You are on page 1of 212

This page intentionally left blank

Downloaded by FORDHAM UNIV on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.fw001

Chemical Reaction
Engineering—Plenary Lectures

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

Downloaded by FORDHAM UNIV on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.fw001

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

2012 | http://pubs.1021/bk-1983-0226.. 1983 | doi: 10.. . EDITOR Massachusetts Institute of Technology Based on the 7th International Symposium on Chemical Reaction Engineering in Boston. D. J. 1983 In Chemical Reaction Engineering—Plenary Lectures.C. Massachusetts. et al. EDITOR Downloaded by FORDHAM UNIV on December 2. Wei. 1982 ACS SYMPOSIUM SERIES 226 AMERICAN CHEMICAL SOCIETY WASHINGTON. October 4-6. 1983.fw001 Massachusetts Institute of Technology Christos Georgakis. DC.Chemical Reaction Engineering—Plenary Lectures James Wei. ACS Symposium Series.acs.org Publication Date: July 28. American Chemical Society: Washington.

W e i . TP5. Christos. use. .1021/bk-1983-0226. American Chemical Society: Washington. Chemical engineering—Congresses. or sell any patented invention or copyrighted work that may in any way be related thereto. Georgakis. however. 1930II.2'99 83-11876 Copyright © 1983 American Chemical Society A l l Rights Reserved. Chemical reactions—Congresses.acs. such as for general distribution. specification. James. for creating new collective work. or other data be regarded as a license or as a conveyance of any right or permission. for copying beyond that permitted by Sections 107 or 108 of the U. 1983 | doi: 10. or any other person or corporation. 2. or for information storage and retrieval systems. chemical process. nor should the mere reference herein to any drawing.org Publication Date: July 28. reader. DC. The appearance of the code at the bottom of the first page of each article in this volume indicates the copyright owner's consent that reprographic copies of the article may be made for personal or internal use or for the personal or internal use of specific clients. 1983.Downloaded by FORDHAM UNIV on December 2. I. 1. This consent does not extend to copying or transmission by any means—graphic or electronic—for any other purpose. The copying fee for each chapter is indicated in the code at the bottom of the first page of the chapter.S. ISSN 0097-6156. 1947. to manufacture. (ACS symposium series. Inc. J. Series. for advertising or promotional purposes. reproduce. for resale. This consent is given on the condition. that the copier pay the stated per copy fee through the Copyright Clearance Center. III.I67 1982a ISBN 0-8412-0793-3 660. Copyright Law. 226) Includes bibliographies and index... 2012 | http://pubs. Mass. ACS Symposium Series.fw001 Library of Congress Cataloging in Publication Data International Symposium on Chemical Reaction Engineering (7th: 1982: Boston. to the holder. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein. PRINTED IN THE UNITED STATES OF AMERICA In Chemical Reaction Engineering—Plenary Lectures.) Chemical reaction engineering—plenary lectures. et al. Wei.

1021/bk-1983-0226.Downloaded by FORDHAM UNIV on December 2. Satterfield W. Marvin Margoshes Charles S. DC. Temple.. Grant Willson In Chemical Reaction Engineering—Plenary Lectures. 1983. Allara Robert Ory Robert Baker Geoffrey D .acs. ACS Symposium Series. et al. Jeffrey Howe Dennis Schuetzle Herbert D . Jr. 1983 | doi: 10. Harney Charles N . Series Editor Advisory Board David L . American Chemical Society: Washington.fw001 ACS Symposium Series M . . Joan Comstock. Moreland C.org Publication Date: July 28. Kaesz Davis L . J. 2012 | http://pubs. Wei.. Parfitt Donald D . Dollberg Theodore Provder Brian M. Tuesday Donald E .

Wei. however. 1983. Papers are reviewed under the supervision of the Editors with the assistance of the Series Advisory Board and are selected to maintain the integrity of the symposia. et al.1021/bk-1983-0226. ACS Symposium Series. 1983 | doi: 10.acs.. The format of the Series parallels that of the continuing A D V A N C E S I N C H E M I S T R Y SERIES except that in order to save time the papers are not typeset but are reproduced as they are submitted by the authors in camera-ready form. J. 2012 | http://pubs. verbatim reproductions of previously published papers are not accepted. American Chemical Society: Washington. DC.org Publication Date: July 28.. In Chemical Reaction Engineering—Plenary Lectures. . Both reviews and reports of research are acceptable since symposia may embrace both types of presentation.fw001 FOREWORD The A C S S Y M P O S I U M SERIES was founded in 1 9 7 4 to provide a medium for publishing symposia quickly in book form.Downloaded by FORDHAM UNIV on December 2.

This page intentionally left blank .

you will find the chemical reactor as a small unit in a very large network. . The main difference between chemical reaction engineering and unit operations lies in the presence or absence of chemical reactions.. When you look over the flowchart of a process. The peripheral equipment of unit operations (the tail) usually wags the chemical reactors (the dog). 2012 | http://pubs. yet.. American Chemical Society: Washington. ix In Chemical Reaction Engineering—Plenary Lectures.org Publication Date: July 28. CHEMICAL REACTION ENGINEERING (CRE) is concerned with the design. the design of all other equipment revolves around the chemical reactors.acs. thermodynamics. the conversion of a harmful feed to harmless products is the main objective. ACS Symposium Series. et al. Except for purely separational processes. and transport phenomena that seek to isolate and analyze an individual aspect of a complex piece of machinery or to understand and describe quantitatively the material behavior at microscopic or molecular scales. and the unit operations equipment serves the needs or compensates for the inadequacies of the chemical reactors. and control of processing equipment called chemical reactors. such as the production of oxygen from air. the heart of any chemical process is one or more chemical reactions that transform less valuable feed material to more valuable products. Chemical reactors lie in the heart of any chemical plant. J. C R E is the counterpart to unit operations (UO). operation. They differ from the engineering science subjects of kinetics.pr001 PREFACE IN T H E NARROW SENSE. In the case of pollution control equipment. the main products are heat and energy rather than material products. which usually run 10-20% of the total plant cost. DC.Downloaded by ILLINOIS STATE UNIV on December 2. 1983 | doi: 10. Wei. In the case of combustion. The optimum design of a chemical reactor does not necessarily lead to the optimum design of a chemical plant. Both chemical reaction engineering and unit operations integrate many disciplines to attain practical engineering goals. optimization. which is concerned with processing equipment in which no chemical reactions take place. A good design engineer chooses the dog that has the smallest tail.1021/bk-1983-0226. fluid mechanics. The design of a chemical plant must start with the chemical reactors. 1983.

J. such as kinetics.. but are hardly ever studied. or by adoption into this tribe of brilliant outsiders with brand new ideas.pr001 Design kinetic dependence on temperature and concen­ trations Intellectual Chemists and chemical Collaborators engineers Mechanical engineers In the broader sense. fluid me­ chanics and transport in fixed and fluidized beds. They share a common set of textbooks and tools. . and solid movement mechanics in moving and fluidized beds. catalyst design. the same vocabulary and analytical scheme to analyze problems. paper-making machines would seem to be very suitable subjects for reaction engineers.. Whatever is accomplished by a member of this tribe will be shared with the rest of the members and is by definition chemical reaction engineering. chemical reaction engineering is also concerned with the components needed for the synthesis of chemical reactors. the following may be noted: Function Chemical Reactors Unit Operations Chemical reactions Physical operations needed to service the reactors Individually tailored Modular. 1983. mixing. but this subject is very seldom studied by the major researchers in fluid mechanics. multiphase systems. American Chemical Society: Washington. χ In Chemical Reaction Engineering—Plenary Lectures. ACS Symposium Series.acs. Study of the maldistribution of gas and liquid flow in trickle beds can be considered as a branch of fluid mechanics. They agree on what are proper problems to be tackled and what are proper standards for admissible reports and papers. and the same set of triumphant classic achievements in the past. et al. Reaction engineers form a living and changing tribe that keeps in touch through professional meetings and journals.org Publication Date: July 28. Polymerization reactors are enormously impor­ tant in the chemical industries and are beginning to attract serious re­ searchers with backgrounds in reaction engineering. 2012 | http://pubs. However. it is a subject that is studied by major re­ searchers in reaction engineering. they form a paradigm of their own. In short.In a comparison of the salient features.1021/bk-1983-0226. catalysis. New people are constantly recruited by this tribe through the process of apprenticeship and junior partnership. Wei. 1983 | doi: 10. often can be for each reaction ordered from catalogs Cost 10-20% of total plant 80-90% of total plant Performance Highly nonlinear due to Nearly linear Downloaded by ILLINOIS STATE UNIV on December 2. DC. O n the other hand.

acs. Combustion should have been one of the most central problems in reaction engineering. in which scale up by design engiDownloaded by ILLINOIS STATE UNIV on December 2. we print the six plenary speeches given at the 7th International Symposium on Chemical Reaction Engineering at Boston.In this volume. except for liquid fuels for transportation. ACS Symposium Series. 2012 | http://pubs. These two chapters form a powerful contrast between the academic intellectual approach and the industrial pragmatic approach. DC. 1983. They augment the basic textbooks as part of "what every educated reaction engineer should know. and second. and fluidizedbed combustors are reviewed by Sarofim. there will be little demand for clean synthetic fuels. Micromixing is reviewed by Villermaux. Most textbooks of reaction engineering have rather short sections on polymerization. It is overdue for us to build bridges to these outstanding people. First. a subject found more often in polymer textbooks. American Chemical Society: Washington." JAMES WEI Massachusetts Institute of Technology Cambridge. If fluidized-bed combustors for coal are well engineered. 1982 xi In Chemical Reaction Engineering—Plenary Lectures. . et al. the study of alternative reactors for the methanol-togasoline process is described by Penick. Wei.. the intellectual foundation of chemical reaction engineering is described by Aris. These reviews will go a long way toward remedying this defect.1021/bk-1983-0226. These two chapters are concerned with homogeneous phase and nearly homogeneous phase reactors that are of growing importance. MA October 22. whatever their subspecialty. and one of its most important future applications. Fluidized beds are reviewed by Rowe. These two chapters are concerned with one of the most powerful reactors. and chemists with their own Combustion Institute and highly successful International Symposium series. mechanical engineers. The plenaries serve as a powerful centralizing force among reaction engineers. 1983 | doi: 10.pr001 neers is still done with great trepidation. These plenaries should be read by all students of chemical reaction engineering. J.org Publication Date: July 28.. Only historical events decree that it should be a meeting ground of chemical engineers. who are always in danger of moving off in their own individual rivulets and drying out. and polymerization reactors are reviewed by Ray.

. MN 55455 What. bracket him w i t h Newton as " S y l v e s t e r noster" i n the accolade: "Nonnulla quae Newtonus noster. 1983 | doi: 10. ACS Symposium Series. He t h e r e f o r e went to T r i n i t y C o l l e g e . imperfecta r e l i q u e r u n t .ch001 R. S y l v e s t e r ' s career had not been an easy one ÇL) . the first of the Johns Hopkins University. Department of Chemical Engineering and Materials Science.D. American Chemical Society: Washington. could not comp l e t e h i s degree without s u b s c r i b i n g t o the 39 A r t i c l e s of the Church of E n g l a n d — a s u b s c r i p t i o n he was u n w i l l i n g t o make. J.acs. Iacobius. S y l v e s t e r n o s t e r . quae F r e s n e l i u s .1021/bk-1983-0226. A f t e r h i s s t u d i e s at Cambridge had been i n t e r r u p t e d by i l l n e s s he took h i s degree i n 1837 as Second Wrangler i n the same c l a s s as George Green. The latter was none other than the great James Joseph Sylvester.1 Chemical Reaction Engineering as an Intellectual Discipline Downloaded by ILLINOIS STATE UNIV on December 2. he crossed the A t l a n t i c to the U n i v e r s i t y of V i r g i n i a but 0097-6156/83/0226-0001$06. I take my text from the advice given to President Gilman. when the r e l i g i o u s b a r r i e r s had at length been removed." A f t e r two years at U n i v e r s i t y C o l l e g e . a l i i . With his appointment to Hopkins at the age of 62 there came the second flowering of his genius and with it his exploration of the fundamental system of invariants and the syzygies of algebraic forms.org Publication Date: July 28. Sturmius. ARIS University of Minnesota. DC. by then. D u b l i n from which he received h i s degrees i n 1841.. let me turn to two of the traditional disciplines and try to sketch some of the characteristics that they may have or induce in their adepts. playing chess and versification on the principles of his "Laws of Verse"—a pamphlet by which he set great store. I n 1890 he was given an honorary Sc.00/0 © 1983 American Chemical Society In Chemical Reaction Engineering—Plenary Lectures. 2012 | http://pubs. at the same time as Benjamin Jowett. Wei. To say that he took h i s degree i s not q u i t e accurate. Henry Perry Liddon and other notables. 1983. His Cambridge degree he d i d not r e c e i v e u n t i l 1872. f o r S y l v e s t e r . et al. Minneapolis. retired from Woolwich since 1870 and spending his time in the enjoyment of the classics. to start with the best classical scholar and the best mathematician that he could find. who says of himself that he was one of the f i r s t h o l d i n g "the f a i t h i n which the founder of C h r i s t i a n i t y was educated" t o compete f o r the mathematical t r i p o s .. aut e l e g a n t i u s e x p l i c a v i t aut argumentis v e r i s comprobavit. The P u b l i c Orator c o u l d . you are entitled to ask. do you mean by an intellectual discipline? Before attempting any formal answer.

2012 | http://pubs. During that time he e s t a b l i s h e d graduate s t u d i e s i n the c l a s s i c a l d i s c i p l i n e s . d i r e c t i n g no l e s s than 67 d o c t o r a l d i s s e r t a t i o n s thus having a profound i n f l u e n c e on c l a s s i c a l s t u d i e s throughout the country. H i s colleague i n c l a s s i c s was a l s o of the g r e a t e s t d i s t i n c t i o n . G i l d e r s l e e v e was. ACS Symposium Series." Much l a t e r i n the A t l a n t i c Monthly of January 1892 he s t i l l was "not c e r t a i n t h a t a l l " readers might " a p p r e c i a t e the e n t i r e clearness of conscience w i t h which we of the South went i n t o the war" ( 4 ) . . a much younger man—45 to S y l v e s t e r ' s 62—when he came to Hopkins b u t .1021/bk-1983-0226. h i s f r i e n d s h i p w i t h Cayley matured and he took p r i v a t e p u p i l s . though I would t h i n k t h a t .acs.. w i t h the exception of the q u e s t i o n of s t a t e s r i g h t s .ch001 2 C H E M I C A L REACTION ENGINEERING remained there only a matter of months ( 2 ) . however. government quarters and the r i g h t of a pasturage on Woolwich Common.f i v e of h i s o l d p u p i l s put together a volume of l a r g e l y p h i l o l o g i c a l s t u d i e s i n h i s In Chemical Reaction Engineering—Plenary Lectures. During t h i s p e r i o d .by sharing the fortunes of t h e i r f a t h e r s and b r o t h e r s at the f r o n t f o r three.. et al. 1983. he presided over the d e s t i n y of the c l a s s i c s there f o r the next 39. He continued there u n t i l 1870 when he r e t i r e d over what he regarded as an u n f a i r change i n the r e g u l a t i o n s and w i t h some b i t t e r n e s s over h i s pension. I n 1901 some f o r t y .Downloaded by ILLINOIS STATE UNIV on December 2. I have not been able to f i n d any reference to the d i r e c t i n t e r c o u r s e of these two men. At a l l events the move f o r the second time to America was a great success and he found h i m s e l f able to teach mathematics w i t h great freedom and play a l e a d i n g r o l e i n the i n t e l l e c t u a l l i f e of Baltimore s o c i e t y .. a drudgery which might have s t i f l e d the mathematical genius of a l e s s robust man. 1983 | doi: 10.org Publication Date: July 28. which he founded i n 1880 e a r l y i n h i s time at Hopkins and published from there f o r many y e a r s — a pleasant f o i l to S y l v e s t e r ' s American J o u r n a l of Mathematics. I t was S y l v e s t e r s d e l i g h t to read the c l a s s i c s and G i l d e r s l e e v e would have approved the motto which he gave the American J o u r n a l of Mathematics which was founded at Hopkins i n 1878 and e d i t e d by Sylvester: 1 1 1 G i l d e r s l e e v e does r e f e r to S y l v e s t e r s m e t r i c a l theory of "phonetic syzygy" i n one of the B r i e f Mentions of the American J o u r n a l of P h i l o l o g y . DC. i n coming to Johns Hopkins.. the most i l l u s t r i o u s of whom was Florence N i g h t i n g a l e who went out to Crimea i n 1854. J. Perhaps i t was t h i s that made him. C a l l e d from the same u n i v e r s i t y i n which S y l v e s t e r had had so unhappy an experience years b e f o r e . Wei. American Chemical Society: Washington. of course. He returned to academic l i f e as p r o f e s s o r of mathematics at Woolwich w i t h a s a l a r y of £550. be paid i n gold ( 3 ) . the c o n s i d e r a b l e sum of $5. B a s i l Lanneau G i l d e r s l e e v e was a Southerner born and bred who served w i t h the Confederate Army w h i l e the C i v i l War was i n progress during the summer months i n order (as he says) "to earn the r i g h t to teach Southern youth f o r nine months.000. i n c o n t r a s t to S y l v e s t e r ' s b r i e f tenure of 8 y e a r s . Returning to England he spent some time as an actuary f o r a l i f e insurance company. they would have had much i n common. the year of S y l v e s t e r ' s r e l e a s e from the l e g a l world. request that h i s s a l a r y .

