisorption is then related to the electronic properties of the cata- lyst. For example, the ease or difficulty of removal or donation of an electron to or from the lattice is considered, as predicted by applying band theory developed for metals and semiconductors. This approach, of considerable interest in the 1950s, is now seen to be too broad and inadequate or inapplicable to most cases. More re- cently attention has been directed to the properties of atoms as indi- vidual entities and to the electronic effects caused by the nearest neighbors in the solid rather than by the solid as a whole. In many cases separating geometrical effects from localized electronic effects is difficult; the relative importance of the two probably varies greatly from case to case. 8. The two foregoing theories reflect a primarily physical approach in that the catalyst is regarded as essentially a static material havingIntroduction and Basic Concepts 3 the property of converting reactant to product. The chemical approach, on the other hand, regards the catalyst as a chemical intermediate that forms an unstable, surface, transitory complex with the reac- tants. This intermediate decomposes into the final products, returning the catalyst to its initial state. The rates of these processes and the structures formed are assumed to obey chemical principles. If the en- ergy of formation of the unstable intermediate is low, the affinity be- tween catalyst and reactants is weak and the overall rate limited by the rate of formation of the intermediate. If the energy of formation is high, the intermediate compound is stable and the rate limited by the rate of breakup of this intermediate. This theory leads to the concept that the maximum rate is obtained when the bonds between the adsorbed complex and the catalyst sur- face are neither too strong nor too weak. ‘his concept is useful but limited in that the energetics are generally unknown, more than one intermediate is frequently involved, and one is more generally con- cerned with selectivity rather than activity. Each of these groups of theories has evolved with time, and the rel- ative emphasis on each has changed. The pioneering work of Sabatier (1918) emphasized the chemical approach. In subsequent decades geo- metrical factors received much attention under the impact of Balandin's multiplet hypothesis (Balandin 1969), although geometri- cal factors alone cannot explain most variations of catalytic activity. In the 1950s the solid-state properties of catalysts received much at- tention after the vigorous development of solid-state electronic de- vices, such as the transistor, and the availability of ultrapure materi- als into which controlled trace amounts of known additives could be incorporated. However, the interpretation of catalytic effects by elec- tronic theories has usually been ambiguous, and recent years have seen a rcemphasis on the chemical viewpoint, incorporating a more so- phisticated understanding of the nature and behavior of chemisorbed species and bonding, an approach that stems particularly from rapid advances in various instrumental methods. Schwab (1981) has briefly reviewed the history of these and other concepts in catalysis. An ear- lier book by Rideal (1968) shows the general concepts of catalysis as of the 1960s, with particular emphasis on theory and ideas on mecha- nism. Both physical and chemical viewpoints may provide insight. To be able to relate catalytic activity to certain specific properties of the cat- alyst surface is desirable. Yet an understanding of the mechanism of action and a successful search for new and more effective catalysts may proceed predominantly through the chemical approach, which re- lates catalytic behavior to the vast body of knowledge concerning chemical reactions. The approaches are, of course, interrelated. Thefundamental question about which little is yet known is how the sur- face structure of a solid catalyst causes the reactants to be adsorbed, the chemical bonds to be rearranged, and the products to be desorbed. There is no such thing as a “good” catalyst per se. A substance is or is not a good catalyst only with respect to a specific reaction. The temperature range of practical interest in catalysis is primarily (although not exclusively) between about 20 and 500°C.