Mass Transfer Chemical Reaction in w~h Multiphase Systems Volume I: Two-Phase Systems NATO ASI Series Advanced Science Institutes Series A sefles presentmg the results of actIVItIes sponsored by the NATO SCIence CommIttee. whIch alms at the dlssemmatlon of advanced sCIentifIC and technologIcal knowledge. wIth a VIew to strengthenmg ImkS between SCIentific communitIes The series is published by an Internahonal board of publishers In conjunction with NATO SClenhfic Affairs DIVISion A Life Sciences Plenum Publishing Corporahon B Physics London and New York C Mathematical and D. Reidel Publishing Company Physical Sciences Dordrecht and Boston 0 Behavioural and Martlnus NiJhoff Publishers Social Sciences The Hague/Boston/Lancaster E Applied Scie ,ces F Computer and Springer Verlag Systems Sciences Berlin/Heldelberg/New York G Ecological Sciences Series E: Applied Sciences - No. 72 Mass Transfer with Chemical Reaction in Multiphase Systems Volume I: Two-Phase Systems edited by Erdogan Alper, B.Sc., Ph.D. (Cantab) Professor of Chemical Engineering University of Ankara. Besevler. Ankara. Turkey Anadolu University. Eskl~hir. Turkey 1983 Springer-Science+Business Media, B.V. Proceedings of the NATO Advanced Study Institute on Mass Transfer with Chemical Reaction in Multiphase Systems, Cesme- izmir, Turkey, August 10- 21. 1981 Llbrary of Congress Cataloglng In Publlcatlon Data NATO Advanced Study Inatitute on Maae Tranafer vith Che.ical Reaction in Multiphaee Syete.a (1981 : Cefee, Turkey) ~ •• transfer vith ch~ical reaction in •ultiphaae ayat~e. (NATO ASI aerlee. Seriee E, Applied aciencea ; no. 72-13) MPubliahed in cooperation vith NATO Scientific Affaire Diviaion.M MProceedinsa of the NATO Advanced Study Institute on Mase Transfer vith Che.ical Reaction in Multiphaee Syateaa, yef.e--Izmir, Turkey, August 10-21, 1981"--T.p. vereo. Includea bibliographical referencea. Contenta: v. 1. Two-phaee ayateee -- v. 2. Three -phaae ayat~a. 1. Masa tranafer--Congreaaea. 2. Chemical reactiona --Congreaaea. I. Alper, Erdofan. II. North Atlantic Treaty Or&&nization. Scientific Affaira Diviaion. III. title. IV. Seriea: NATO advanced acience inatitutes aeriea. Seriea E, Applied aciencea ; no. 72-73. TP156.M)N38 1981 66o.2'8423 83-13285 ISBN 978-94-015-8902-8 ISBN 978-94-015-8900-2 (eBook) DOI 10.1007/978-94-015-6900-2 Ali rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, mechanical, photocopying, recording, or otherwlse, without the prior written permission of the publishers, Springer-sdence+Business Media, B.V. Copyright © 1983 by Springer Science+Business Media Dordrecht Originally published by Martinus Nijhoff Publishers, The Hague in 1983 Softcover re print of the hardcover 1s t edition 1983 v NATO ADVANCED STUDY INSTITUTE on "MASS TRANSFER WITH CHEMICAL REACTION IN ~lULTIPHASE SYSTEr~S" DIRECTOR E. Alper Department of Chemical Engineering, Faculty of Sciences, Ankara University, Be~evler,Ankara,Turkey, SCIENTIFIC ADVISOR w. -D. Deckwer Institut fur Technische Chemie, Universitaet Hannover, D -3000 Hannover 1, F.R.Germany. HONORARY SCIENTIFIC ADVISORS P. V. Danckwerts Chemical Engineering Department, University of Cambridge, Pembroke Street,Cambridge,England. M.M.Sharma Department of Chemical Technology, University of Bombay, Matunga Road,Bombay,India. LECTURERS VI E. Alper Department of Chemical Engineering, Faculty of Sciences, Ankara University,Be~evler,Ankara,Turkey. Istituto di orincipi di Inp.egneria Chimica, G.Astarita Piazzale Tecchio, 80125 Napoli.Italia. CNRS,Laboratoire des Sciences du Genie J.C.Charpentier Chimique, 1, rue grandville, 54042 Nancy Cedex,France. Institut far