i n a d v e r t i n g t o the then r e c e n t l y published book e n t i t l e d "Value of the C l a s s i c s " (Princeton U n i v e r s i t y P r e s s ) . he remarks " I have not had l e i s u r e of mind. He published a paper i n the American J o u r n a l of Mathematics i n 1882 e n t i t l e d "A C o n s t r u c t i v e Theory of P a r t i t i o n s . Newman of I l l i n o i s ) i n our gropings through the room of i n t e l l e c t .. A volume of h i s s t u d i e s and essays appeared i n 1890 (6) and a s e l e c t i o n of h i s B r i e f Mentions published over the years i n the American J o u r n a l of P h i l o l o g y was e d i t e d w i t h a b i o g r a p h i c a l sketch by h i s successor and devoted p u p i l i n the c h a i r of Greek at Johns Hopkins ( 7 ) . which Downloaded by ILLINOIS STATE UNIV on December 2. the f u r n i t u r e . I s t a t e i t t h e r e f o r e w i t h due reserve. 1983 | doi: 10. American Chemical Society: Washington. however f a s c i n a t i n g they may be. The very name " c l a s s i c s " i s an acknowledgement of our debt t o the c u l t u r e s of ancient Greece and Rome." But we must t u r n from the b i o g r a p h i c a l d e t a i l s of these g i a n t s . Wei. . e d i t e d by H. DC. Whether we l i k e i t or not. and ask about the characters of t h e i r subjects as d i s c i p l i n e s . G i l d e r s l e e v e remarks that "appended to these impressive d e l i v e r a n c e s there i s a formidable array of s t a t i s t i c s drawn up i n r e f u t a t i o n of those other s t a t i s t i c s that have been used only too e f f e c t i v e l y t o s t i r up the pure minds of b e l i e v e r s i n L a t i n and Greek." Act One i s on p a r t i t i o n s regarded as e n t i t i e s and i s prefaced w i t h the quotation from Twelfth-Night. Arranged i n Three A c t s ."seeming parted.org Publication Date: July 28. which we bump i n t o (to borrow a metaphor from J .1. K.acs. but yet a union i n p a r t i t i o n . he was a p r o l i f i c p u b l i s h e r on a wide range of s u b j e c t s . et al. I n our everyday and s c i e n t i f i c language we pay hidden t r i b u t e t o the notions of c l a s s i c a l times using words that were c o n s c i o u s l y coined t o r e f l e c t t h e i r thought. but the book w i l l strengthen the f e e b l e knees of those who are a f r a i d that they w i l l have to bow thems e l v e s down i n the House of Rimmon. f o r a l l our neglect of t h e i r sources. G i l d e r s l e e v e s papers were as numerous though not as completely c o l l e c t e d . i s s t i l l a standard reference book. L i k e S y l v e s t e r . " In a paper on the three laws of motion i n the world of u n i v e r s a l algebra published i n 1884 he has a charming footnote i n which. S y l v e s t e r ' s " C o l l e c t e d Works" run t o 4 quarto volumes. and I n t e r a c t and an Exodion. s t i l l observe today. r e v i s e d w i t h the cooperation of P r o f e s s o r Lodge. of thought that we. being much occupied i n preparing f o r my departure. J. 2012 | http://pubs.. 1983. Thus "gas" f o r the t h i r d e s t a t e of matter has now been common f o r more than three c e n t u r i e s but goes back t o the a l c h e m i c a l n o t i o n of the i n d w e l l i n g s p i r i t of a t h i n g . was b u i l t and put there by the Greeks. t o reduce t h i s theorem t o a p o d i c t i c c e r t a i n t y . f o r i n u s i n g i t we are reminding ours e l v e s that i t i s they who f i r s t recognized the c l a s s e s .. o r c a t e g o r i e s . ACS Symposium Series. For example. F.1021/bk-1983-0226.. a f t e r r e f e r r i n g t o a theorem i n the t e x t . My missionary days are long overpast and s t a t i s t i c s have l o s t whatever charm they had f o r me even i n the s y n t a c t i c a l l i n e .ch001 1 In Chemical Reaction Engineering—Plenary Lectures. Both men r e j o i c e d i n an amplitude of s t y l e that betrays a more l e i s u r e d age than ours. Baker i n 1912." Compare S y l v e s t e r . G i l d e r s l e e v e published more books than S y l v e s t e r and h i s L a t i n grammar. ARis Reaction Engineering as an Intellectual Discipline 3 honor ( 5 ) .

In Chemical Reaction Engineering—Plenary Lectures. a 'lucidus ordo'. 1983. I t i s almost l i k e the c o n t r a s t you can experience by t u r n i n g aside from Watling S t r e e t or the Fosse Way i n t o a country road or lane as you go "to Birmingham by way of Beachy Head. i s n a t u r a l enough and was so t r a n s f e r r e d by Pythagoras to the world as expressing that ordered beauty whose a p p r e c i a t i o n i s the b a s i s f o r a l l s c i e n t i f i c — n o t to say humanistic—endeavour ( 8 ) .. and not to know L a t i n i s to have missed an admirable t r a i n i n g i n p r e c i s e and l o g i c a l thought" (11). To study of the c l a s s i c s i s s u r e l y to submit to a d i s c i p l i n e that r e j o i c e s i n the r e l a t i o n of words and ideas. By c o n t r a s t E n g l i s h . I t i s not j u s t to l u x u r i a t e i n e t y m o l o g i c a l overtones (a v i c e i n t o which I have j u s t allowed myself to be betrayed) but to l e a r n the r e l a t i o n of word and thought as expressed by the p r e c i s e usage of words and t h e i r p l a c e i n the s y n t a c t i c a l s t r u c t u r e of a sentence. and i s p a r t i c u l a r l y c a l l e d f o r t h by an i n f l e c t e d tongue and one. . nos lucentum mundum nominamus". For of i t s o r i g i n a l meaning—adorning or ornament—the only t r a c e l e f t to us i n E n g l i s h i s a s u p e r f i c i a l . American Chemical Society: Washington. mist or d i s t i l l e d O y l i n e s s e s . The act of t r a n s l a t i o n from one language i n t o another demands t h i s hard s t r i v i n g f o r p r e c i s i o n . 2012 | http://pubs. being not f a r severed from the Chaos of the A u n t i e n t s . o n e — c o s m e t i c ." This was charmingly t r a n s l a t e d i n Chandler's "Van Helmont's O r a t i o n s " (1662) as: " I have c a l l e d that vapour. although as y e t i t be many times t h i c k e r than a i r .org Publication Date: July 28.acs. a f a r more s u b t i l e or f i n e t h i n g than vapour. non longe a Chao veterum secretum. m a t e r i a l l y taken." The very f a m i l i a r i t y of our n a t i v e speech and i t s c o l l o q u i a l u s e — c o r r e c t and e f f e c t i v e though t h i s b e — d e n i e s i t the c u t t i n g edge needed to shape our minds. But Gas i t s e l f . where the thought i s marshalled i n t o p r i n c i p a l and subordinate clauses. rambling comfortably on i n coordinated measures. f o r a l l i t s m e r i t s . Gas. But that i t should a l s o mean order. the c u r r e n t l y popular study of mathematical chaos uses the Greek work i n simple t r a n s l i t e r a t i o n . i s water as y e t masked w i t h the Ferment of composed Bodies.. Yet i t i s pleasant to r e f l e c t that a recent meeting on t h i s s u b j e c t i n Los Alamos (May 1982) could be s u b t i t l e d "ΚΟΣΜΟΣ EN ΧΑΩ" and thus make i r o n i c comment on the world as w e l l as r e c a l l i n g the o r i g i n a l sense of the beauty of order inherent i n the word κόσμοβ. As L i v i n g s t o n e wrote years ago "No doubt there are more important things i n education than the study of grammar. almost m e r e t r i c i o u s . has a l a x and i n d i v i d u a l s t r u c t u r e . DC." I f 'gas' i n the p h y s i c a l sense s t i l l bears echoes of the formless darkness over the f a c e of the deep. eum nos a p e r f e c t a absolutaque e l e g a n t i a mundum": or C i c e r o ' s : "Hunc hac v a r i e t a t e d i s t i n c t u m bene G r a e c i κόσμον. et al. 1983 | doi: 10. Wei. ACS Symposium Series.1021/bk-1983-0226. J. .ch001 4 C H E M I C A L REACTION ENGINEERING Van Helmont (1577-1644) i n h i s "Ortus Medecinae" (1652) r e f e r r e d to as " h a l i t u m i l i u m Gas v o c a v i . but i t i s not an overstatement to say that not to know Greek i s to be ignorant of the most f l e x i b l e and s u b t l e instrument of expression which the human mind has d e v i s e d . .Downloaded by ILLINOIS STATE UNIV on December 2. such as L a t i n . 'Mundus' i n L a t i n f o l l o w s a p a r a l l e l course as we see i n P l i n y ' s comment: "Quem κόσμον G r a e c i nomine ornamenti a p p e l l a v e r u n t .

" i n v o l v e s c o n c e n t r a t i o n . 2012 | http://pubs.Downloaded by ILLINOIS STATE UNIV on December 2. This necessary occupation w i t h w o r d s — t h e i r p r e c i s i o n of meaning & the exactness of the way they are put t o g e t h e r — i s fundamental t o the c a r e f u l r e c o n s t r u c t i o n of a t e x t and i t s c r i t i c a l e v a l u a t i o n . and i t too has i t s own d i s c i p l i n e s — i t s sherds o f t e n to be handled as d e l i c a t e l y as p a r t i c l e s . and considerable l o g i c a l reasoning. but he never p u b l i s h e d i t as was customary. The manuscript was destroyed a f t e r h i s death but a f u r t h e r copy found among h i s papers was published i n T. I t was not u n t i l a f t e r In Chemical Reaction Engineering—Plenary Lectures. there i s the p h i l o l o g i c a l foundation. Housman gave h i s i n a u g u r a l as Kennedy P r o f e s s o r of L a t i n a t the U n i v e r s i t y of Cambridge on 9 May 1911. T h i s . i t s a r t i f a c t s as l o v e l y as odes and epodes.. Wei. b u t . i s not the p l a c e to e x t o l the c l a s s i c s — n o r do they need i t — w h a t I am concerned w i t h i s the f e a t u r e s of i n t e l l e c t u a l l i f e that t h e i r study c u l t i v a t e s . 1983.. American Chemical Society: Washington. the passage of S h e l l e y (and Swinburne's remarks on i t ) that he had been unable to v e r i f y (17).S. Language i s the entry t o l i t e r a t u r e as l i t e r a t u r e i s the r e f l e c t i o n of the l i f e and thought of i t s time.acs. ARis Reaction Engineering as an Intellectual Discipline 5 Of the converse d i s c i p l i n e . he says.org Publication Date: July 28. o m i t t i n g . et al.d e f e n s e . i t s p e n e t r a t i o n should be the envy of the modern s o c i a l s c i e n t i s t . DC. there are no short c u t s .ch001 1. f o r he was never able to V e r i f y a statement i t contained as t o the t e x t of S h e l l e y ' s Lament of 1821' (16). As s o c i o l o g y or s o c i a l psychology. no formulae as i n the science problem. J. I n the f i r s t p l a c e . . as I have ventured t o comment e l s e where i n reviewing " I n s i g h t s i n t o Chemical Engineering" (13). The advocate of extreme measures was always trustworthy. the Greek and L a t i n c u l t u r e s have an uncanny way of a n t i c i p a t i n g and i l l u s t r a t i n g modern p o l i t i c a l and s o c i a l problems. As l i t e r a t u r e . C l a s s i c indeed i s Thucydides' d e s c r i p t i o n of the i n t e r n a l corrosiveness of war and r e v o l u t i o n "Words had t o change t h e i r o r d i n a r y meaning and to take that which was now given them. 1983 | doi: 10. the reasoning i n v o l v e d cannot be avoided by mere e f f o r t of memory as i n the w r i t i n g out of a p r o p o s i t i o n i n geometry" (12). i n 1968. however. and i t s s i t e s as complex and i n t r i c a t e as the p l o t of a tragedy or i n t e r play of a dialogue.. I t has been popular among great men from Winston C h u r c h i l l to P e t e r Danckwerts t o deplore the hours spent on L a t i n and e x t o l t h e i r i n s t r u c t i o n i n E n g l i s h .1021/bk-1983-0226. A t r a i n i n g i n t h i s sometimes leads t o a c e r t a i n cautiousness and care i n q u o t a t i o n . Archaeology r e v e a l s the c i r c u m s t a n t i a l l i f e as l i t e r a t u r e does the i n t e l l e c t u a l . cautious p l o t t i n g a j u s t i f i a b l e means of s e l f . ACS Symposium Series.L.Frantic v i o l e n c e became the a t t r i b u t e of manliness. that o f t u r n i n g E n g l i s h i n t o L a t i n or Greek i t i s i n t e r e s t i n g t o quote the P h y s i c s master a t Winchester.. i t s quick a n t i t h e s e s "breathe an almost human a l i v e n e s s " i n t o an otherwise a b s t r a c t a n a l y s i s (15). But the study of the c l a s s i c s i s not merely a matter of language however great the general b e n e f i t to our general understanding of language t h i s may a f f o r d . h i s opponent a man to be suspected" (14). c l o s e a t t e n t i o n t o d e t a i l . From t h e i r p l a c e at the root of western c i v i l i z a t i o n . t h e i r E n g l i s h may owe more t o the d i s c i p l i n e of the c l a s s i c s than they a f f e c t t o admit. however. "The t a s k " .