* Below ambi- ent temperatures, most catalytic reactions of practical interest go too slowly and indeed would become more costly because of the necessity of providing refrigeration or cryogenic cooling. Above approximately 500°C, achieving good selectivity is increasingly difficult unless the desired product is unusually stable. ‘Technologists must understand the method of thinking and frame- work of theory within which fundamental investigators view their studies, so as to be able to utilize theories and advances in fundamen- tal understanding and yet not be sidetracked by trying to apply them under the wrong conditions. Practicing technologists are primarily concerned with the effect of the catalyst: how the rate and direction of the reaction are altered by changes in catalyst composition and by changes in feed composition, pressure, temperature, degree of recycle, and reaction time. ‘hey are concerned with the incorporation of the catalyst into a pro- cess, how poisons may inadvertently be introduced into the catalyst system by the other portions of the process, and how this can be guarded against. The catalysts are usually highly active and of com- plex composition; they must be mechanically rugged, show good sta- bility over long periods of time, and have the requisite activity and selectivity. The reactions with which technologists are concerned are determined by the economic utility of the process. Frequently a vari- ety of catalysts give nearly the same performance, and the final selec- tion involves an economic balance on the entire process, which in- cludes such factors as catalyst cost, along with the frequency and difficulty of replacement and/or regeneration. Scientific investigators, on the other hand, are concerned primarily with mechanism. In trying to simplify their systems for more funda- mental interpretation, they frequently use catalysts of as simple a composition as possible, such as pure metal films or single pure metals “Some major exceptions are ortho-to-para hydrogen conversion, which is carried out industrially at cryogenic temperatures; ammonia oxidation to form nitrogen oxides, hy- drogen cyanide synthesis by the Andrussow process, partial oxidation of methanol to formaldehyde on a silver catalyst; and steam reforming of natural gas and naphthas— all of which are high-temperature reactions. Catalysts for the oxidation of such pollut- ants as carbon monoxide and hydrocarbons and removal of nitrogen oxides from auto- mobile engine exhaust must also be stable and effective at high temperatures.Introduction and Basic Concepts 5. or compounds, even if they are relatively inactive and would not be used in practice. The problem of mechanical strength and stability over long periods of time is of lesser importance. Scientific investiga- tors’ reactants are usually highly pure and chosen either for experi- mental convenience or for some unusual feature of the reaction. Fre- quently they consist of small and simple molecules. Many of the fundamental studies that are valuable in providing insight into the causes of catalyst behavior have not been made with reactions at all, but rather have been studies either of the structure of catalyst sur- faces or of the nature and properties of adsorbed species. Every theory is based on a model, and in catalysis the model may depart to a significant extent from reality. Although the theoretical framework of the model may provide a structure for organization and correlation of facts or suggest a direction for profitable investigation, theories of catalysis at present must be used with caution in attempt- ing to predict behavior under new conditions. These theoretical ap- proaches can be of value to technologists provided they understand the limitations of these approaches and do not confuse theoretical, enthu- siastic assertions for verified fact. 1.2 Industrial Heterogeneous Catalysts The first heterogeneous catalytic process of industrial significance, in- troduced about 1875, utilized platinum to oxidize SO, to SOs, which was then converted to sulfuric acid, H,SO,, by absorption in an aque- ous solution of the acid. This came to replace the lead chamber process for manufacture of H,SO,, in which the same series of reactions were catalyzed by a homogeneous catalyst, nitrogen oxides, probably through the formation of nitrosylsulfuric acid, HNOSQ,. In this “con- tact process” platinum in turn was superseded by a catalyst compris- ing vanadium oxide and potassium sulfate on a silica carrier, which was less susceptible to poisoning; essentially this same composition is used in present-day SO, reactors. Other inorganic chemical catalytic processes followed. Notable was the development about 1903 by Ostwald of the oxidation of ammonia on a platinum gauze to form nitrogen oxides for conversion to nitric acid, followed in the period from about 1908 to 1914 by the synthesis of ammonia from the elements by a process developed