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CATALYTIC PROCESSES in APPLIED CHEMISTRY a SERIES of MONOGRAPHS on APPLIED CHEMISTRY Under the Editorship of E Ollass 54 1 .33 y&vok^o. 16971 pkary p CHEMfSTRY LIBRARY RULES This book may be kept... Q/?.£? weeks. A fine of two cents will be charged for each day books or magazines are kept overtime. Two books may be borrowed from the Library at one time. Any book injured or lost shall be paid for by the person to whom it is charged. No member shall transfer his right to use the Library to any other person. CATALYTIC PROCESSES IN APPLIED CHEMISTRY A SERIES OF MONOGRAPHS ON APPLIED CHEMISTRY Under the Editorship of E. Howard Tripp, Ph.D. Already Published. THE MANUFACTURE OF ARTIFICIAL SILK. With Special Reference to the Viscose Process. By E. Wheeler, M.B.E., A.C.G.I., A.I.C., with a Foreword by Sir William J. Pope, K.B.E., D.Sc. Demy8vo. 165 pages. 50 illustrations. 12/6 net. CATALYTIC PROCESSES IN APPLIED CHEMISTRY. By T. P. Hilditch, D.Sc, F.I.C. Demy 8vo. 370 pages. 16/- net. In the Press. HYDROGEN ION CONCENTRATIONS. Their Determination and Industrial Importance. By H. T. S. Britton, D.Sc, B.Sc, D.I.C., F.I.C. In Preparation. SOLVENTS. T. H. Durrans, D.Sc, F.I.C. MINERAL LUBRICATING OILS. A. E. Dunstan, D.Sc, F.I.C. ARTIFICIAL RESINS AND RELATED COLLOIDS. A. A. Drummond, M.Sc, A.I.C. METHODS OF CELLULOSE CHEMISTRY. C. Doree, M.A., D.Sc, F.I.C. <><> Other volumes are in course of preparation, and detailed particulars will be sent from time to time to anyone sending a request. CATALYTIC PROCESSES IN APPLIED CHEMISTRY BY T. P. HILDITCH D.Sc.(Lond.), F.I.C. CAMPBELL BROWN PROFESSOR OF INDUSTRIAL CHEMISTRY IN THE UNIVERSITY OF LIVERPOOL BEING VOLUME TWO OF A SERIES OF MONOGRAPHS ON APPLIED CHEMISTRY Under the Editorship of E. HOWARD TRIPP, Ph.D. NEW YORK D. VAN NOSTRAND COMPANY, Inc. 250 Fourth Avenue 1929 a_> Printed in Great Britain by The Whitefriars Press, Ltd., London and Tonbridge. EDITORIAL PREFACE In these days of intensive and extensive research, every worker in science or its applications knows how rapidly the contents of text-books and encyclopaedias become out of date ; and those who wish to see new work published know the difficulties which abnormal taxation and high labour costs offer to the realisation of their desire. The one obvious solution of the problem is the publication of monographs that would focus attention upon recent work, or upon new aspects of old work, and upon their theoretical implications. Such books are usually written by experts for other experts in related fields of science, or for the well- educated layman whose thirst for new knowledge has not been quenched by the more sensuous outpourings of the ephemeral press. It is interesting at times to speculate upon what aspects of our civilisation the future historian will select as the most characteristic of our time. Scientific discoveries and their application to human welfare, we may be sure, will find a place ; and to these many will add the growth of our sense of " values.' 3 The value of new work in science varies greatly : the golden grain is always accompanied by chaff, and there is no precious ore without country rock. Owing to the difficulty of assessing the value of work at the time of its production, we find that our scientific periodicals stand in danger of being swamped by the mass of second- and third-rate material that is thought to be worth publishing, but which posterity will decree would have been better left in manuscript form. It is the first duty of the monograph writer to estimate the value, either actual or potential, of recent work upon the subject of which he writes : he must pick out the plums vi EDITORIAL PREFACE to save others from the indigestion that follows eating the whole pie. Further, in addition to being accurate, his work must be presented in a form that is both assimilable and attractive ; in other words, he must show that lucid exposition can be achieved by the use of few words, if they are rightly chosen, and that attractive presentation is attained rather by clear think- ing than by superficial display. The present series of monographs has been designed with these objects and ideals in view. The task which the authors have been set is no easy one ; so that should performance occasionally fall short of intention, the critical reader is asked to echo the words of Goethe that " higher aims, even if unfulfilled, are in themselves more valuable than lower aims quite attained/ 3 E. Howard Tripp. AUTHOR'S PREFACE The applications of catalytic action in the chemical industries of the present day are so numerous that a very large volume, or even series of volumes, would be needed for a complete and detailed treatment of the whole subject ; again, there are not a few processes in which catalysis plays a minor, or sometimes an