. 1983. Wei. To the n i c e a p p r e c i a t i o n of language the c l a s s i c a l s c h o l a r must add a c e r t a i n copiousness of l e a r n i n g . S i r Andrew Aguecheek's lament i n "Twelfth Night" (provoked you w i l l r e c a l l by S i r Toby's "Pourquoi") "0 that I had but f o l l o w e d the A r t s " (19) i s a r e a l cry of the h e a r t . i t invades the province of science".. w i t h i t s f a c i l e emotions and i t s i n c a p a c i t y f o r s e l f . the passion f o r elegance and the p u r s u i t of r i g o u r . philosopher and a r c h a e o l o g i s t a l l need i t — b u t the d i s c i p l i n e demands that t h i s imagination should be c o n t r o l l e d by p r e c i s i o n of s c h o l a r s h i p r a t h e r than the r a m i f i c a t i o n of fancy. 2012 | http://pubs. h i s t o r y and philosophy i s p a r t of the g r a i t h of c l a s s i c a l s c h o l a r s h i p j u s t as a wide experience of d i f f e r e n t aspects of ancient c i v i l i z a t i o n and a keen and d i s c e r n i n g eye f o r i t s a r t i f a c t s i s needed by the a r c h a e o l o g i s t . Indeed the c o n t r a s t that most f o r c i b l y s t r i k e s a s c i e n t i s t i n t a l k i n g to the humanist i s the comparatively immense amount of reading t h a t the l a t t e r must do and the recourse that must be had to primary sources. J. f o r . the power of a b s t r a c t i o n i n mathematics i s In Chemical Reaction Engineering—Plenary Lectures.a young man's game"— mathematics (20). ACS Symposium Series.. As an i n t e l l e c t u a l d i s c i p l i n e . Against n e i t h e r could he give an i n f a l l i b l e a l e x i k a k o n . . p. but because Housman used i t to show the k i n d of confusion that can a r i s e i f e x a c t i t u d e of t h i s order i s not maintained. s o o f t e n found i n company w i t h l a c k of due v e n e r a t i o n towards the dead" (18.. the one breeding the fatuousness of " t a s t e " . . But l e t us t u r n to a d i s c i p l i n e which. though he warned against that " s e r v i l i t y shown towards the l i v i n g " that " i s .ch001 6 C H E M I C A L REACTION ENGINEERING f u r t h e r work on S h e l l e y manuscripts had j u s t i f i e d the quotation as Housman had used i t . DC. 1983 | doi: 10. 44). the a c q u i s i t i o n of the v a r i e d and extensive knowledge which i s needed i n ancient s t u d i e s i s an impossible task i f not begun i n childhood. the other the m e n t a l i t y of the s l a v e . though they share these c h a r a c t e r i s t i c s i n some degree w i t h other d i s c i p l i n e s .Downloaded by ILLINOIS STATE UNIV on December 2.org Publication Date: July 28. et al. that John Carter published the l e c t u r e as "The Confines of C r i t i c i s m " i n 1969 (18). " But the l i n e that so t h r i l l e d Swinburne's veins was a m i s p r i n t and the "sovereign sweetness" of the stanza not S h e l l e y ' s c r a f t but some unknown compositor's carelessness. l i t e r a r y c r i t i c . save f o r the e x c e p t i o n a l l y g i f t e d . i s "more than any other a r t or science. .1021/bk-1983-0226. which by some might be thought excessive. American Chemical Society: Washington. A very broad reading of l i t e r a t u r e . i t s l e a d i n g c h a r a c t e r i s t i c s are the power of a b s t r a c t i o n . "added Housman s e v e r e l y . f o r . " are the performances of the l i t e r a r y mind when..e x a m i n a t i o n . Swinburne had p r a i s e d an u n m e t r i c a l l i n e i n the commonly p r i n t e d v e r s i o n of the second stanza as "a t h i n g to t h r i l l the v e i n s and draw t e a r s to the eyes of a l l men whose ears were not closed against a l l harmony" by "the melodious e f f e c t of i t s e x q u i s i t e i n e q u a l i t y . I mention t h i s example not merely because of t h i s care f o r exactness. I f the c l a s s i c s demand exactness they do not r u l e out i m a g i n a t i o n — t h e t e x t u a l c r i t i c . "These. I put them i n that order.acs. as Hardy says. I t i s only f a i r to add that having smitten the E n g l i s h tool i t e r a r y carelessness he went on to denounce the German methodisch unimaginativeness.

or Luxemburg on whom he l e a n s . I t i s thus that we p e r c e i v e t h a t .1021/bk-1983-0226. but h i s proof (or r a t h e r the proof which goes back to h i s school i n the s i x t h century B. A t the same time we are conscious of the f a c t that stoicheiometry i s not everything and that we may have to move beyond i t t o an aspect i n which a p a r t i c u l a r set has a p r e f e r r e d character. DC. 1983. ARis Reaction Engineering as an Intellectual Discipline 1 r a i s e d to a height u n a t t a i n a b l e i n any other s u b j e c t . I f I may. et al. We 1 T In Chemical Reaction Engineering—Plenary Lectures.C. I would l i k e t o advert f o r a moment t o the recent development of non-standard a n a l y s i s and sketch how i n f i n i t e and i n f i n i t e s i m a l numbers can be presented.Downloaded by ILLINOIS STATE UNIV on December 2. I suppose the root of these notions goes back to Pythagoras who discerned the pervasive i n f l u e n c e of number i n the order of nature. Perhaps we can r e c a l l the i n i t i a l con­ f u s i o n and u l t i m a t e d e l i g h t of r e c o g n i z i n g that the c a r d i n a l number of a c l a s s was indeed the c l a s s of a l l c l a s s e s s i m i l a r t o i t . w i t h the understanding of the n o t i o n of f u n c t i o n . American Chemical Society: Washington.. The group. . not to have perceived i t s l i m i t a t i o n s i s to have f a i l e d to understand the nature of a b s t r a c t i o n .. We take the concept o f number so completely f o r granted that we tend t o f o r g e t what an achievement t h i s a b s t r a c t i o n of concept must have been.Χη.. In this I follow a b e a u t i f u l expository a r t i c l e of Ingleton (22) though.···. but as a b s t r a c t e n t i t i e s forming our powers of apprehension. As a r e s u l t connections can be found between things which are very f a r from obvious. 3/6. From now on we can consider the e n t i t y Χ to be the equivalence c l a s s and representable by any of i t s members j u s t as the r a t i o n a l 1/2 i s the c l a s s (1/2. Of course t h i s was not developed u n t i l much l a t e r when. r i n g or f i e l d i n algebra w i t h the notions of equivalence r e l a t i o n s . 2012 | http://pubs. Χ Ξ X i f χ = x f o r a l l but η η a f i n i t e number of n. Hardy (20) as opening up the whole realm of r e a l numbers. 2/4. an immensely important step forward i n the h i s t o r y of thought when i t was f i r s t r e a l i z e d that there was a commonality of some s o r t between a p a i r of twins and a brace of pheasants. I t i s of course a long way from the f i v e and country senses of the engineering world t o the t h i n a i r o f the heights that mathematicians seem to breathe so e f f o r t l e s s l y . making that d e f i n i t i v e step beyond the everyday common­ places of i n t e g e r s and r a t i o n a l e . yet we are f o r ­ tunate to have had as p a r t of our t e c h n i c a l t r a i n i n g a t l e a s t a brush w i t h some o f the s t r u c t u r e s that pervade mathematics. 1983 | doi: 10. save perhaps music. H.χ^. i n my haste s c a r c e l y doing him. ···) and l e t two such e n t i t i e s be equivalent i f they d i f f e r only i n a f i n i t e number of elements i . Not to have perceived the equivalence i s to be l e f t i n a confusion of c o n c r e t i o n s . or at a more lowly l e v e l our l i b e r a t i o n from χ and y as apples and oranges i n our kindergarten s t r u g g l e s w i t h elementary algebra. any non-singular transformation of a set of chemical r e a c t i o n s gives an equivalent s e t .) of the i r r a t i o n a l i t y of the square root of two i s c i t e d by G.acs. Consider a l l i n f i n i t e sequences of r e a l numbers Χ (χ^. not only i n t h e i r i n s t a n t i a t i o n s . Wei. and mappings are p a r t of our mental f u r ­ n i t u r e .org Publication Date: July 28. J. ACS Symposium Series.).ch001 1. I t was. .. e . i t became p o s s i b l e t o express p h y s i c a l laws i n mathematical form. morphisms. from a purely s t o i c h e i o m e t r i c point of view. as Whitehead pointed out (21). f u l l j u s t i c e .

Ζ = N. Two h y p e r r e a l numbers a r e i n f i n i t e s i m a l l y c l o s e i f t h e i r d i f f e r e n c e i s i n f i n i t e s i m a l . This makes the d i s c u s s i o n of convergence r a t h e r simple. J.4.ch001 1 q Q Q Ν. We have h y p e r r e a l numbers l i k e Ζ = (1. (Z+N) . But these are a p p l i c a t i o n s and p a r a d o x i c a l l y I have been d e s c r i b i n g the a b s t r a c t i o n that i s the non-standard world i n very concrete terms. 2 z 2 11 2 V M f In Chemical Reaction Engineering—Plenary Lectures. I n f a c t every f i n i t e h y p e r r e a l number i s i n f i n i t e s i m a l l y c l o s e t o a r e a l number and every r e a l number has an i n f i n i t y of i n f i n i t e s i m a l l y c l o s e h y p e r r e a l s . (N.···) and the r u l e f ( X ) = (f(x ). On the other hand 1/Z = (1.|7i»'* » y '' > x 1 1 η e η x ee n = a n d n 1/X = (1/x-^. l / x .3. ff^ = Ν $ or K = Ν + fÎ f o r any f i n i t e n Downloaded by ILLINOIS STATE UNIV on December 2.Z = (Ν.χ···)(ί. This i s no p l a c e t o go back and t r y t o present i t a b s t r a c t l y ..···. But now we n o t i c e t h a t we have i n R* a much r i c h e r e n t i t y than we had i n R.···ί(x )···) i s a n a t u r a l extension of the f u n c t i o n f from R to R*. 1/Z e t c .N+n. Then i s an element of a non-standard sequence i f Υ ε R* and Μ ε Ν*.acs.2N.···.···) provides a mapping between R* the space of h y p e r r e a l s X = (χ-. These d e f i n i t i o n s a l l o w us to comprise the o r d i n a r y operations of the a r i t h m e t i c of r e a l s w i t h i n t h i s new world of h y p e r r e a l s .Z)/N=Z and (N.Z)/Z = N.2. Products of i n f i n i t e and i n f i n i t e s i m a l numbers can be f i n i t e however as can be q u o t i e n t s of i n f i n i t e s or of i n f i n i t e s i m a l s . the h y p e r r e a l i n t e g e r s .···.24)) .···.n ) o r Z = (1.Χ ±Υ . Yet we have not the u n d i f f e r e n t i a t e d world of aleph-zero. The r e a l number i n f i n i t e s i m a l l y c l o s e t o any h y p e r r e a l i s c a l l e d i t s standard p a r t . C o n t i n u i t y and d i f f e r e n t i a b i l i t y can be s i m i l a r l y d e f i n e d . 1983 | doi: 10.···) i s an " i n f i n i t e s i m a l " .···) X. · · · . e . you r e c a l l . · · · .η .org Publication Date: July 28.···. DC.χ. Sums of i n f i n i t e s i m a l s are i n f i n i t e s i m a l s . For example (Z+l)/Z and Z/(Z+1) are both i n f i n i t e s i m a l l y c l o s e t o 1 though a l l three are d i s t i n c t h y p e r r e a l numbers.1021/bk-1983-0226. 2012 | http://pubs. · · ·) provided χ ^ 0 — i f i t i s .8 C H E M I C A L REACTION ENGINEERING r e t a i n the r e a l numbers χ as the elements (χ.···.Y = < . I f we use the u s u a l n o t a t i o n f o r the r e a l s we can say that χ ε R. A sequence y^ i n R i s a mapping from Ν the space of i n t e g e r s t o R.4.χ .χ.n.27.Χ. χ Ξ (Χ.f ( a ) } / h f o r a l l i n f i n i t e s i m a l s h.···. f o r example f ( a ) = s t {f(a+h) . χ χ f o r a l l η) and can d e f i n e a r i t h m e t i c a l operations such as X±Y = (χ ±Υ . s t X = χ i f (X-x) i s i n f i n i t e s i m a l . i . ACS Symposium Series. as are products of i n f i n i t e s i m a l s w i t h f i n i t e h y p e r r e a l s .···.nN· · ·) are w e l l . but i t stands as an example of a recent step forward i n the path of a b s t r a c t i o n that began two and a h a l f m i l l e n i a ago (see a l s o (23.Ν = Z.1/n. as are 1/(Z+N). i n t o R*.···.···) and or N. et al.ε.···) a r e t r u l y " i n f i n i t e " numbers. 1983. American Chemical Society: Washington.···) which i s i n any sense of the word an i n f i n i t e i n t e g e r . S i m i l a r l y Z = (1. The D i r a c d e l t a f u n c t i o n can be defined pointwise and new approaches t o the theory of p r o b a b i l i t y and s t o c h a s t i c d i f f e r e n t i a l equations a r e opened up. i n which.d e f i n e d and g i v e (Z+N) . . ignore i t and use 1 i n s t e a d of 1/x s i n c e t h i s can only happen a f i n i t e number of times.. Wei. We say that Y^ converges to Y i f Y = s t Y^ f o r a l l i n f i n i t e i n t e g e r s M. But here Z+N = (N+l.1/2. This can be extended i n the non-standard r e a l s as a mapping from the extension of Ν t o N*.

I t i s not that s l o p p i n e s s of reasoning can be t o l e r a t e d i n the l e a s t . and capable of a s t e r n p e r f e c t i o n such as only the g r e a t e s t a r t can show. w i t h out the gorgeous trappings of p a i n t i n g o r music." But from the realm of the c l a s s i c s . Thus e l e g a n c e — a much deeper q u a l i t y than p r e t t i n e s s . but r a t h e r that r i g o u r i s a d i s c i p l i n e learned w i t h care and p r a c t i c e d w i t h scrupulousness. . but to be a s s i m i l a t e d as p a r t of d a i l y thought. DC. R u s s e l l (26) has w r i t t e n e l o q u e n t l y of the a e s t h e t i c appeal of mathematics i n one of h i s e a r l y essays.org Publication Date: July 28. which i s the touchstone of the h i g h e s t e x c e l l e n c e . Yet he paid f u l l t r i b u t e to Ramanujan's "profound and i n v i n c i b l e o r i g i n a l i t y " . without appeal t o any p a r t of our weaker n a t u r e . 1983. Though denying that mathematicians have c o n s c i o u s l y aimed a t beauty r a t h e r than l o g i c . I n t h i s leap the d r i v i n g f o r c e i s i m a g i n a t i v e rather than l o g i c a l and i t i s the i n s t i n c t f o r beauty which i s the avenue t o t r u t h . f o r so i t appears t o the mathematically c u l t i v a t e d mind.ch001 1. ACS Symposium Series.Downloaded by ILLINOIS STATE UNIV on December 2. i f I remember r i g h t l y . et al. the sense of being more than man. and brought again and again before the mind w i t h ever-renewed encouragement. r i g h t l y viewed. possesses not only t r u t h . I n i t s h i g h e s t forms.. but supreme b e a u t y — a beauty c o l d and austere. I t was.acs. 1983 | doi: 10. Hardy's judgment. 2012 | http://pubs. whereas i t i s the i m a g i n a t i v e leap that reaches out t o a r e s u l t and f e e l s that i t i s r i g h t before the perhaps lengthy c o n f i r m a t i o n i s undertaken that the mathematician c h i e f l y p r i z e s . and the " c o l d and a u s t e r e " beauty of mathematics we must t u r n t o the banausic domain of chemical r e a c t i o n engineering. J. But important though the business of wine making may be i t i s but one of many r e a c t i o n s which l i e at the cores of the d i f f e r e n t processes o f chemical i n d u s t r y and In Chemical Reaction Engineering—Plenary Lectures. Wei. l i k e that of s c u l p t u r e . so r i c h and warm w i t h human a s s o c i a t i o n s . the e x a l t a t i o n .1021/bk-1983-0226. as a mathematician. mathematics has "the s i m p l i c i t y and i n e v i t a b l e n e s s " of great a r t and. y e t sublimely pure. What i s best i n mathematics deserves not merely to be l e a r n t as a task. i s to be found i n mathematics as s u r e l y as i n poetry. at one of these meetings that P r o f e s s o r Wei (27) gave us the connection by p o i n t i n g out that one of the o l d e s t t e c h n o l o g i c a l processes i s the fermentation r e a c t i o n . v a s t l y though he admired him. o f the mathematician Ramanujan was that h i s work f e l l short of t h i s — " i t would be g r e a t e r i f i t were l e s s strange" (25) was Hardy's way of expressing i t . though more r e s t r i c t e d by context than beauty i n the l a r g e r s e n s e — i s g r e a t l y valued i n mathematical c i r c l e s . as pure a r e a c t i v e process as we could wish f o r — r i c h and humane w h i l s t i t stayed w i t h i n our domain and took not up w i t h d i s t i l l a t i o n p r o c e s s e s — a n d r i g h t l y respected i n the very t i t l e of our meeting. "Mathematics. The t r u e s p i r i t o f d e l i g h t .. American Chemical Society: Washington. ARis Reaction Engineering as an Intellectual Discipline 9 In d e s c r i b i n g the c h a r a c t e r i s t i c s o f mathematics I put elegance before r i g o u r .