by Haber and Bosch utilizing a catalyst developed by Mittasch. ‘The industrial syn- thesis of methanol from carbon monoxide and hydrogen appeared in about 1923, and the synthesis of hydrocarbons from carbon monoxide and hydrogen by the Fischer-Tropsch process in the 1930s. The cata- lytic partial oxidation of methanol to formaldehyde as an industrial process started in Germany about 1890; that of naphthalene to6 Chapter One phthalic anhydride was commercialized in the 1920s; and that of ben- zene to maleic anhydride, in 1928. The partial oxidation of ethylene to ethylene oxide was commercialized by Union Carbide in 1937. In the processing of petroleum for fuels the first catalytic process, catalytic cracking, appeared in about 1937. This first used an acid- treated clay, then later a synthetic silica-alumina catalyst, and more recently zeolite crystals incorporated in a silica-alumina matrix. Re- forming, using a molybdena/alumina catalyst to increase the octane number of gasoline by cyclization of paraffins and dehydrogenation to aromatics, was introduced in the United States and Germany just prior to World War IT. In che early 1950s this was superseded by a cat- alytic reforming process using a platinum/alumina catalyst. Catalytic hydrocracking first came into use in England and Germany prior to World War II; subsequently it became relatively uneconomic, but it was revived more recently, with the advent of new types of catalysts. Hydrodesulfurization and hydrotreating processes have grown rapidly during the past three decades and are now of major importance in pe- troleum processing. Table 1.1 lists these and a representative selec- tion of the catalysts used in the principal industrial heterogeneous catalytic processes of present or recent importance, together with the type of reactor commonly utilized. In addition to the compositions listed, small amounts of other substances, “promoters,” are frequently added in catalyst preparation. Heinemann (1981) presents a brief history of industrial catalysis. A book edited by Pearce and Patterson (1981), and written by a group at Imperial Chemical Industries (ICI), gives an overall treatment of ca- talysis and related chemical processes. The book by Weissermel and Arpe (1978) on industrial organic chemistry covers important raw ma- terials and intermediates including information on processes and cat- alysts for a number of reactions not considered in the present volume. Davis and Hettinger (1983) have edited an extensive collection of his- tories of catalysis research in America having industrial impact. 1.3. Definitions 1.3.1 Catalyst The basic concept of a catalyst is a substance that in a smal] amount causes a large change. More precise definitions of catalysis and of what constitutes a catalyst have gradually evolved as understanding of the causes of catalytic phenomena has grown. Even today there is no universal agreement on definitions; the point of view varies some- what depending on the investigator, for example, between the funda- mental investigator and the practitioner, and among researchers con-TABLE 1.1 Introduction and Basic Concepts 7 Selected Heterogeneous Catalysts of Industrial importance Reaction Catalyst and reactor type (continuous operation unless otherwise noted) Dehydrogenation CyHjo (butane) — butenes Batenes -+ C,H (butadiene) CcHsCaHe + CoHsCH=CH, (ethy] benzene — styrene) CH, or other hydrocarbons + H,0 + CO + Hy {steam reforming) Cr,03 + Al; (fixed bed, cyclic) FeO, promoted with Cr,03 and K,CO, Fe,0, promoted with C0, and K,CO, (fixed bed, in presence of steam) ‘Supported Ni (fixed bed) (CH,),CHOH — CH,COCH, + Hy 2n0 isopropanol — acetone + hydrogen) CH,CH(OH)C,Hy -+ CHxCOC;H, +Hy 2n0 Hydrogenation Of edible fats and oils Various hydrogenations of fine organic chemi- cals CyHg + Ha > Cal N, + 3H, -* 2NHy C,H, ~ CzH, (selective hydrogenation of C,H, impurity in C,H, from thermal. plant) cking Ni on a support (slurry reactor, batch) Pd or Pt on carbon (slurry reactor, usually batch) Ni or noble metal on support (fixed bed or slurry reactor) Fe promoted with Al,03, K,0, CaO, and MgO (adiabatic fixed beds) Pd on Al,0, or sulfided Ni on support (adia- bativ fixed bed) Oxidation 80, + 0, (air) + SO, 2NH, + %0, (air) + 2NO + 8H,0 NH, + CH, + air + HCN (Andrussow process) CyoHy OF 1,2-GgHy(CHylz + Oz > CcHH,(CO),0 (naphthalene or o-xylene + air -» phthalic an hydride) a-C4Hyo + O2 +» C,H203, (butane + air -> maleic anhydride HH, + VO, + (CH,),0 (ethylene oxide) CH,OH + 0, + CH,0 + Hy and/or HyO CyHy + 0 + CHy=CHCHO (acrolein) and/or Cl -CHCOOH {acrylic acid) CyHg + NHy + %0, + CH,=CHCN + 3H,0 