Technische Chemie, W. -D. Deckwer Universitaet Hannover. D -3000 Hannover 1, F.R.Germany, A.Germain Universit~ de Liege, Facult~ des Sciences Appliqu~es, Chimie Industrielle, Le Rue A.Stevart,2 B -4000 Li~ge,Be18ique. Technisch-Chemisches Laboratorium S.Hartland ETH - Zentrum eH -M09~ Zurich, Switzerland. H.Hofmann Institut fUr Technische Chemie, Er,erlandstrasse 3, d -8250 Erlangen, F.R,Germany. G.A.L'Homme Universit~ de Li~ge, Laboratoire de G~nie Chimique, Institut de Chimie-H~tallurgie, 2, rue A.Stevart, B -4000 Li~ge,Belp.ique. UHIST,The University of lmnchester, R. Afann PO Box 38, l'anches ter t1 60 lQD England. H.Sawistowski Imperial Coller,e of Science and Technology, Department of Chemical Enp,ineerinp., London SW7 2BV, England. K. Schiiger1 Institut fur Technische Chemie Univesitaet Hannover, D -3000 Hannover,F.R.Germany. Y.T. Shah University of Pittsburgh, School of Engineering, Chemical and Petroleum En~ineering, 1249 BenedUM Hall,Pittsburgh, P.A. 15261, U.S.A. VII PP.EFACE The phenomenon of "mass transfer with chemical reaction" takes place whenever one phase is brought into contact with one or more other phases not in chemical with it. This e~ui1ibrium phenomenon has industrial, bio10qica1 and importance. physio10~ica1 In chemical process it is encountered in both separ engineerin~, ation processes and reaction engineering. In some cases, a chemical reaction may deliberately be for speeding up the e~p10yed rate of mass transfer and/or for increasing the capacity of the solvent; in other cases the Mu1tiphase reaction is a part syste~ of the process \',i th the specific aim of nroduct formation. Finally, in some cases, for instance "distillation \.,ith chemical reaction", both objectives are involved. Although the subject is clearly a chemical enqineering undettakinn, it requires often a good understanding of other subjects, such as chemistry and fluid mechanics etc., to publications in diversified areas. On 1eadin~ the other hard, the subject has been a major field and one ~lways of the most fruitful for engineers. ~hemica1 It is for these reasons that the editor decided to organi~e a NATO Advanced Study Insti tute coveri n9 all aspects, with the ultir:late aim of an overvi2\'1 of the 1andscane to identify features that provide orientation. After discussions "lith Professors ~an~' \/.-0. Deck\'/er, P.V. Danck\'/erts, C. Hanson and tLM. Sharma, it \'/as decided to limit the ASI to (1) (2) liquid-liquid, and 9as-1i~uid, (3) systems. Thus, the only really important gas-1i~uid-so1id area left out was fluid-solid systems, part of which was however dealt with in another NATO Advanced Study Institute on "Analysis of Fluid-Solid Catalytic Systems" under the directorship of Prof. r..F. Froment. The ori9inally planned date for the Institute had to be postponed for one year in order to prevent a clash with another NATO Advanced Study Institute. This two-volume book consists entirely of the proceedings of the NATO Advanced Study Institute, which was held in Cesme, Izmir, Turkey during August 10-22, 1981. It includes review lectures of the eminent scientists as presented during the Institute. Although every attempt was made by director/ th~ editor, it was not a1tooether nossib1e to realise absolute unifor mity as these reviews were written in a relatively short time by authors who did not have the chance of coming together to ~rior the meeting. During the Institute, some short original contri butions were also presented by interested participants on areas closely related to the invited reviews. Due to the large amount of material, these Proceedings are divided into blo volumes. The