the comprehensive d e s c r i p t i o n of a l l forms of p o s s i b l e behavior of r e a c t o r s as dynamical systems the pervasiveness of o s c i l l a t i o n and chaos and. but there has always been a p r o p i t i o u s i n t e r c o u r s e between those c h i e f l y concerned w i t h In Chemical Reaction Engineering—Plenary Lectures. 2012 | http://pubs.) Downloaded by ILLINOIS STATE UNIV on December 2. A great refinement of concepts has taken p l a c e over the years as. t r a n s p o r t processes and chemical k i n e t i c s . ACS Symposium Series. The t a l e of t e x t s has lengthened decade by decade.U. s t o i c h e i o m e t r y or mass a c t i o n k i n e t i c s are at i s s u e here. then a f e e l i n g f o r s t r u c t u r e and f i n a l l y a refinement of concept l e a d i n g to a h i g h degree of awareness. Damkohler's work i n the 3 0 s . DC. Wilhelm's and Amundson's i n the 50's are but p o i n t s of touch-down i n the immense s t r i d e s that have taken us onward.. J. save i n the r a r e i n s t a n c e of a Shinnar at the i n d u s t r i a l . ( I have t r i e d to survey some aspects of the h i s t o r i c a l development e l s e where (28).10 C H E M I C A L REACTION ENGINEERING i t i s out of the experience of these that the d i s c i p l i n e of chemical r e a c t i o n engineering has grown. With the e x p l o r a t i o n of instances of these concepts has come an awareness of the v a r i e t i e s of b e h a v i o r .1021/bk-1983-0226.org Publication Date: July 28. The nature of the c o n s t r a i n t s i m p l i e d by t h i s and the inherent s t r u c t u r e o f . Hougen's and Watson's i n the 40's.acs. 1983 | doi: 10. American Chemical Society: Washington. I t was e a r l y recognized that r e a c t o r s presented p e c u l i a r scale-up problems and the height of r e a c t i o n u n i t never a t t a i n e d the popul a r i t y of the H. they range from the four of Damkohler (29) or the modulus of T h i e l e (30) to the Carberry number that B i s c h o f f (31) minted a year or two ago. I t i s t r u e t h a t . the wen of papers has grown year by year and I h e s i t a t e to mention any more names for I am sure to leave out people of great s i g n i f i c a n c e . S i m p l i f i e d s t r u c t u r e s p l a y an important r o l e as i n the i n s i g h t gained from Wei and P r a t e r ' s (32) monomolecular systems and the r e s u l t i n g shape i n v a r i a n c e (33).T. Chemical r e a c t i o n engineering has been n o t a b l e f o r the balance between experiment and theory that has marked i t from the beginning.. t h i s blood and judgment have seldom been "so w e l l commingled" i n one person.a c a d e m i c i n t e r f a c e or a Schmitz i n the more p u r e l y academic context. f o r example. an exhanced a b i l i t y to f e e l a f t e r the form of the s o l u t i o n . m u l t i p l i c i t y and s t a b i l i t y (34). C e r t a i n ideas have been of great importance i n t h i s development and no p a r t of chemical e n g i neering i s r i c h e r i n dimensionless numbers. 1983. . et al. Those are r a t h e r vague terms so l e t my t r y to make them more p r e c i s e and then i l l u s t r a t e some aspects i n greater d e t a i l . I t i s a recent growth i n a s u b j e c t of no long h i s t o r y f o r I suppose that i t i s only i n the l a s t f i f t y years that i t has emerged as a d i s t i n g u i s h a b l e t r a i n of thought. Under balance I t h i n k of the balance t h a t needs to be s t r u c k between theory and p r a c t i c e on the one hand and between the general and the p a r t i c u l a r on the other. w i t h a l l t h i s . f o r example.ch001 T But what has emerged as c h a r a c t e r i s t i c i n t h i s development? I would suggest f i r s t a sense of balance. By s t r u c t u r e I mean the way i n which we have come to see the subject standing on the foundation of thermodynamics. i n the way that we now d i s t i n g u i s h s e n s i t i v i t y . Wei.

chemical engineers are f o r c e d t o t h i n k of the general shape and s t r u c t u r e of r e a c t o r a n a l y s i s i f they are to r e t a i n i t as an i n t e l l e c t u a l d i s c i p l i n e . 1983 | doi: 10.ch001 1 In Chemical Reaction Engineering—Plenary Lectures. Carberry's spinning basket (38) and the Berty r e a c t o r . . 2012 | http://pubs. I t i s a p r a c t i c a l i n g e n u i t y matched on the t h e o r e t i c a l s i d e by some of the devices that have been used i n a n a l y s i n g r e a c t o r models.acs. f o r example. ACS Symposium Series. together w i t h that of Hougen and Watson. They use a r e d u c t i v e scheme which allows the system w i t h Ν r e a c t i o n s t o be analysed by l i m i t i n g cases i n which only η r e a c t i o n s proceed at a f i n i t e r a t e and the Downloaded by ILLINOIS STATE UNIV on December 2. ARIS 11 Reaction Engineering as an Intellectual Discipline p r a c t i c e and those pursuing the e u r i s t i c s of mathematical modelling. of the c a r e f u l c r a f t of the e x p e r i m e n t a l i s t . The i n g e n u i t y of the p r a c t i c i n g r e a c t i o n a r y i s always r e f r e s h i n g : on the i n d u s t r i a l s c a l e we have the c l a s s i c a l case of the f l u i d i z e d bed as w e l l as the s e r e n d i p i t y of the t r a n s f e r l i n e or the i n t r i c a c y of some of the p o l y m e r i z a t i o n r e a c t o r s .f l o w monoliths or Schmitz' polythene bag. The l a t t e r show. the S t e i n e r symmetrization p r i n c i p l e used by Amundson and Luss (42) and the l a t t e r ' s e x p l o i t a t i o n of the formula f o r Gaussian quadrature (43)—perhaps the p r e t t i e s t connection ever made i n the chemical engineering l i t e r a t u r e — a r e t h e o r e t i c a l counterparts. There are many l e v e l s of s t r u c t u r e from the r a t h e r obvious f a c t that stoicheiometry i s a manifes­ t a t i o n of l i n e a r algebra t o the profound a n a l y s i s of mass a c t i o n k i n e t i c s that Feinberg (46) has developed so f u l l y from h i s e a r l i e r work w i t h Horn and Jackson.. 1983. More r e c e n t l y Shinnar has shown how fundamental thermodynamic con­ s t r a i n t s . American Chemical Society: Washington. on the research s c a l e there i s Wicke's creeping zone (35)» Rony s bundle of m i c r o f i l a m e n t s (36). DC. as Amundson's was on the t h e o r e t i c a l (45).o r d e r r e a c t i o n s showed how the s t r u c t u r e of l i n e a r d i f f e r e n t i a l equations leads to both theo­ r e t i c a l and p r a c t i c a l i n s i g h t s i n t o k i n e t i c systems..1021/bk-1983-0226. Wei and P r a t e r ' s (32) now c l a s s i c treatment o f f i r s t . Petersen's s i n g l e p e l l e t r e a c t o r (37).1. was as formative on the engineering s i d e . the s t r i n g of beads used by Hegedus and Oh (39) and Wei and Degnan's (40) combination of c r o s s . g i v e shape t o the problem of understanding a r e a c t i v e system and i n c o r p o r a t i n g i t i n t o u s e f u l design objectives. l a r g e and s m a l l . The i n t r o d u c t i o n of s i n g u l a r i t y theory by G o l u b i t s k y and K e y f i t z (47) and i t s development by Luss and B a l a k o t a i a h (43. Gavalas' use of the index theorem (41). J. such as the requirement that the f r e e energy decrease along a r e a c t i o n path. that a l l the p o s s i b l e b i f u r c a t i o n diagrams can be determined f o r c e r t a i n networks of r e a c t i o n s . So perhaps a l s o the very important i n s i g h t that Danckwerts c o n t r i b u t e d i n h i s f o r m u l a t i o n of the residence time d i s t r i b u t i o n i s a happy f o i l t o h i s h e r o i c ambition t o t r a c e a b l a s t furnace (44). et al. Faced w i t h the enormous v a r i e t y of p r a c t i c a l reactor.org Publication Date: July 28. Amundson's e x p l o i t a t i o n o f the phase plane (34) .48) i s another s t r u c t u r a l landmark. Wei. Wilhelm used t o speak of the "morphology" of the subject years ago i n h i s l e c t u r e s a t P r i n c e t o n and h i s i n f l u e n c e on t h i s s i d e of the A t l a n t i c . The n o t i o n of an e f f e c t i v e n e s s f a c t o r introduced by T h i e l e .

to judge by the demand f o r o f f p r i n t s . the second. DC.. As a p r a c t i c a l device f o r making a product the chemical r e a c t o r presents i t s e l f as a matter of design and c o n t r o l and the engineer may be' s a t i s f i e d to o b t a i n economy i n the one and r e l i a b i l i t y i n the other. T h i s i s where such t o o l s as s i n g u l a r i t y theory or that of catastrophes. But there has been a steady i n c o r p o r a t i o n of prec i s e l y defined concepts as f o r example i n the burgeoning study of Downloaded by ILLINOIS STATE UNIV on December 2. stemming from the mathematical component of the s u b j e c t . as I have t r i e d to expound i t elsewhere (see Chap. A f u r t h e r c h a r a c t e r i s t i c of chemical r e a c t i o n engineering i s i t s f a c i l i t y i n r e f i n i n g concepts. even i f i t were n e c e s s a r i l y r e l e v a n t . but i t has been t y p i c a l of i t s development s i n c e the d i s t i n c t i o n between s t a b i l i t y and s e n s i t i v i t y was f i r s t drawn (34).acs. a l a s . which I w i l l advert to at the end. the r e a c t o r must be regarded comprehensively. There have been l a p s e s . 1983 | doi: 10. f o r i t s t i t l e was "On the s t a b i l i t y c r i t e r i a of chemical r e a c t i o n engineering" w h i l e i t s burden was as much the m u l t i p l i c i t y c r i t e r i a as the s t a b i l i t y c o n d i t i o n s . However i t would take us too f a r a f i e l d and. ACS Symposium Series. American Chemical Society: Washington. to say more on t h i s s i n c e a paper at t h i s meeting w i l l b r i n g us up to date on t h e i r t h i n k i n g . when r i g h t l y used.ch001 s In Chemical Reaction Engineering—Plenary Lectures. But i t r a i s e s two p o i n t s of importance. I t i s a d e r i v e d c h a r a c t e r i s t i c . Thus i t could be s a i d that the dynamical behavior of any such system was t o p o l o g i c a l l y e q u i v a l e n t to any other w i t h the same l a b e l . 2012 | http://pubs. however. I t i s tempting to d i g r e s s at t h i s p o i n t and enlarge on the v i r t u e s of chemical r e a c t i o n engineering as a source of m a t e r i a l f o r the c r a f t of f e e l i n g out a s o l u t i o n . as i n the case of an e x p o s i t o r y paper (52) which. o f t e n g i v e comprehensive i n f o r m a t i o n . the immensity of many dimensions. The f i r s t i s the i n s t i n c t f o r comprehensiveness. T h i s i s as important a technique to l e a r n and teach as i t i s enjoyable i n i t s e x e r c i s e .12 C H E M I C A L R E A C T I O N ENGINEERING others are e i t h e r instantaneous or g l a c i a l l y slow. but which r a t e d a very low Watkins number (53). proved q u i t e u s e f u l . we have the r i g h t and duty to enquire of i t s behavior f o r any. J. I w i l l r e s i s t the temptation even though I have a brand new example making p r o p i t i o u s ferment i n my v i t a l s . et al. Wei. . As an object f o r i n t e l l e c t u a l comprehension. 2 of 28. 50.51). I t i s not a q u e s t i o n of c o n s i d e r i n g a l l p o s s i b l e r e a c t o r s but of a c h i e v i n g a working r e a c t o r that w i l l be i n t e g r a t e d i n t o a whole p l a n t and come on stream i n time to make a p r o f i t .1021/bk-1983-0226. A case i n which the s t r i c t numerical d e f i n i t i o n of regions of parameter space could be replaced by geom e t r i c a l l y d i s t i n c t p o s s i b i l i t i e s arose w i t h the competition of two m i c r o b i o l o g i c a l populations f o r a s i n g l e n u t r i e n t i n a continuous fermentor which Arthur Humphrey and I considered a few years ago (49). 1983.c a l l e d " r e a l i s t i c " .org Publication Date: July 28. I t would be i n a p p r o p r i a t e . We were able to show how the r e l a t i v e d i s p o s i t i o n s of the two growth curves and the p o i n t r e p r e s e n t i n g the d i l u t i o n r a t e and feed c o n c e n t r a t i o n could be encoded i n t o a l a b e l which was a s s o c i a t e d w i t h a phase p o r t r a i t .. not j u s t the s o . f o r they can. values of the parameters. the q u a l i t a t i v e theory of d i f f e r e n t i a l equations or t o p o l o g i c a l methods are so important.

an open set of i n i t i a l s t a t e s which would l e a d t o the same steady s t a t e . J.a t o r s which i t would be rash t o rush i n t o here. DC. But even as the n o t i o n of p e r i o d i c s o l u t i o n s t o the n o n l i n e a r d i f f e r e n t i a l equations of chemical r e a c t o r theory was growing i n c r e a s i n g l y f a m i l i a r i n the '60*s and 7 0 s . R b s s l e r . The B e l o u s o v .Downloaded by ILLINOIS STATE UNIV on December 2. I t i s dangerous to mention names when I am sure to omit many important ones but those of Y a b l o n s k i i . 1983. ARis Reaction Engineering as an Intellectual Discipline 13 chaos which i s evoking i n t e r e s t from mathematicians.ch001 1. desorption and rearrangement on the c a t a l y s t surface may themselves produce m u l t i p l e r e a c t i o n r a t e s o r o s c i l l a t i o n s . Uppal. This stemmed from a v a s t l y s i m p l i f i e d m e t e o r o l o g i c a l model of three modestly n o n l i n e a r equations s t u d i e d by Lorenz (60) which e x h i b i t e d s o l u t i o n s which were n e i t h e r p e r i o d i c nor asymptotic to p e r i o d i c s o l u t i o n s . Takoudis. Jensen over here s p r i n g to mind i n a d d i t i o n to those already mentioned. Ray and Poore (56) were able to show that the u n c o n t r o l l e d non-adiabatic s t i r r e d tank w i t h a s i n g l e exothermic r e a c t i o n — t h e s i m p l e s t non-isothermal s y s t e m — could e x h i b i t a wide v a r i e t y of behavior i n c l u d i n g m u l t i p l e steady s t a t e s and l i m i t c y c l e s w i t h i n l i m i t c y c l e s . Eigenberger and Hugo i n Germany. Ray. I n the 50's i t seemed l i k e l y that o s c i l l a t i o n s i n r e a c t o r s would be most l i k e l y t o a r i s e when a c o n t r o l system was added t o the r e a c t o r (54) . The n o t i o n of m u l t i p l i c i t y c a r r i e d w i t h i t the p i c t u r e of the a s s o c i a t e d r e g i o n of a t t r a c t i o n . the exothermic sequence T T f In Chemical Reaction Engineering—Plenary Lectures. The p r o p e r t i e s of such s o l u t i o n s soon a t t r a c t e d a t t e n t i o n of mathematicians and others and there i s a t h r i v i n g i n d u s t r y t r y i n g to put order i n t o chaos a t the moment (61).1021/bk-1983-0226. Denbigh (55) had shown t h i s i n h i s p i o n e e r i n g work using the n o t i o n of " e q u i f i n a l i t y " adumbrated i n a b i o l o g i c a l context by Burton. there was s p r o u t i n g beside i t the new ideas of chaos and non-periodic behavior.and the other endothermic. . American Chemical Society: Washington. one exo.org Publication Date: July 28. Kenney i n England and Luss. d i s s i p a t i v e systems and l o c u s . S l i n k o and t h e i r colleagues i n R u s s i a . T h e i r t a l e of p o s s i b l e modes of behavior was s c a r c e l y t o l d before a group of Russian authors (57) augmented i t .Z h a b o t i n s k i i r e a c t i o n has of course generated a minor i n d u s t r y of experimental and t h e o r e t i c a l s t u d i e s . ACS Symposium Series.. Wei. An important r e a l i z a t i o n that has been a t t a i n e d i n recent years i s that the processes of a d s o r p t i o n . But. Pismen (62) i n h i s e x c e l l e n t review of k i n e t i c i n s t a b i l i t i e s was able t o g i v e s e v e r a l references and has h i m s e l f shown how data sampling can c o n t r i b u t e i t s meed of randomness. Schmidt. et al. 1983 | doi: 10.acs. u s i n g the newly r e v i v e d notions of Hopf b i f u r c a t i o n . 2012 | http://pubs. Lynch and others (64) have used p a r a l l e l r e a c t i o n s . Wicke (35) and h i s colleagues found t h i s some years ago and the reviews of Sheintuch and Schmitz (58) and Scheintuch (59) show how wide-spread the phenomenon i s . I t i s c r e d i b l y h e l d that at l e a s t three equations are needed f o r c h a o t i c behavior and i t i s not s u r p r i s i n g that i t has been found i n the s t i r r e d tank when two r e a c t i o n s are t a k i n g p l a c e . Already a t the l a s t of these symposia. p h y s i c i s t s and chemists as w e l l as engineers. Varma and K a h l e r t (63) have found i t f o r consecutive r e a c t i o n s ..