Complete oxidation of CO and hydrocarhons, for pollution contro) Simultaneous control of CO, hydrocarbons, and NO, in auto exhaust Simultaneous control of NO, and SO, in flue gases C:H, + 4.0, + CH,COOH + CH,COOCH=CH, (vinyl avetate) CyHy + 40, + C,H, + HO V0, plus K,SO, on silica (adiabatie, fixed beds) 90% Pt-10% Rh wire gauze, oxidizing condi- tions 90% Pt-10% Rh wire gauze, under net reduc- ing conditions V,0; on titania (multitube fixed bed) Vanadia-phosphate (multitube fixed bed or fluidized bed) Ag on e-Al,O;, promoted with Cl and Cs (multitube fixed bed) ‘Ag (adiabatic reactor) or Fea (MoO,)s (multitube fixed bed) Bismuth molybdate plus other components Complex metal molybdates (fluidized bed) PL or Pd, or both, on monolith support Same, plus Rh, with careful control of oxidizing/reducing conditions Vunadia on titania with addition of NHy Pd on acid-resistant support (vapor phase, multitube fixed bed) Promoted ferrite spinels© Unapter Une TABLE 1.1 Selected Heterogeneous Catalysts of Industrial Importance (Continued) Catalyst and reactor type Reaction (continuous operation unless otherwise noted) ‘Acid-catalyzed Reactions Catalytic eracking Zeolite in Si0z"Al,Og matrix plus other in- gredients (transport reactor) Hydrocracking Pd on zeolite in an amorphous matrix; NiMo on silica-alumina, various other dual-funetion catalysts (adiabatic fixed beds) Paraffin isomerization Pt on H-mordenite zeolite in alumina matrix Catalytic reforming Pt, Pt-Re or Pt-Sn on acidified Al,0, or on zeolite in matrix (adiabatic, fixed beds, or moving bed, with interstage heating) Polymerization H,PO, on clay (fixed bed) Hydration, e.g., propylene to isopropyl alcohol ‘Mineral acid or acid-type ion-exchange resin fixed bed) CH,OH + isoC,H, > methyl tert. butyl ether Acid-type ion-exchange resin (MBE) Reactions of Synthesis Gas CO + 2H, + CH,OH Cu!-ZnO promoted with Al,O, (adiabatic, fixed beds with interstage cooling or multitube fixed bed) CO + 3H, + CH, + H,0 (methanation) Supported Ni (fixed bed) CO + Ha -» paraffins, etc. (Fischer-Tropsch Fe or Co with promoters (multitube fixed bed : or transport reactor) Other ation (e.g., CoH, + 2HCl + 40. CuCl/Al,0 with KCI promoter H,0) Hydrodesulfurization, hydrodenitrogenation, CoMo/Alz0, or NiMo/Al,0q, sulfided tadia- hydrotreating batie, fixed beds with interstage cooling) SO, + 2H,S — 38 + 2H,0 (Clans process) Al,0, (fixed beds) H,O + CO + CO, + Hy (water-gas shift) FeO, promoted with Cr20q (adiabatic fixed bed); for a second, lower temperature stage, Cu-Zn0 on Alz0g; CoMe on support cerned with heterogeneous catalysis, homogeneous catalysis, poly- merization reactions, and enzymes. For present purposes, however, our definition is: A catalyst is a substance that increases the rate of re- action toward equilibrium without being appreciably consumed in the process. This definition is basically operational. The fundamental concept, stemming from the chemical approach to catalysis, is that a reaction involves a cyclic process in which a site on a catalyst forms a complex with reactants, from which products are desorbed, thereby restoring the original site and continuing the cycle. This concept may lead to the idea that a catalyst is unaltered by the reaction it catalyzes, but this is misleading. A catalyst may undergo major changes in its structure and composition as a result of the mech- anism of its participation in the reaction.Introduction and Basic Concepts 9 A pure metal catalyst, on use, frequently changes in surface rough- ness or crystal structure. The ratio of oxygen to metal in a metal oxide catalyst frequently changes with the temperature and composition of the contacting fluid. In both cases, however, there is no stoichiometric relationship between such changes and the overall stoichiometry of the catalyzed reaction. Many so-called polymerization catalysts or ini- tiators are not termed catalysts within the foregoing definition. Thus, in the use of an organic peroxide to initiate a polymerization reaction, the ratio of peroxide consumed to the quantity of monomer reacted is indeed nonstoichiometric, but the peroxide becomes completely con- sumed in the process; hence it cannot be regarded as a true catalyst. A catalyst is defined as a substance; the acceleration of a rate by an energy-transfer process is not regarded as catalysis by this definition. Excluded cases include excitation by thermal energy (increased tem- perature), by bombardment of reactants with charged or high-energy particles, by electric discharge, or by photochemical irradiation. For example, the reaction of hydrogen and oxygen is increased by irradi- ation