first volume includes the (lenera1 introductory reviews involving the mathematical lay-out, physico- VIII chemical data, reaction kinetics and transport data, gas-liquid and liquid-liquid systems, and systems. The second bioche~ical volume is devoted entirely to the three-~hase system and its application to coal technology and Fischer-Tropsch synthesis. Special features of this Institute reflected fully in these Proceedings, are the treatments of biolooical reactions, facilitated transport, reactive distillation, solvent extraction of metals and some related aspects of coal utilisation. Here, I ~lOuld very much like to compliment and thank all lecturers not only for their very clear oral and \'/ritten contri butions but also for wholeheartedly supporting the Institute. I feel particularly obliged to make a special acknOl'iledgement to Prof. H. -D. Dec k\'ier, who involved from the very beginning to ~/as the very end, to Professors P.V. Danck\'/erts 3nd t1.t1. Sharma who contributed immensely to the scientific organisation, and to Prof. Sharma \·/ho was also very kind in material prior to r~.r1. providin~ publication. I would also like to thunk all participants for their con tributions to the Advanced Study Institute. Indeed, it was their active participation which brought a real sense of satisfaction to the director/editor. I exnress, of course above all, my deenest to the ~ratitude Scientific Affairs Divisicn of NATO and their officers, in particular Dr. M. di Lullo and Mr. Sudarskis, who not only ~. almost entirely sUP!1orted the Institute financially, but also helped a local objective of mine, i.e. promoting scientific affairs of Turkish chemical engineers. I gratefully acknowledge also the financial contributions of the Turkish Scientific and Technological Research Council and the Ankara Office of the Briti sh Council. I \·muld also like to thank my assistants and co-workers at various universities in Turkey for doing many tedious chores, and to thank Mrs. Bilge Goksidan for the drawings. Last, but by no means least, my efforts in organisinq this ASI could not have succeeded without the patience and thp under standing of my wife, Ayse, and our Gizem, who have on dau~hter, too many occasions been neglected during last two years; for th~ their co-operation and inspiration I am particularly grateful. Anka ra, Turkey ErmOGAN ALPER IX TABLE OF CONTENTS: Volume I LECTUREHS VI PHErACE VII E. ALPER Introduction to Mass Transfer with Chemical Reaction Operations (with Heavy Emphasis on Gas-Liquid Systems) G. ASTAR ITA General Mathematical Layout of Mult iphase Systems 17 G. ASTARITA Chemical Desorption 37 B.I. MORSI and J.C. CHARPENTIER Review of Obtaining and Estimation Methods of Physico Chemical and Related Data: Part 1 - Solubil ities and Diffusivit ies of Gases in Liquids 53 B.I. MORSI and J.C. CHARPENTIER Review of Obtaining and Estimat ion Methods of Physico Chemical and Related Data: Part 2 - Gas-Liquid Mass Transfer Parameters. Measurement and Some Data in Several Types of Reactors 101 R. MANN Heat and Mass Transfer in Exothermic Gas Absorption 189 R. MANN Absorption with Complex Reaction in Gas-Liquid Reactors 223 E. ALPER Process Design Aspects of Gas Absorbers 291 J. ANDRIEU and J.M. SMITH Gas-Liquid Rate Constant Heasurements by Chromatography 341 R. SICK, P. WEILAND and U. ONKEN Determination of Gas-Liquid Hass Transfer by Ox idat ion of Hydraz ine 351 P.M.H. BLAUWHOFF, G.J.B. ASSINK and W.P.H. VAN SWAAIJ Simultaneous Hass Transfer of Two Gases with Complex Reversible Reactions: An Example Being the Simultaneous Absorption of H2S and CO2 into Aqueous Solutions 357