1021/bk-1983-0226. says the p r a c t i c a l l y . et al.. 2012 | http://pubs. σ.l i n e a r i t y E(w) = expiyw/(γ+w)} Downloaded by ILLINOIS STATE UNIV on December 2. These cascaded i n t o chaos. the r a t i o of the heats of r e a c t i o n .acs. As a branch of p r a c t i c a l engineering chemical r e a c t o r s may be t o l e r a b l y w e l l understood without a l l the refinements of t h i s i n t r i c a t e behavior. the question of how to master the daunting "espaces i n f i n i s " (68) of In Chemical Reaction Engineering—Plenary Lectures. Wei. s t a b i l i t y and i n p a r t i c u l a r the Hopf b i f u r c a t i o n l o c i .u{l+aE(w)} ν w = = auE(w) . γ. which subsided i n t o regimes of o s c i l l a t i o n s of s i x times the p e r i o d of the p r i n c i p a l .ch001 (which reduces to expw i f γ—*») and are: ύ = 1 . ACS Symposium Series.7. to be constant she v a r i e d t h i s over an i n t e r v a l (5 < κ < 8) i n which there was a s i n g l e unstable steady s t a t e and t h e r e f o r e at l e a s t one o s c i l l a t o r y s o l u t i o n . The g r e a t e r p a r t of each i n t e r v a l was occupied by a c y c l e of approximately twice the p e r i o d of the p r i n c i p a l o s c i l l a t o r y s o l u t i o n . recovered as p e r i o d 10 o s c i l l a t i o n s . But n e v e r t h e l e s s i t moves and i t i s not so many years s i n c e Amundson's c r i t e r i a f o r s t a b i l i t y were thought to be i d l e s o p h i s t r i e s . the temperature. 3. They c o n t a i n a c h a r a c t e r i s t i c n o n .29). 1983. κ. 1983 | doi: 10. w i t h i n which two i n t r i c a t e l y complex p a t t e r n s of t r a n s i t i o n s could be seen. DC. a dimensionless heat t r a n s f e r c o e f f i c i e n t . v.5. the p r i n c i p a l o s c i l l a t i o n .49.95.m i n d e d engineer: " s t u l t i t i a est enim i l l i " (6 7). and w.14 C H E M I C A L REACTION ENGINEERING A->B->C has a l s o been considered by Jorgensen (65) . i t s dimensionless heat of r e a c t i o n . the Damkôhler number f o r A-*B. the r a t i o of the Damkohler numbers.org Publication Date: July 28. the concentrations of A and B. i t s A r r h e n i u s number. w i t h seven parameters: a. "Morris a n t i c s " (6_6) indeed and a l l w i t h i n the f i f t h decimal p l a c e ! "So what". There were two s u b i n t e r v a l s . Then t a k i n g a l l parameters except κ. they show that the v e i n . the c o o l i n g r a t e parameter. r i c h as i t has proved to be. (5. There may indeed be systems f o r which some of these regions of complexity have a s i g n i f i c a n t s i z e or are s i t u a t e d i n an otherwise d e s i r a b l e r e g i o n of parameter space. As an o b j e c t of i n t e l l e c t u a l study these apparently e s o t e r i c f e a t u r e s are of great moment. . The v a l u e of comprehensiveness makes demands t h a t open up a question which I b e l i e v e w i l l be a l l important i n t h i s decade. cascades of p e r i o d doublings l e d to chaos. i s not mined out y e t . American Chemical Society: Washington. J. p. the p a t t e r n s being t o p o l o g i c a l m i r r o r images of each other. This l a s t i s a system of three equations f o r u and v. but then as the values of κ moved outward through the l a s t f r a c t i o n s of the s u b i n t e r v a l s .60) and (6.v { l + a a E ( w ) } -(1+K)W + a3uE(w) + α$ρσ vE (w) V V 1 Jorgensen s f i r s t endeavour was to map out the regions of m u l t i p l i c i t y . the r a t i o of a c t i v a t i o n energies of the two r e a c t i o n s . r e l a p s e d and recovered as p e r i o d 8's b e f o r e t h e i r f i n a l widdershins as fandangos f o r c h a o t i c and p e r i o d i c s o l u t i o n s ..

H. however. 75. The Johns Hopkins Press. E d . but how can we tread the edge of chaos? Even t h i s . L. 2012 | http://pubs. F . 1912 (biographical notice in V o l . . such as those of Feinberg i n k i n e t i c s . P r a c t i c a l i t y can sometimes come t o our a i d by c o n f i n i n g a t t e n t i o n t o subspaces which a r e . "Studies in Honor of Basil L .1021/bk-1983-0226. 2. "An Introduction to J. r e v e a l i n g the power of a s u b j e c t apparently so humdrum as chemical r e a c t i o n engineering t o charm "the wide casements opening on the foam of k e e l l e s s seas i n f a i r y lands f o l o r n " (69). F. But u l t i m a t e l y i t w i l l r e q u i r e some new i n s i g h t t o expand our imaginations. the Johns Hopkins Centenial Lectures: Supplement to the American Journal of Mathematics. Sylvester". We need theorems of great power. We need ways of keeping i n the important i n t e r f a c e s so that the boundaries of d i f f e r e n t regions do not have t o be determined by t r i a l and e r r o r . ARIS Reaction Engineering as an Intellectual Discipline 15 a l a r g e number of parameters. . E d . 1902. According to Ε. H. 7.. B e l l (Men of Mathematics) he resigned after three months on account of the "refusal of the University authorities to discipline a student who had insulted him.Downloaded by ILLINOIS STATE UNIV on December 2. i n some sense.. "Such a considerable change deserved a better fate than b e f e l l . "The Creed of the Old South". J. . I t i s f a i r l y easy t o see how t o keep on the margin of s t a b i l i t y . 3.. 4). 5.. i n some sense. 1983. Gildersleeve.org Publication Date: July 28. The outcome was his almost immediate return. "The Collected Mathematical Papers of James Joseph Sylvester" (four volumes). Baltimore. American Chemical Society: Washington. T. o p t i m a l o r . Cambridge. s a f e . Gildersleeve". 1930. ACS Symposium Series. Baker. in "Algebraic Geometry".. Baker writes in the Biographical Notice in Volume 4 of the Collected Mathematical Papers. DC. 4. E d . and Sylvester had a horror of slavery. et al. convinced that he had k i l l e d a student in self defense—a conviction that fortunately proved to be false". In Chemical Reaction Engineering—Plenary Lectures. Baltimore. "Selections from the Brief Mention of B. Literature Cited 1. Of his experiences in 1841 H. Baltimore. There is some confusion over the reason for Sylvester's untimely departure from the University of V i r g i n i a . J-I. 1892. that w i l l b l o c k out whole subspaces and ensure that no e x o t i c type of behavior can hurt o r devour there. 1983 | doi: 10.. J. B." According to Woolf "within three months he was on his way back to England. C. Johns Hopkins Press. Gildersleeve". only reduces the d i m e n s i o n a l i t y by one or two and enormous d i f f i c u l t i e s s t i l l remain. "Essays and Studies—Educational and Literary"." Woolf. Wei. apparently he had intervened vigorously in a quarrel between two of his students. 1890. W.acs. 6. .ch001 1. Igusa. L . E. Atlantic Monthly Jan. in Virginia at this time the question of slavery was the subject of bitter contention.. M i l l e r .

. R. American Chemical Society: Washington.org Publication Date: July 28. 16. Applies. 27. 18.. 37.. ii. 34. Proc. Peloponesian War III. 49. 1939. 1910. Wicke. 1982. seems to have escaped the public record..E. Ch. Damköhler. Z. Review of "Insights into Chemical EngineeringSelected Papers of P. 1982. Math. De Plac. A. Academic Press: New York. 15. Math. Eng. . Bull. 1940. Wei. A. 1925. Chem. 15. Bull. 1955.. "Ramanujan—Twelve Lectures Suggested by His Life and Work"..8. "Physical Phenomena in Catalysis and in Gas-Solid Surface Reactions". 26. D. Aris. 1. Housman. 1st Int.16 8. Applies. Applies. 19. W. V. 1123. A. 1. W. Cicero. Carter. A. 13. Macmillan: London. Macmillan: London. Cambridge University Press: Cambridge. 43. Whitehead. 32.. Diffusion und Wärmeiiberganges auf die Leistung von Reacktions öfen. 33. 18. 73. 1940. Finley. C H E M I C A L REACTION ENGINEERING Plutarch. 35.. Hardy. Gow. Κ. 9 May 1968. 21.. 1983 | doi: 10. Inst. Thiele. and Bilous. "Reflections on Some Trends in Chemical Reaction Engineering". Cambridge University Press: Cambridge. 10. 846. 17. 42. D. Hardy. S. and Prater. 12. "The Structure and Analysis of Complex Reaction Systems". "Four Stages of Greek Thought". "A Mathematician's Apology". iii..ch001 14.. Bischoff. 52. D. on Chem. Shakespeare. A. 10. 20. "The Confines of Criticism". O. 1983. Engng. R. i. 22. Nat. 513. 5. In Chemical Reaction Engineering—Plenary Lectures.. 23. Downloaded by ILLINOIS STATE UNIV on December 2. I. Η. 1969. 5. 13. 18.. N. Einflüsse der Strömung... E. Danckwerts". R. E.82-3. Math. Conf. 24.. Advances in Catalysis. 28. Times Literary Supplement. G....I. Engng. A. Hist. Cutland. Longmans Green: London. 1916. Aris. Wei.E. G. Bull. 1938. despite its interest and importance. R. B. Chem. F. J.. Vol. J. 1970. 2012 | http://pubs. Amundson. 1936. 1972. Aris. "Twelfth Night".. Clarendon Press: Oxford. Livingstone. 1936. "Science and the Modern World". American Chemical Society: Washington. 916. J. Russell. Inst. Ind.. Cambridge University Press: Cambridge. Eng. 30. "A Defense of Classical Education".. Chap. DC. 44. ACS Symposium Series. Sci. A.acs. This observation. 18.. 31. 29. 240. De Universo. J. 1982. 31.Ch. N. W. N. p. University of Wisconsin Press: Madison. Reac. Washington. J. 9. W. H.C. Vol. Electrochem... J. C. Pliny. J. Chem. 3. 34. Phil. R. R. 223. 25. Fundamentals 1976. Inst. Ibid.. E. Wei. Cambridge University Press: Cambridge. p. 99-101. 1937. Ingleton. "The Mathematical Theory of Diffusion and Reaction in Permeable Catalysts". 229. I. "The Study of Mathematics" in "Philosophical Essays". 11. Β. 4 of "Chemical Engineering in the University Context". 1982.. 1982.W. "Housman. F. Ind. Η. A Sketch". Ed. Thucydides. et al. Hoskins.1021/bk-1983-0226.

1.

36.
37.
38.
39.

Downloaded by ILLINOIS STATE UNIV on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch001

40.

41.

42.
43.
44.
45.
46.

47.
48.
49.
50.
51.
52.
53.

54.
55.
56.
57.
58.
59.
60.

ARIS

Reaction Engineering as an Intellectual Discipline

17

Rony, P. R., J. Am. Chem. Soc. 1972, 94, 8247.
Petersen, Ε. E. and Hegedus, L. L., Ind. Eng. Chem.
Fundamentals 1972, 11, 579.
Carberry, J. J., Ind. Eng. Chem. 1964, 56, 39.
Oh, Se H., Hegedus, L. L., Baron, K. and Cavendish, J. C.,
"Carbon Monoxide Oxidation in An Integral Reactor. Transient
Response to Concentration Pulses in the Regime of Isothermal
Multiplicities";
Proc. ISCRE5 ACS Symposium Series 65,
American Chemical Society: Washington, D.C., 1978, p. 461.
Wei, J. and Degnan, T. F., "Monolithic Reactor-Heat Exchanger";
Proc. ISCRE5 ACS Symposium Series 65, American Chemical
Society: Washington, D.C., 1978, p. 83.
Gavalas, G. R., "Nonlinear Differential Equations of
Chemially Reacting Systems"; Springer-Verlag:
Heidelberg,
1968.
Amundson, N. R. and Luss, D., A.I.Ch.E. J. 1967, 13, 759.
Luss, D. and Balakotaiah, V. Chem. Engng. Sci. (to appear).
Danckwerts, P. V., "Insights into Chemical Engineering
(Selected Papers of P. V. Danckwerts)"; Pergamon Press:
Oxford, 1982.
I have touched on some aspects of this in the Wilhelm
Lecture for 1981 and in 24.
Feinberg, Μ., Chemical Oscillations,
Multiple Equilibria and
Reaction Network Structure
in "Dynamics and Modelling of
Reactive Systems"; Stewart, W. E., Ray, W. H. and Conley,
C. C., Eds.
Golubitsky, M. and Keyfitz, B. L., SIAM Journal Math. Anal.
1980, 11, 216.
Balakotaiah, V. and Luss, D., A.I.Ch.Ε.
J. (to appear).
Humphrey, A. E. and Aris, R., Biotech, and Bioeng. 1977, 19,
1375.
Aris, R., "Mathematical Modelling Techniques"; Pitman: London,
1978.
Aris, R., Chem. Eng. Educ. 1976, 10, 114.
Aris, R., Chem. Engng. Sci. 1969, 24, 149.
The Watkins number is a dimensionless measure of appropriate­
ness in the closed interval 0 ≤Wa ≤ 1. It was introduced
by Re in "a conversation on some aspects of mathematical
modelling"; Appl. Math. Modelling 1977, 1, 386.
Amundson, N. R. and Aris, R., Chem. Engng. Sci. 1958, 1, 122.
Denbigh, Κ. G., Trans. Faraday Soc. 1944, 40, 352.
Uppal, Α., Ray, W. H. and Poore, A. B. Chem. Engng. Sci. 1974,
29, 967.
Vaganov, D. Α., Samoilenko, N. G. and Abramov, V. G., Chem.
Engng. Sci. 1978, 33, 1133.
Sheintuch, M. and Schmitz, R. Α., Cat. Rev. Sci. and Eng.
1977, 15, 107.
Sheintuch, M., Kinetic Instabilities
in Catalytic Oxidation
Reactions (a review to appear).
Lorenz, Ε. N., J. Atmos. Sci. 1963, 20, 130.

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

C H E M I C A L REACTION

18

61.

62.
63.

Downloaded by ILLINOIS STATE UNIV on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch001

64.
65.
66.
67.
68.
69.

ENGINEERING

It would be impossible to give an adequate bibliography of
the work on chaos and strange attractors, but the proceedings
of a Los Alamos Conference held in May 1982 under the title
of "Order in Chaos" will, when they appear, give a good
picture of the variety of activity.
An introductory sketch
of one aspect is given in 53.
Pismen, L. Μ., Chem. Engng. Sci. 1980, 35, 1950.
Rössler, O., Varma, A. and Kahlert, C. in "Modelling Chemical
Reaction Systems"; Ebert, K. and Jaeger, W., Eds., Springer
Verlag: Heidelberg, 1981.
Lynch, D. T., Rogers, T. D. and Wanke, S. Ε., Math. Modelling
1982, 0, 000.
Jorgensen, D. V. and Aris, R. will be in the Jan. 1983 issue
of Chem. Engng. Sci.
Bridges, R. W., "The Testament of Beauty. III"; Oxford, 1929,
1. 938.
Hieronymus, E., Vulgate version of I. Cor. 2, 14.
Pascal, B., Pensées.
III, 206.
Keats, J., Ode to a Nightingale, u. 69-70. I quote Keats'
original version so that the reader may have the enjoyment
of discussing its variations from the well-known final text.