un- certain, part, which might or might not be deemed to be within the scope of a treatise on applied catalytic processes. The enormous range and rapid extension of catalytic methods in industry involves a tendency towards over- specialisation on the part of those engaged in actual practice. It is of primary importance to maintain the broadest possible view of the whole subject, and the present volume has been written with this in mind, both as regards those who may already be well acquainted with one or more phases of catalyst techno- logy, and those who may be concerned to apply catalytic action to manufacturing problems in which its aid has not previously been invoked. The book is an attempt to give, within a reasonable space, a general account of how the principles of catalytic action are being applied in practice. In- stances have therefore been selected for more detailed discussion, not necessarily because of the intrinsic importance of the products concerned, but mainly where it has appeared that the specific methods applied have a wider interest or are of potential application in other cases. The specialist in any given branch of applied catalysis will, therefore, not expect to find more in the part of this book dealing with his own corner than he vii viii AUTHOR'S PREFACE already knows ; but it is hoped that in other portions of the work he may find matter which will assist him to bring new ideas to apply to the local problems which are his immediate concern. The difficulties suggested in the first paragraph have been met, as far as possible, by referring to practically all the contemporary processes in which, so far as the writer is aware, catalysts are usefully employed (not forgetting the increasingly important developments in the use of " natural " catalysts (enzymes) in fermenta- " " tion processes) ; but certain borderland topics such as the hydrogenation of coal (the role of catalysis in which, at the present stage of development, appears somewhat vague) or the technically important pheno- mena of anti-oxidants and autoxidation (which are definitely catalytic in nature, but are hardly, perhaps, applied catalytic processes) have been left over as distinctly outside the limits which the author has set himself. The manifold instances available have been grouped, roughly, into firstly, the contact actions at solid surfaces which have been in general more thoroughly worked out than other types of catalysis, and perhaps are therefore more likely to stimulate further progress ; secondly, cases in which fermentation methods have " been successfully applied ; and thirdly, the homo- geneous " actions of hydration, hydrolysis, esterifica- tion, dehydration, condensation, oxidation, etc., which are of high importance in technological organic chemistry, but which have not always been so thoroughly developed from a scientific standpoint as the more conventional and striking examples of " contact " processes. It was felt desirable to preface the work with a short theoretical section, but theoretical principles have been considered, frankly, from their utility in guiding the practitioner ; for more general discussion of the funda- mental aspects of catalysis the reader is recommended to one or other of the admirable books on this side of AUTHOR'S PREFACE ix the subject to which reference is made in the course of this volume. It may be pointed out that, in order to economise space (since adequate illustration would have required a very large number of diagrams), as graphic descrip- tion as possible has been attempted without recourse that to pictorial illustration ; it may also be mentioned all temperatures quoted in the book are given in degrees Centigrade. Dr. E. Frankland Armstrong, F.R.S., Professor I. M. Heilbron and the editor of this Series have given the author the advantage of their criticism and advice during the preparation of the manuscript, for which his cordial thanks are recorded. He also expresses his grateful appreciation of the help rendered by Miss M. Tadman, M.Sc, whilst the book was in the press, especially in the matters of proof-reading and in compilation of the various indexes which, it was felt, were desirable in view of the somewhat heterogeneous mass of products, raw materials, and catalysts dealt with in the course of the work. T. P. H. University of Liverpool, November , 1928. ... CONTENTS CATALYTIC PROCESSES IN APPLIED CHEMISTRY PAGE Classified List of Processes dealt with in Sections II to IV. ......... xiii Classified List of Products dealt with in Sections II to IV. ......... xvi SECTION I The General Principles of Catalytic Action CHAT i . General Development of the Use and Understanding of Catalytic Processes ...... i 2. Theoretical Aspects of Catalysis at Solid Surfaces . 15 3 The Action of Enzymes .....
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