with ultraviolet light and even more so if a small amount of mercury vapor is present and illumination is by a mercury vapor lamp. Here the reaction is accelerated by energy transfer to the react- ing gases from mercury atoms, which in turn are activated by irradi- ation. As a second example, the rate of thermal decomposition of a va- por at low pressure is usually increased by the addition of a second “inert” gas, which furnishes activation energy by collisions. These various methods of accelerating the rate of a reaction are more clearly understood as aspects of the mechanisms of homogeneous gas-phase reactions rather than as catalysis. The same substance may act as a catalyst in one set of circum- stances but as a reagent in another. Thus the oxidation of a mixture of o-xylene and air to phthalic anhydride is catalyzed by V,O,. o-Xylene by itself may also be oxidized by contacting it alone with V,O;, in which case the V,O, acts as a reagent and becomes stoichiometrically reduced to a lower oxide. Indeed, the ability to alternate easily be- tween two or more oxidation states is characteristic of many oxidation catalysts. Thus insight into the reasons for their catalytic activities may come from studies using the same substance as a reagent. A catalyst cannot change the ultimate equilibrium determined by thermodynamics; its role is restricted to accelerating the rate of ap- proach to equilibrium. This point is developed later. 1.3.2 Catalyst activity ‘The activity of a catalyst refers to the rate at which it causes the re- action to proceed to chemical equilibrium. The rate may be expressed10 Chapter One in any of several ways (Sec. 3.2). The performance of an industrial re- actor is frequently given in terms of a space-time yield (STY), which is the quantity of product formed per unit time per unit volume of reac- tor. The rate of reaction depends on pressure, temperature, concentra- tion of reactants and products, and other variables. For comparison of the activity of different catalysts, any of several methods may be used. Four possibilities are as follows: Rates may be determined at a standard condition. 2. Sometimes a single rate constant may be reported, but this implies detailed knowledge of the true kinetics and ability to apply a rate expression with but a single constant. 3. To avoid having to determine rates over a range of concentrations and temperatures for comparison, catalyst activity may be ex- pressed as the temperature required for a given conversion at a fixed feed composition and pressure. 4. The space velocity required to achieve a specified conversion at a fixed temperature is determined for a fixed feed composition and pressure. 1.3.3 Catalyst selectivity and functionality There are usually many chemical compositions having a free- energy intermediate between that of the reactants and that of the state of complete chemical equilibrium. The selectivity of a catalyst is a measure of the extent to which the catalyst accelerates the re- action to form one or more of the desired products, which are usu- ally intermediates, instead of those formed by reaction to the over- all state of lowest free energy. The selectivity usually varies with pressure, temperature, reactant composition, and extent of conver- sion, as well as with the nature of the catalyst. For precision one should refer to the selectivity of a catalyzed reaction under speci- fied conditions. The selectivity is determined in the first instance by the functionality of the catalyst, but also in part by thermody- namic equilibrium considerations. Thus, a certain undesired prod- uct may be largely avoided if it is possible to operate under condi- tions in which the equilibrium concentration of the product is negligible (see Sec. 1.4). A frequently cited example of catalyst selectivity caused by function is the conversion of ethanol. Over copper the reaction proceeds as C,H,OH > CH,CHO + H, (LDIntroduction and Basic Concepts 11 Over alumina it proceeds as C,H;OH — C,H, + H.O (1.2) or 2C,H,OH — C,H;OC,H, + H,O (1.3) Selectivity here is associated with the fact that copper adsorbs hydro- gen and is a mild hydrogenation/dehydrogenation catalyst, whereas alumina adsorbs water and can act as a dehydration catalyst. To a first approximation, certain types of functionality can be char- acterized by selective chemisorption of suitable reagents. For exam- ple, many hydrogenation reactions are catalyzed by metals, and reac- tions such as hydrocarbon isomerization are catalyzed by solid acids. The availability of metal surfaces on a catalyst can be studied by the degree of chemisorption of