RECEIVED March 10, 1983

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

2
Development of the Methanol-to-Gasoline
Process
1

J. E. PENICK, W. LEE, and J. MAZIUK

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch002

Mobil Research and Development Corporation, New York, N Y

10017

Mobil has developed a new process for
conversion of methanol to high quality gasoline
using a unique class of shape-selective zeolite
catalysts.
This process provides a novel route
to gasoline from either coal or natural gas via
intermediate methanol. Two reactor systems have
been devised by Mobil for this process—fixed
bed and fluid bed. The f i r s t commercial
application of the fixed-bed process w i l l be i n
a 14,000 B/D (gasoline) plant based on natural
gas which w i l l be located in New Zealand. The
fluid-bed process i s being scaled up to a
100 B/D (methanol) demonstration plant located
in W. Germany. In this paper, the chemistry of
the process is reviewed and the engineering
involved i n selection, scale-up, and design of
an appropriate reactor system to produce an
acceptable product i s discussed.
M o b i l has developed a novel process f o r converting methanol
i n t o high q u a l i t y g a s o l i n e . ( 1 ) Since methanol can be made from
n a t u r a l gas o r c o a l by w e l l - e s t a b l i s h e d commercial technology,
the Methanol-to-Gasoline (MTG) process provides a unique
approach to the p r o d u c t i o n of g a s o l i n e from e i t h e r raw m a t e r i a l
as shown i n Figure 1. In the MTG process, methanol i s
q u a n t i t a t i v e l y converted to hydrocarbons and water. The
hydrocarbons are p r i m a r i l y g a s o l i n e b o i l i n g range m a t e r i a l s
s u i t a b l e f o r use as high q u a l i t y automotive f u e l .
1

Correspondence should be sent to W. Lee, Mobil Research and Development Corporation, Paulsboro, NJ 08066

0097-6156/83/0226-0019$08.50/0
© 1983 American Chemical Society

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

Ash

τ

Coal
Gasifier

Stearn

MTG
Process

GASOLINE
Τ
Water

Making gasoline from c o a l o r n a t u r a l gas v i a MTG.

Raw
Methanol

Water

Τ

MTG
r-*-GASOLINE
Process

F i g u r e 1.

Methanol
Process

Methanol
Process

Raw
Methanol

Synthesis
Gas
(CO + hh)

(CO + H2)

Synthesis
Gas

Steam
Reforming
Process

NATURAL G A S

Steam

Oxygen

COAL

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch002

the development of the MTG process w i l l be reviewed. . In t h i s l e c t u r e . the key element i n the MTG process. et al.1021/bk-1983-0226. scheduled f o r completion i n 1985. 1983 | doi: 10.Downloaded by UNIV OF ARIZONA on December 2.and f l u i d . Two 2.t r a i n MTG p l a n t . Wei. The pore-opening of these channels i s about 6 A and i s j u s t wide enough t o produce hydrocarbons b o i l i n g p r i m a r i l y i n the g a s o l i n e range. These u n i t s j o i n through edges t o form chains and sheets. tortuous channels. Methanol-to-Gasoline Process 21 The MTG process w i l l soon see i t s f i r s t commercial a p p l i c a t i o n i n a p l a n t c u r r e n t l y being constructed f o r the New Zealand S y n t h e t i c Fuels Corporation L i m i t e d . and the narrow-pore z e o l i t e s . l e a d i n g to the three dimensional s t r u c t u r e r e p r e s e n t a t i o n shown i n the f i g u r e . The l i n e s i n Figure 2 represent oxygen atoms i n a s i l i c e o u s framework.b e d processes. the choices f o r the conversion system w i l l be presented along w i t h the dual-pronged s t r a t e g y f o r development of both the f i x e d .s e l e c t i v e s y n t h e t i c z e o l i t e w i t h a unique channel s t r u c t u r e as shown i n Figure 2. chemistry. 2012 | http://pubs.(2) This s t r u c t u r e i s d i s t i n c t i v e l y d i f f e r e n t from the f a m i l i a r wide-pore z e o l i t e .ch002 2.org Publication Date: July 28. PENICK E T A L . This p l a n t . This i s e q u i v a l e n t t o about 1/3 of New Zealand's g a s o l i n e consumption. Catalyst The ZSM-5 c a t a l y s t . There are c u r r e n t l y f i v e l i c e n s e d processes (other than MTG) based on the ZSM-5 f a m i l y : 1 D i s t i l l a t e dewaxing Xylene i s o m e r i z a t i o n Toluene d i s p r o p o r t i o n a t i o n Ethylbenzene synthesis L u b r i c a t i n g o i l dewaxing In Chemical Reaction Engineering—Plenary Lectures. J.000 BPSD) of unleaded g a s o l i n e averaging 92 t o 94 research octane. I t contains a novel c o n f i g u r a t i o n of l i n k e d t e t r a h e d r a c o n s i s t i n g of e i g h t five-membered r i n g s . w i l l produce g a s o l i n e from methanol derived from New Zealand n a t u r a l gas. Since the mid-1970 s. our f u t u r e development plans f o r t h i s general area o f technology w i l l be h i g h l i g h t e d . and i t s s p e c i a l r e a c t o r design aspects — w i l l be d i s c u s s e d .acs.. Next. i s a s h a p e . f a u j a s i t e . F i n a l l y . I t contains two i n t e r s e c t i n g channels: e l l i p t i c a l 10-membered r i n g s t r a i g h t channels and s i n u s o i d a l . I t w i l l produce some 570.200 tonnes-per-day methanol p l a n t s w i l l provide the feed f o r the s i n g l e .000 tonnes per year (14. 1983.. more than 25 commercial p l a n t s have been commissioned using t h i s c a t a l y s t f a m i l y . the unique aspects o f MTG — the c a t a l y s t . F i r s t . American Chemical Society: Washington. ACS Symposium Series. DC.

.acs. American Chemical Society: Washington. Copyright 1978. 1983 | doi: 10.org Publication Date: July 28. .) In Chemical Reaction Engineering—Plenary Lectures. ZSM-5 s t r u c t u r e . Macmillan..1021/bk-1983-0226. 1983. et al. J. (Reproduced "with p e r m i s s i o n from Ref. ACS Symposium Series.Downloaded by UNIV OF ARIZONA on December 2. Wei. 2. 2012 | http://pubs. DC.ch002 22 C H E M I C A L REACTION ENGINEERING Figure 2.

2.

PENICK E T A L .

23

Methanol-to-Gasoline Process

A l l o f these a p p l i c a t i o n s use fixed-bed r e a c t o r s , and, very
i m p o r t a n t l y , a l l were scaled up from bench-scale p i l o t p l a n t
data. This s u c c e s s f u l scale-up experience w i t h the ZSM-5
c a t a l y s t was an important c o n s i d e r a t i o n i n f o r m u l a t i n g the MTG
development s t r a t e g y .
Chemistry
The conversion of methanol t o hydrocarbons over ZSM-5 i s
well-represented by the f o l l o w i n g s i m p l i f i e d r e a c t i o n
network(3):
-H 0
^
^
+H 0

-H 0

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch002

2

2CH OH
3

2

2

CH3OCH3

> C -C
Olefins
2

5

Paraffins
> Aromatics
Cycloparaffins

The i n i t i a l dehydration r e a c t i o n i s s u f f i c i e n t l y f a s t t o
form an e q u i l i b r i u m mixture of methanol, dimethyl e t h e r , and
water. These oxygenates dehydrate f u r t h e r t o g i v e l i g h t
o l e f i n s . They i n t u r n polymerize and c y c l i z e t o form a v a r i e t y
of p a r a f f i n s , aromatics, and c y c l o p a r a f f i n s . The above
r e a c t i o n path i s i l l u s t r a t e d f u r t h e r by Figure 3 i n terms o f
product s e l e c t i v i t y measured i n an isothermal l a b o r a t o r y
r e a c t o r over a wide range of space v e l o c i t i e s . ( 3 )
The r a t e
l i m i t i n g step i s the conversion of oxygenates t o o l e f i n s , a
r e a c t i o n step that appears t o be a u t o c a t a l y t i c . I n the absence
of o l e f i n s , t h i s rate i s slow; but i t i s a c c e l e r a t e d as the
c o n c e n t r a t i o n of o l e f i n s i n c r e a s e s .
Under MTG c o n d i t i o n s , almost no hydrocarbons are found
higher than C ^ Q due to the shape s e l e c t i v i t y o f ZSM-5. While
higher molecular weight compounds may be formed w i t h i n the
c a t a l y s t channels, they do not escape due t o the s p a t i a l
hindrance of the c a t a l y s t s t r u c t u r e .
Reactor Design
Although the design of a r e a c t o r system f o r the MTG process
i n v o l v e s c l a s s i c a l chemical engineering p r i n c i p l e s , the unique
c a t a l y s t and r e a c t i o n mechanisms impose important design
c o n s t r a i n t s . These i n c l u d e the h i g h l y exothermic nature of the
r e a c t i o n , the need f o r e s s e n t i a l l y complete methanol conversion,
steam d e a c t i v a t i o n of the c a t a l y s t , the "band-aging" phenomena,
and durene formation.

Exotherm - The heat of r e a c t i o n i s 1740 kJ/kg of
methanol which i f u n c o n t r o l l e d would g i v e an
a d i a b a t i c temperature r i s e of about 600°C.
Therefore, a p r i n c i p a l c o n s i d e r a t i o n i n designing a
r e a c t o r system i s r e a c t i o n heat management.

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

Wt. %

Products,

( ^ )

i l ι 111

ι

1

1—I

Olefins)

5

ι ι 1 1 ifr—Q-o-i

Olefins
1

Aromatics

P—D-D-

Paraffins
(and C $ +

10

M i l l

o-o o- W a t e r

ι ι ι 111

C2-C5

1—τ—ι

Figure 3. E f f e c t o f space v e l o c i t y a t 101 kPa and 371 C.
(Reproduced w i t h permission from Ref. 3. Copyright 1977
Academic Press.)

S p a c e Time

1

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch002

2

w
w
S
ο

3

δ
w
ο

H

ο

m
>

ο
w

to
-Ρ»

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch002

2.

PENiCK E T A L .

Methanol-to-Gasoline Process

25

Complete Methanol Conversion - The major products
of the MTG conversion are hydrocarbons and water.
Consequently, any unconverted methanol w i l l
d i s s o l v e i n t o the water phase and be l o s t unless a
d i s t i l l a t i o n step to process the very d i l u t e water
phase i s added to the process. Thus, e s s e n t i a l l y
complete conversion of methanol i s h i g h l y p r e f e r r e d .

C a t a l y s t D e a c t i v a t i o n - Under MTG r e a c t i o n
c o n d i t i o n s , ZSM-5 c a t a l y s t undergoes two types of
aging which c o n t r i b u t e to a gradual l o s s of
c a t a l y s t a c t i v i t y . A r e v e r s i b l e l o s s r e s u l t s from
"coke" formed on the c a t a l y s t as a r e a c t i o n
byproduct.
This d e a c t i v a t i o n i s a t y p i c a l
c a t a l y t i c process design problem. What i s unusual
about the MTG process i s that a r e a c t i o n product,
steam, i s a l s o r e s p o n s i b l e f o r a gradual l o s s o f
a c t i v i t y . However, low r e a c t o r temperatures and
low p a r t i a l pressure of water w i l l minimize t h i s
aging and favor a long c a t a l y s t l i f e .

Band-Aging - E s p e c i a l l y w i t h f r e s h c a t a l y s t s , the
r e a c t i o n occurs over a r e l a t i v e l y s m a l l zone i n a
f i x e d bed. This r e a c t i o n f r o n t marches down the
c a t a l y s t bed as the coke d e p o s i t s f i r s t d e a c t i v a t e
the f r o n t part of the bed (Figure 4 ) . Use o f a
s u f f i c i e n t c a t a l y s t volume permits a fixed-bed
design i n which on-stream periods are long enough
to avoid o v e r l y frequent regeneration c y c l e s .

Durene Formation - An aromatic compound, durene ( 1 ,
2, 4, 5-tetramethylbenzene) i s produced i n the MTG
process. Durene has e x c e l l e n t research octane
blending q u a l i t y (110 RON c l e a r ) and b o i l s w i t h i n
the g a s o l i n e d i s t i l l a t i o n range (197°C); however,
i t s f r e e z i n g p o i n t i s r e l a t i v e l y high a t 79°C.
Based on our current designs, the g a s o l i n e d i r e c t l y
from the ZSM-5 r e a c t o r s could c o n t a i n 4 t o 7 wt%
durene. These concentrations of durene could lead
to problems w i t h s o l i d s build-up i n carburetors
during c o l d s t a r t s . While durene i s present i n
conventional g a s o l i n e , the t y p i c a l concentrations
are low enough not t o cause problems.

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch002

26

CHEMICAL

II

0

n

«frft»^frofr;ii^

0.1

0.2

0.3

ENGINEERING

ι

ι

ι

ι

ι

ι

1

0.4

0.5

0.6

0.7

0.8

0.9

1

Fractional Bed

Figure k.
bed.

REACTION

Length

Movement o f normalized temperature p r o f i l e through

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

. PENICK E T A L . DC.1021/bk-1983-0226.b e d r e a c t o r v a r i a n t s . t o m a i n t a i n p a r t i a l conversion a t a given l e v e l f o r a reasonable amount o f time.acs. S p e c i a l a t t e n t i o n must be given t o reduce the r e c y c l e r a t i o . Fixed-Bed Systems The major advantage of these fixed-bed systems i s that the fixed-bed technology can be simple.2. One common method f o r managing the a d i a b a t i c temperature r i s e i n fixed-bed r e a c t o r s i s t o d i l u t e the reactant stream w i t h a gas that would provide the mass to absorb the heat of r e a c t i o n .. durene i s mostly formed by a l k y l a t i o n of lower molecular weight aromatics w i t h methanol and/or ether. ACS Symposium Series.b e d r e a c t o r s and t u b u l a r r e a c t o r s . and w i l l r e q u i r e minimum scale-up s t u d i e s . Thus. In Figure 6a. Use of m u l t i p l e beds/reactors i n s e r i e s w i t h i n t e r c o o l i n g or quenching i s a method which can be used t o reduce the amount of r e c y c l e and i t s a s s o c i a t e d c o s t s . Wei. However. t h i s type o f design has been s u c c e s s f u l l y scaled-up t o commercial s i z e d i r e c t l y from bench-scale p i l o t p l a n t data many times. 2012 | http://pubs. M u l t i p l e c a t a l y s t beds reduce c o s t s by using the r e c y c l e m a t e r i a l s e v e r a l times before i t i s separated from the r e a c t i o n products. a multibed r e a c t i o n system i s shown f o r which only p a r t i a l conversion i s taken across each bed. The band-aging phenomena p r e v i o u s l y discussed would complicate the development o f such an MTG process s i n c e the c a t a l y s t appears t o age from the f r o n t t o the back.org Publication Date: July 28. presumably by reducing the c o n c e n t r a t i o n overlap of methanol/ether w i t h the aromatics formed.ch002 In the MTG process. As a consequence the e a r l y fixed-bed development work was conducted using 1 mm diameter extrudates. American Chemical Society: Washington. propane) can be r e c y c l e d f o r t h i s purpose. A l l of the above f a c t o r s must be considered i n the v a r i o u s r e a c t o r systems f o r the MTG process: fixed-bed r e a c t o r s . ethane. e s p e c i a l l y f o r the f i r s t bed. 1983. J. . As i n d i c a t e d e a r l i e r . the e f f l u e n t i s cooled before e n t e r i n g each succeeding bed such that the e f f l u e n t from each bed does not exceed a s p e c i f i e d maximum temperature. i t might be d i f f i c u l t . Methanol-to-Gasoline Process 27 Downloaded by UNIV OF ARIZONA on December 2. L i g h t hydrocarbon r e a c t i o n products (methane. et al. 1983 | doi: 10. This overlap tends t o i n c r e a s e w i t h l a r g e r c a t a l y s t p a r t i c l e s . Low methanol p a r t i a l pressures and high r e a c t i o n temperatures tend t o reduce the durene l e v e l . Figure 5a shows three v a r i e t i e s of fixed-bed r e a c t o r s and Figure 5b i l l u s t r a t e s heat-exchanger and f l u i d . In Chemical Reaction Engineering—Plenary Lectures. f l u i d . the c o s t s a s s o c i a t e d w i t h the r e c y c l e o p e r a t i o n could be s u b s t a n t i a l i f the r e a c t i o n i s s t r o n g l y exothermic.