hydrogen, and the availability of solid acids by the amount of adsorption of bases such as ammonia or organic amines (Sec. 7.2.1). Many catalytic reactions, however, are affected by subtleties not readily revealed by these “titration” procedures. Consequently, one may characterize certain catalyst functionalities by the response of a well-known and relatively simple “probe” reaction. From a study with ethanol (or similarly propanol), the extent to which an olefin, rather than an aldehyde, is formed is a measure of dehydration functionality versus dehydrogenation functionality. Similarly, with an unsaturated hydrocarbon, products formed by an isomerization versus a hydroge- nation path indicate the extent of functional acidity versus functional hydrogenation (see also Chap. 9). This approach of letting a reaction characterize the catalyst can be especially helpful in dealing with complex and ill-defined catalysts that are more or less multi- functional. Some reactions involve the formation and subsequent reaction of var- ious intermediates. Some of the reaction steps may be catalyzed by one kind of site, and others by a second kind of site. When these steps occur in series, both kinds of sites must be in proximity to one another in order for the overall reaction to occur, and usually they are both on the same catalyst particle. In some eases an intermediate can be desorbed from one kind of site into the bulk fluid and adsorbed on a second site. Then, an intimate mechanical mixture of two kinds of particles, each possessing only one kind of site, can effectively catalyze the overall reaction, al- though either one by itself is relatively ineffective. An example is the isomerization of an n-paraffin to an iso-paraffin on a platinum catalyst supported on an acidic base. The n-paraffin is first dehydrogenated to an n-olefin. This isomerizes to an isoolefin, which is hydrogenated to an iso-12 Chapter One paraffin. The hydrogenation and dehydrogenation steps occur on plati- num; the isomerization steps, on an acid site (Sec. 9.5). This mechanism is significant in some of the reactions occurring in catalytic reforming and in catalytic hydrocracking. A catalyst may be useful for either its activity or its selectivity or both. If a variety of products are possible, selectivity is usually the more important. Activity can usually be stepped up by raising the temperature, although frequently increased temperature shortens the life of the catalyst or increases undesirable reactions that may be cat- alytic or thermal or both. A higher temperature may also decrease the maximum conversion obtainable if the reaction is exothermic and is limited in extent by thermodynamic equilibrium. If a variety of products are thermodynamically possible, increased temperature may either increase or decrease selectivity, depending on the overall kinetics and the desired product. Thus, for the general case of A> B-—C, if B is the desired product, some intermediate temper- ature is usually optimum; if C is desired, increased temperature helps drive the reaction to completion. If B is desired, the maximum selec- tivity for this type of kinetics occurs at the lowest conversion. Control of catalyst selectivity is primarily a matter of minimizing the rates of undesired reactions while maximizing that of the desired reaction. This is determined not only by catalyst structure, but also by feed composition, operating conditions, degree of conversion, and reactor design and operation (Chap. 11). Selectivity is defined as the percentage of the consumed reactant that forms the desired product. It is usually a function of degree of conversion and reaction conditions. Yield is an engineering or indus- trially used term that refers to the quantity of product formed per quantity of feedstock (reactant) consumed in the overall reactor oper- ation. Within this operation there may be a recycle of various reac- tants and/or intermediates, as after separation from the product. Yield is frequently reported on a weight basis; hence a yield exceeding 100 percent (w/w) may be obtained, for example, in a partial oxidation pro- cess in which oxygen is introduced into the product molecule with high selectivity. In the fuels industry, products are conventionally sold on a volume rather than a weight basis; hence a yield exceeding 100 percent (v/v) may be obtained when the products are of lower den- sity than the reactants. 1.3.4 Negative catalyst A negative catalyst is a substance that decreases the rate of reaction. ‘This is usually found only when the reaction proceeds by the forma- tion and disappearance of free radicals.