. Wei.1021/bk-1983-0226.acs. Nonadiabatic r e a c t o r s .org Publication Date: July 28. In Chemical Reaction Engineering—Plenary Lectures.28 C H E M I C A L REACTION ENGINEERING Standard Downloaded by UNIV OF ARIZONA on December 2. 1983. American Chemical Society: Washington.ch002 Feed _ Quench Radial Flow Recycle Feed ^ ^Recycle Feed _ _ Recycle Figure 5a. 1983 | doi: 10. DC. et al. Tubular Isothermal Feed Heat Exchange Medium m Fluid-Bed Systems Recycle Φ Heat Exchange Medium Heat Exchange Medium Feed Figure 5b. ACS Symposium Series. J.. 2012 | http://pubs. A d i a b a t i c r e a c t o r s ..

ch002 X r Steam H 0' 2 χ Gas Recycle % -C Gas Make • Raw Gasoline H0 2 Figure 6a. et al. I n t e r s t a g e feed quenching. M u l t i b e d designs. MeOH Feed I n t e r s t a g e heat removal.acs.1021/bk-1983-0226. 2012 | http://pubs. Wei.PENICK E T A L . 1983. In Chemical Reaction Engineering—Plenary Lectures. Methanol-to-Gasoline Process MeOH Feed ^ ^Recycle i Downloaded by UNIV OF ARIZONA on December 2. 1983 | doi: 10.. . M u l t i b e d design. American Chemical Society: Washington. DC. J.org Publication Date: July 28. ACS Symposium Series. Recycle^ Gasoline Figure 6b..

a multibed r e a c t i o n system i s shown i n which only part of the reactant i s fed to each bed.acs. dimethyl ether and water over a dehydration c a t a l y s t .b e d operation.b e d MTG process. the other i s to develop a f l u i d c a t a l y s t s u f f i c i e n t l y rugged to withstand the a b r a s i v e f o r c e s inherent i n f l u i d . About 15% of the r e a c t i o n heat i s released i n t h i s f i r s t step. One i s the need to ensure the complete conversion of methanol. In the second step. However. A l k y l a t i o n of these o l e f i n s w i t h product isobutane and blending gives an increased g a s o l i n e y i e l d compared to that of the f i x e d bed.. American Chemical Society: Washington. 2012 | http://pubs. With a f l u i d bed. Fluid-Bed Reactor Systems A r e a c t o r system which has s e v e r a l a t t r a c t i v e f e a t u r e s f o r heat removal i s the f l u i d bed. In such a r e a c t i o n system the methanol feed to each succeeding bed would be mixed w i t h aromatics made i n the preceding beds . t h i s two stage r e a c t o r system i s the simplest of the fixed-bed systems to develop.r e a c t o r approach i s to d i v i d e the MTG r e a c t i o n i n t o two steps as shown i n Figure 7. the heat of r e a c t i o n can be recovered e f f i c i e n t l y as high pressure steam. 1983.ch002 30 In Figure 6b. Two f a c t o r s complicate the development of a f l u i d .. the f l u i d . p a r t l y because l i g h t product gas i s not r e c y c l e d . J. Heat t r a n s f e r i n a f l u i d bed i s so r a p i d that the danger of l o c a l overheating i s minimal. In Chemical Reaction Engineering—Plenary Lectures. ACS Symposium Series. S t i l l another m u l t i . or c a t a l y s t can be c i r c u l a t e d to an e x t e r n a l c o o l e r f o r heat recovery.b e d y i e l d p a t t e r n i s d i f f e r e n t from that of the f i x e d bed. As expected. i t leaves one w i t h a s u b s t a n t i a l amount of the r e a c t i o n heat (85%) s t i l l to be taken over one c a t a l y s t bed.org Publication Date: July 28. .C H E M I C A L REACTION ENGINEERING Downloaded by UNIV OF ARIZONA on December 2. et al. the r e a c t i o n heat can be removed by using heat exchange c o i l s i n the bed. This r e q u i r e s a f a i r l y high r e c y c l e stream to moderate the temperature r i s e over the second r e a c t o r . methanol i s p a r t i a l l y dehydrated to form an e q u i l i b r i u m mixture of methanol. 1983 | doi: 10. DC.. In the f i r s t step. Such a high r e c y c l e design would r e q u i r e c a r e f u l engineering i n order to t r a n s f e r heat e f f i c i e n t l y from the r e a c t o r e f f l u e n t to the r e c y c l e gas and r e a c t o r feed. Though t h i s two step approach does not have any of the inherent complications of the p r e v i o u s l y mentioned multibed r e a c t i o n systems.1021/bk-1983-0226.an arrangement that tends to increase durene formation. Furthermore. The reactant fed to each bed i s e s s e n t i a l l y completely converted and the r e a c t i o n products from that conversion become part of the temperature-moderating m a t e r i a l f o r each succeeding bed. Wei. C 5 + g a s o l i n e y i e l d i s lower. but the l i g h t o l e f i n s y i e l d s are much higher. t h i s e q u i l i b r i u m mixture i s converted to hydrocarbons and water over ZSM-5 c a t a l y s t w i t h the concomitant release of about 85% of the r e a c t i o n heat.

DC.Downloaded by UNIV OF ARIZONA on December 2. Wei. . American Chemical Society: Washington.ch002 PENICK E T A L . et al.1021/bk-1983-0226.. J.org Publication Date: July 28. 1983 | doi: 10.acs. Two-stage fixed-bed MTG. ACS Symposium Series. In Chemical Reaction Engineering—Plenary Lectures. Methanol-to-Gasoline Process Figure T. 2012 | http://pubs.. 1983.

. From our viewpoint the heat exchange r e a c t o r has the f o l l o w i n g disadvantages: (1) m o l t e n . i t was necessary to focus the development e f f o r t s . 2012 | http://pubs. Strategy f o r Commercialization Since there are many p o s s i b l e r e a c t i o n systems f o r an MTG process. Wei.and long-term o b j e c t i v e s . 1983.ch002 Tubular. Heat t r a n s f e r s a l t and b o i l i n g mercury are other p o s s i b i l i t i e s .C H E M I C A L R E A C T I O N ENGINEERING 32 Since i n a l a r g e diameter f l u i d bed. otherwise. elaborate hydrodynamic s t u d i e s are required to scale-up the r e a c t o r i n t e r n a l s to accomplish the complete conversion of methanol. Of these.1021/bk-1983-0226.s a l t c o o l i n g presents s i g n i f i c a n t o p e r a t i o n a l problems.. e s s e n t i a l l y complete conversion of methanol i s a process requirement. DC. L i g h t gas r e c y c l e can be reduced s i g n i f i c a n t l y compared to fixed-bed systems. Thus. (2) t u b u l a r r e a c t o r s g e n e r a l l y c o n t a i n l e s s c a t a l y s t per u n i t of v e s s e l volume than other r e a c t o r types. a c o s t l y d i s t i l l a t i o n step must be added to recover unconverted methanol. Downloaded by UNIV OF ARIZONA on December 2. M o b i l decided to pursue a double-pronged approach i n order to ensure both s h o r t . heat t r a n s f e r s a l t probably represents the best compromise f o r an MTG a p p l i c a t i o n p r i m a r i l y because the s a l t could a l s o be used to c o n t r o l the p e r i o d i c c a t a l y s t regeneration o p e r a t i o n which e n t a i l s temperatures of about 500°C. The scale-up would have to proceed through s e v e r a l stages before i t would be ready f o r commercialization. the f l u i d .b e d MTG process was assessed as being a d e s i r a b l e but a long-term development.acs. (3) the maximum p r a c t i c a l c a p a c i t y f o r a s i n g l e r e a c t o r i s l e s s than f o r other types and (4) very c a r e f u l mechanical design w i l l be required f o r a t u b u l a r r e a c t o r which can r e l i a b l y withstand both the conversion and c a t a l y s t regeneration c y c l e s . American Chemical Society: Washington. et al. 1983 | doi: 10.. f o r example. As mentioned e a r l i e r . ACS Symposium Series. each presents p a r t i c u l a r design c h a l l e n g e s . Good temperature c o n t r o l can be achieved i n the t u b u l a r r e a c t o r i f the coolant approximates an i s o t h e r m a l heat s i n k . J. Heat-Exchange Reactor Systems Another r e a c t o r system which has s e v e r a l a t t r a c t i v e f e a t u r e s f o r heat removal i s the t u b u l a r .org Publication Date: July 28. While o i l c o o l i n g might conceivably be used. heat-exchange r e a c t o r . the temperatures are above the range u s u a l l y considered p r a c t i c a l f o r such a design and l a r g e f l o w r a t e s would be required to achieve uniform c o o l i n g . The plan was: 1 In Chemical Reaction Engineering—Plenary Lectures. Tubular reactors have been used f o r Fischer-Tropsch r e a c t i o n s and f o r s y n t h e s i s of methanol and p h t h a l i c anhydride. bubbles may bypass the c a t a l y s t . In the mid-1970 s. The MTG r e a c t i o n temperature of approximately 400°C e s s e n t i a l l y precludes the use of b o i l i n g water as a coolant due to the h i g h steam pressures i n v o l v e d .

Such a development would p a r a l l e l extensive experience i n s u c c e s s f u l commercialization of many fixed-bed processes using s i m i l a r c a t a l y s t s and operating c o n d i t i o n s . d i r e c t . more e f f i c i e n t heat recovery. By making the l e n g t h o f the c a t a l y s t bed i n the demonstration In Chemical Reaction Engineering—Plenary Lectures. This system was s t u d i e d e x t e n s i v e l y i n bench-scale u n i t s . LONG-TERM — P r o c e e d w i t h an o r d e r l y development of the f l u i d ... This study i s a j o i n t p r o j e c t w i t h URBK. and M o b i l supported i n part by the U.q u a l i t y g a s o l i n e .S.b e d process. . 2012 | http://pubs. I n support of the New Zealand e f f o r t . Wei. The simplest fixed-bed MTG system was the one which employed dehydration and ZSM-5 r e a c t o r s .b e d process. Such a demonstration t e s t could be f i t i n t o the o v e r a l l schedule f o r the New Zealand venture and would provide l a r g e q u a n t i t i e s of product g a s o l i n e f o r road t e s t i n g i n cars t y p i c a l l y s o l d i n New Zealand. a 100 B/D f l u i d .s i z e r e a c t o r . ACS Symposium Series. and uncomplicated fixed-bed technology. The major o b j e c t i v e of the demonstration t e s t was t o v e r i f y the bench u n i t r e s u l t s i n a l a r g e r p l a n t operating a t c o n d i t i o n s s i m i l a r to a commerc i a l . The f i v e l i c e n s e d processes using ZSM-5 c a t a l y s t f a l l i n that category. C u r r e n t l y .b e d p i l o t p l a n t i n Germany i s nearing s t a r t up.org Publication Date: July 28. PENICK E T A L . i n 1978. Fixed-Bed Development and Commercialization Fixed-Bed Demonstration P l a n t .2. 1983. which may o f f e r an a t t r a c t i v e a l t e r n a t i v e to the fixed-bed process f o r the f u t u r e w i t h i t s p o s s i b l y higher g a s o l i n e y i e l d .1021/bk-1983-0226. American Chemical Society: Washington. DOE and the German government. i t was decided t o demonstrate the fixed-bed process i n a 4 B/D p i l o t p l a n t . J. However. 1983 | doi: 10. Methanol-to-Gasoline Process 33 Downloaded by UNIV OF ARIZONA on December 2. These s t u d i e s i n a 3 cm diameter by 30-50 cm l e n g t h r e a c t o r s were considered t o be s u f f i c i e n t f o r scale-up. et al. The other operating c o n d i t i o n s are normally the same f o r both r e a c t o r s .acs. DC. Uhde. the New Zealand government expressed strong i n t e r e s t i n applying the MTG technology f o r conversion of indigenous n a t u r a l gas to h i g h . S u c c e s s f u l completion of the 100 B/D program w i l l be a p r e r e q u i s i t e f o r proceeding w i t h c o m m e r c i a l i z a t i o n of the f l u i d . and economy of s c a l e . The l i n e a r v e l o c i t y of the reactant i s the only v a r i a b l e which i s s i g n i f i c a n t l y d i f f e r e n t between a bench-scale u n i t and a commercial-size r e a c t o r .ch002 NEAR-TERM — P r o c e e d w i t h commercialization of a simple.

1983. et al. there i s a strong i n c e n t i v e to have the bed l e n g t h be as short as p o s s i b l e to hold down the pressure drop and thus compression c o s t s . A t e s t f l e e t designed to simulate the New Zealand automobile p o p u l a t i o n was used f o r the d r i v e a b i l i t y t e s t s . Of the 12 cars t e s t e d at -18°C. one has to be concerned w i t h m a l d i s t r i b u t i o n s i n the c a t a l y s t packing and consequently i n the flow through the bed. 2012 | http://pubs. M o b i l came to the c o n c l u s i o n that w i t h a r e a c t o r bed l e n g t h of 2. (4_) The data show the weight percent durene that could be t o l e r a t e d before encountering any abnormal d r i v e a b i l i t y c h a r a c t e r i s t i c s .. J. But as c a t a l y s t beds get s h o r t . i t could e f f e c t i v e l y load the c a t a l y s t and ensure even d i s t r i b u t i o n of the gas i n r e a c t o r s having l a r g e diameters. American Chemical Society: Washington.org Publication Date: July 28.ch002 34 C H E M I C A L REACTION ENGINEERING p l a n t i d e n t i c a l to that of the proposed commercial-size r e a c t o r . T y p i c a l c y c l e s were about 50% longer. I f there were regions of high flow i n an MTG c a t a l y s t bed. The c a t a l y s t bed l e n g t h f o r the demonstration t e s t was set at the l i k e l y l e n g t h f o r a commercial p l a n t . the most c r i t i c a l car encountered a s l i g h t l y rougher-thannormal engine i d l e c o n d i t i o n . unconverted methanol could breakthrough e a r l y . For the demonstration u n i t . and 3 were good at 6 wt% durene.5 meters. The a d i a b a t i c temperature r i s e and the band aging behavior were a l s o the same. eleven had no decrease i n d r i v e a b i l i t y at 4 wt% durene. 7 were good at 5 wt%.. Wei. which i s s i g n i f i c a n t l y l a r g e r than c a t a l y s t p a r t i c l e s i z e to minimize w a l l e f f e c t s .1021/bk-1983-0226. A l l cars performed normally on g a s o l i n e c o n t a i n i n g 3 wt% or l e s s durene.acs. However. In a d d i t i o n . . To ensure that there would be no d r i v e a b i l i t y or handling problems w i t h MTG g a s o l i n e . The r e s u l t s of the demonstration plant are compared w i t h those of the bench u n i t i n Table I . 1983 | doi: 10.Downloaded by UNIV OF ARIZONA on December 2. p a r t i c u l a r a t t e n t i o n was given to the e f f e c t of durene on automobile performance and g a s o l i n e handling since i t s content i n the MTG g a s o l i n e i s the only s i g n i f i c a n t d i f f e r e n c e from conventional g a s o l i n e s . Figure 8 i l l u s t r a t e s the r e s u l t s of one t e s t s e r i e s conducted at -18°C ambient temperature. though the MTG In Chemical Reaction Engineering—Plenary Lectures. and thus a l l the process v a r i a b l e s become i d e n t i c a l . With 4 wt% durene. S i m i l a r behavior of longer c y c l e lengths have been observed i n commercial operation w i t h other ZSM-5 c a t a l y z e d processes. In the product q u a l i t y t e s t s . For a simple gas r e c y c l e system. the gas v e l o c i t i e s a l s o become i d e n t i c a l . Much higher durene t o l e r a n c e s were observed at higher temperatures. DC. a t a r g e t of 2 wt% durene i n g a s o l i n e was set as the company s p e c i f i c a t i o n . The two u n i t s were operated at i d e n t i c a l c o n d i t i o n s except f o r gas v e l o c i t y . the i n t e r n a l diameter was s e l e c t e d to be about 10 cm. The product y i e l d s and s e l e c t i v i t i e s over the f i r s t c y c l e were remarkably s i m i l a r . the demonstration u n i t performed considerably b e t t e r w i t h respect to c y c l e l e n g t h . ACS Symposium Series. r e s u l t i n g i n e i t h e r short c y c l e s or i n methanol l o s s to the water phase. heat t r a n s f e r along the r e a c t o r w a l l would a l s o be n e g l i g i b l e .

00 1.acs.2 2. R+0 1.156 Average F i r s t Cycle Y i e l d (Wt%) Hydrocarbon Products Methane Ethane Ethylene Propane Propylene Isobutane n-Butane Butènes C 5 + Hydrocarbons Gasoline (Wt%) Octane. DC. .54 0.2 95 80. American Chemical Society: Washington.1021/bk-1983-0226.15 8. et al. J. 49 9 2.39 4.6 52 9.15 8.163 407 1. Methanol-to-Gasoline Process Table I ..78 100. 1983 | doi: 10.92 100. PENICK E T A L . ACS Symposium Series.60 0. (W/W) Conversion Reactor I n l e t Temperature (°C) Conversion Reactor O u t l e t Temperature (°C) Methanol Space V e l o c i t y (WHSV) Separator Temperature (°C) Recycle R a t i o (mol/mol chg) Pressure (kPa) 83/17 83/17 358 360 404 1.00 80.86 0.org Publication Date: July 28. 35 Scale-Up R e s u l t s of Fixed-Bed MTG Bench Unit 4 B/D Unit Downloaded by UNIV OF ARIZONA on December 2.45 4.02 8.82 0.74 75.03 8.06 0..20 0. 1983.25 0.ch002 Conditions Methanol/Water Chg. Wei. 2012 | http://pubs.2.2 95 In Chemical Reaction Engineering—Plenary Lectures.71 75.33 0.

J. Wei..CHEMICAL REACTION ENGINEERING Downloaded by UNIV OF ARIZONA on December 2.1021/bk-1983-0226. DC. 2012 | http://pubs. . American Chemical Society: Washington. et al.org Publication Date: July 28. 1983 | doi: 10.ch002 36 In Chemical Reaction Engineering—Plenary Lectures. 1983.acs.. ACS Symposium Series.

ACS Symposium Series. o r i g i n a l c a t a l y s t . I n f a c t . Consequently. t h i s pressure produces a r e l a t i v e l y hot g a s o l i n e bottoms stream. To meet t h i s s p e c i f i c a t i o n w i t h conventional processing would have required undercutting the g a s o l i n e product. 1983. Methanol-to-Gasoline Process 37 process was producing about 5 wt% at that time. the f u e l value of the hydrogen can be replaced by the small amount of gas produced from the HGT step. The bottom p o r t i o n of the g a s o l i n e (approximately 15% i n the NZ design) i s processed i n a c a t a l y t i c r e a c t o r designed to convert the durene by both i s o m e r i z a t i o n and d e a l k y l a t i o n . The feedstock may be d i s t i l l e d o r crude methanol.acs. Commercial Fixed-Bed Plant Design. In Chemical Reaction Engineering—Plenary Lectures.Downloaded by UNIV OF ARIZONA on December 2. I n c o r p o r a t i o n of the HGT process has g r e a t l y eased the durene c o n s t r a i n t o r i g i n a l l y imposed on the MTG r e a c t o r design.. . The hydrocarbon l i q u i d from the separator (shown i n Figure 9) i s normally s t a b i l i z e d by f r a c t i o n a t i n g a t around 140 p s i g . American Chemical Society: Washington. Although Figure 10 shows f o u r p a r a l l e l o r "swing" conversion r e a c t o r s . DC. I n a short time. Such a change brings about l e s s r e a c t o r pressure drop. J. we are able t o switch t o a l a r g e r c a t a l y s t p a r t i c l e s i z e . durene l e v e l s even higher than 5 wt% could be t r e a t e d down t o the 2% l e v e l . The small amount of hydrogen required f o r the HGT can be r e a d i l y obtained from a p o r t i o n of the methanol s y n t h e s i s purge gas. Neither the f i n i s h e d g a s o l i n e volume nor i t s octane numbers are a f f e c t e d . as a consequence o f i n c o r p o r a t i n g HGT. The minor weight l o s s from the t r e a t i n g step i s o f f s e t by a decrease i n the s p e c i f i c g r a v i t y of the product. This purge stream i s normally used as f u e l . A t y p i c a l design of the r e a c t i o n s e c t i o n of a commercial p l a n t i s shown i n Figure 10.org Publication Date: July 28. Wei. With the HGT. Only small amounts of energy need to be expended since the feed i s so hot and the s e p a r a t i o n can be made w i t h l i t t l e r e f l u x . Sending t h i s high heat content stream d i r e c t l y t o a low-pressure g a s o l i n e s p l i t t e r a l l o w s us t o concentrate the durene i n a small bottoms stream. The dehydration r e a c t o r e f f l u e n t i s mixed w i t h preheated r e c y c l e gas and enters the conversion r e a c t o r s . The t r e a t e d heavy g a s o l i n e i s then s t a b i l i z e d and reblended w i t h the l i g h t g a s o l i n e .. a more e f f i c i e n t p l a n t . a l e s s e r o r g r e a t e r number of r e a c t o r s may be used depending upon the feed rate and regeneration frequency d e s i r e d . a heavy g a s o l i n e t r e a t i n g (HGT) technology evolved. The feed i s vaporized by r e a c t o r e f f l u e n t heat-exchange and enters i n t o the dehydration r e a c t o r . 1983 | doi: 10.ch002 2. and thus o v e r a l l . The HGT e f f i c i e n t l y f i t s i n t o the processing scheme.1021/bk-1983-0226. 2012 | http://pubs. The commercial fixed-bed MTG plant i s very s i m i l a r i n design concept t o the 4 B/D demonstration p l a n t . which makes more durene than the s m a l l e r . an e x p l o r a t o r y program was undertaken t o see i f t h i s s p e c i f i c a t i o n could be met by a d d i t i o n of a simple g a s o l i n e t r e a t i n g step. PENICK E T A L . et al.

In Chemical Reaction Engineering—Plenary Lectures.. Flowsheet o f the r e a c t i o n s e c t i o n o f the fixed-bed MTG process. . American Chemical Society: Washington. 1983 | doi: 10. Wei. J. et al. DC.org Publication Date: July 28. DME Effluent Header MeOH Superheater DME Reactor r f — H MeOH Vaporizer Crude MeOH Hot Excess Effluent From ZSM-5 Reactors To Duplicate Reactor/Effluent Exchanger Trains ZSM-5 Reactors MeOH JrlPreheater Cooling Water To Separator / t [ \ Effluent/Recycle \[ y Exchanger Cooled Effluent From ZSM-5 Reactor .1021/bk-1983-0226.38 C H E M I C A L REACTION ENGINEERING Recycle Gas Gas Make Com pressor cT] • LPG Deethanizer Downloaded by UNIV OF ARIZONA on December 2. 2012 | http://pubs.1 1. 1983. Cooled Reactor Effluent Figure 9.acs.1 I Cooler Compressed Recycle Gas From Separator J-UJ Recycle Gas Header Figure 10.. Fixed-bed MTG separations s e c t i o n . ACS Symposium Series.ch002 Gasoline Stabilizer Steam Product Separator ^^Steam -Stabilized Gasoline Raw Gasoline Waste Water.

ACS Symposium Series. t h i s arrangement has two advantages: • A blowdown of l i q u i d methanol can be taken i f the crude methanol contains any s o l i d s . yet has low pressure drop.ch002 2. the r e a c t o r e f f l u e n t s are combined and cooled by c o o l i n g water before e n t e r i n g the product separator. analogous t o a steam drum. 2012 | http://pubs. pressure waves may be transmitted t o the methanol exchangers. the pressure waves may cause the area used f o r v a p o r i z a t i o n to f l u c t u a t e thereby l e a d i n g t o p o t e n t i a l i n s t a b i l i t y i n the v a p o r i z a t i o n r a t e . v a p o r i z i n g . DC. • As the c o n t r o l valves t o the various MTG r e a c t o r s are adjusted. In Chemical Reaction Engineering—Plenary Lectures. Wei. Gas. A i r i s used as the source o f oxygen t o burn o f f the coke and n i t r o g e n d i l u t i o n i s used t o c o n t r o l the peak burning temperature. t h i s exchanger arrangement received our s p e c i a l attention. A f t e r these s e r v i c e s . 1983 | doi: 10..5 meters e l i m i n a t e d r a d i a l r e a c t o r s from c o n s i d e r a t i o n . The r e a c t i o n engineering i n the MTG plant centered on how deep the c a t a l y s t bed had t o be t o avoid premature methanol break-through. that r e a c t o r i s taken o f f stream and the c a t a l y s t i s regenerated by burning o f f the deposited coke. We have a l s o found i t a d v i s a b l e to vaporize the methanol using a v a p o r . The m a j o r i t y of the e f f l u e n t from a p a r t i c u l a r r e a c t o r i s used t o heat the r e c y c l e gas t o that r e a c t o r . v a p o r i z i n g and superheating the methanol feed. et al.1021/bk-1983-0226. J. When methanol breaks through a c a t a l y s t bed..l i q u i d drum. Most of the gas i s r e c y c l e d . American Chemical Society: Washington. Considerable engineering judgment and e f f o r t are needed t o ensure that the heat recovery i s e f f i c i e n t . The net gas make and l i q u i d hydrocarbon streams are sent t o conventional petroleum f r a c t i o n a t o r s f o r separation and s t a b i l i z a t i o n as shown i n Figure 9.org Publication Date: July 28. However. and superheating the methanol. The excess hot e f f l u e n t s from a l l the r e a c t o r s are combined and used f o r generating steam and heating the methanol feed to the dehydration r e a c t o r .acs. Most of the r e a c t o r e f f l u e n t gases during regeneration are r e c y c l e d back to the r e a c t o r a f t e r water i s removed. . 1983. I f one exchanger i s used f o r preheating.Downloaded by UNIV OF ARIZONA on December 2. Since a l a r g e p o r t i o n of the heat contained i n the r e a c t o r e f f l u e n t has to be t r a n s f e r r e d back t o the c o l d r e c y c l e gas. The d e c i s i o n that the minimum bed depth had t o be 2. l i q u i d hydrocarbon. PENICK E T A L . Such an arrangement increases the loop pressure drop because the excess hot e f f l u e n t flows through separate exchangers i n s e r i e s f o r preheating. Methanol-to-Gasoline Process 39 We have found that to e f f i c i e n t l y recover the high heat content i n the r e a c t o r e f f l u e n t i t i s d e s i r a b l e t o s p l i t the stream i n t o two p a r t s . and water phases are separated i n the product separator.

and the current phase i s a h o r i z o n t a l scale-up to 100 B/D c a p a c i t y . The operation of t h i s 4 B/D f l u i d p i l o t plant was very s u c c e s s f u l . The f l u i d . Higher g a s o l i n e y i e l d and octane number than f o r fixed-bed processing were v e r i f i e d (Table I I ) . et al. American Chemical Society: Washington. A schematic diagram of the r e a c t o r system of the 100 B/D p l a n t i s shown i n Figure 13. and e x t e r n a l c o o l e r .1021/bk-1983-0226. With these encouraging r e s u l t s .. A 100 B/D f l u i d .5 m/sec. i t was decided to scale-up the f l u i d . The i n i t i a l scale-up was v e r t i c a l to a 4 B/D c a p a c i t y . Key data yet to be obtained a r e : • r e a c t o r i n t e r n a l b a f f l e design to maintain complete conversion of methanol i n a l a r g e diameter f l u i d i z e d vessel.b e d program has been formulated to demonstrate h o r i z o n t a l scale-up. H o r i z o n t a l Scale-Up of F l u i d Bed. E x c e l l e n t s t a b i l i t y of the o p e r a t i o n was demonstrated over a 75-day run. a very uniform temperature p r o f i l e was e s t a b l i s h e d . • c a t a l y s t a t t r i t i o n and u l t i m a t e l i f e . regenerator. Wei.C H E M I C A L REACTION ENGINEERING 40 Fluid-Bed Development Downloaded by UNIV OF ARIZONA on December 2. In a d d i t i o n .ch002 From the small bench-scale t e s t s . The 4 B/D r e a c t o r i n t e r n a l diameter was 10 cm. The r e a c t o r c o n s i s t s of a dense f l u i d . the t r a n s i e n t temperature p r o f i l e s during heat-up and cool-down were a l s o uniform and s t a b l e .2 m height) l o c a t e d above a d i l u t e phase r i s e r . f l u i d . Two modes w i l l be studied to remove r e a c t i o n heat : In Chemical Reaction Engineering—Plenary Lectures.acs. 2012 | http://pubs. the f l u i d . DC.b e d process f u r t h e r .b e d process.b e d process was f i r s t scaled up v e r t i c a l l y from the 45 cm t a l l bench-scale r e a c t o r to the 760 cm t a l l 4 B/D r e a c t o r shown s c h e m a t i c a l l y i n Figure 11. ACS Symposium Series. 1983.. There was a complete absence of any troublesome "hot spots".org Publication Date: July 28. 1983 | doi: 10.b e d MTG development has proceeded to two phases of scale-up. There are three major v e s s e l s : r e a c t o r .t o diameter r a t i o (greater than 75) of the r e a c t o r . V e r t i c a l Scale-Up of F l u i d Bed. . E s s e n t i a l l y complete conversion of methanol was achieved at the design c o n d i t i o n s f o r s u p e r f i c i a l gas v e l o c i t i e s up to 0. Despite the h i g h l y exothermic nature of the r e a c t i o n and the unusually high l e n g t h . The 100 B/D p i l o t p l a n t w i l l provide a d d i t i o n a l i n f o r m a t i o n f o r design of a commercials c a l e . J.b e d s e c t i o n (60 cm ID χ 13. A t y p i c a l temperature p r o f i l e i n the r e a c t o r i s shown i n Figure 12.

b e d p i l o t p l a n t . American Chemical Society: Washington. 1983 | doi: 10. 1983.6 m F i g u r e 11. et al. 2012 | http://pubs.2 c m χ 7. ACS Symposium Series.ch002 .In Chemical Reaction Engineering—Plenary Lectures... ( y OO "I Catalyst Recirculation Line Catalyst Storage Vessel Air Regenerator Flue G a s Water H2O Tank h B/D f l u i d .1021/bk-1983-0226.acs. Vapor Feed Liquid F e e d ) Water Tank Car l eF ëeëc¥T Preparation oo Methanol Disengager Filter - Gas Liquid Hydrocarbons HC Prod Tank Separator Off Condenser Downloaded by UNIV OF ARIZONA on December 2. DC. J. Reactor10.org Publication Date: July 28. Wei.

DC.2 100.0 Y i e l d s (Wt.0 5.0 0. . J.0 85. (W/W) Dehydration Reactor I n l e t Temperature (°C) Dehydration Reactor O u t l e t Temperature (°C) Conversion Reactor I n l e t Temperature (°C) Conversion Reactor O u t l e t Temperature (°C) Pressure (kPa) Recycle R a t i o (mol/mol chg.0 100. ACS Symposium Series. 1983.2 43.0 2.7 7.5 1.5 56.2 100.5 0.4 100.42 C H E M I C A L REACTION ENGINEERING Table I I .3 60.) Space V e l o c i t y (WHSV) 316 404 360 413 415 413 2.ch002 Conditions Methanol/Water Chg. % of Methanol Charged) Methanol + Ether Hydrocarbons Water CO.4 5. 2012 | http://pubs. American Chemical Society: Washington.0 43.2 8.0 93 97 Hydrocarbon Product (Wt.0 0.4 56.0 14. et al.0 1.3 1.0 0.9 100. C 0 Coke. Wei.1021/bk-1983-0226.6 100.6 3.0 13.1 79.0 88. 1983 | doi: 10. Other 2 0. %) L i g h t Gas Propane Propylene Isobutane n-Butane Butènes C 5 + Gasoline Gasoline ( i n c l u d i n g A l k y l a t e ) [RVP-62 kPa ( 9 p s i ) ] LPG Fuel Gas Gasoline Octane (R+O) In Chemical Reaction Engineering—Plenary Lectures.0 275 1. Process Conditions and Product Y i e l d s from MTG Processes Fixed Bed F l u i d Bed 83/17 83/17 Downloaded by UNIV OF ARIZONA on December 2.org Publication Date: July 28.acs..6 5.6 1.4 5.0 6.9 5.1 0.4 0..170 9.

. . ACS Symposium Series. et al. 2012 | http://pubs. Wei. J. PENICK E T A L .b e d r e a c t o r temperature p r o f i l e .ch002 Reactor Elevation.1021/bk-1983-0226. 1983. In Chemical Reaction Engineering—Plenary Lectures.acs.. 300 500 Temperature.2. °C 700 F l u i d . 100 B/D f l u i d . 1983 | doi: 10. Meters Above Feed Inlet 100 Figure 12.org Publication Date: July 28. DC. Figure 13.b e d MTG demonstration p l a n t . Methanol-to-Gasoline Process 43 6h Downloaded by UNIV OF ARIZONA on December 2. American Chemical Society: Washington.

The b a f f l e design was optimized to ensure s u f f i c i e n t c a t a l y s t f l u x through the b a f f l e d s e c t i o n .ch002 44 • c i r c u l a t i o n of c a t a l y s t through an e x t e r n a l c a t a l y s t c o o l e r . To m a i n t a i n a constant c a t a l y s t a c t i v i t y i n the r e a c t o r . Wei. We b e l i e v e that the 100 B/D p l a n t represents the f i n a l development step before a commercial-size r e a c t o r can be designed w i t h confidence. and • i n t e r n a l heat exchange pipes immersed i n the dense bed reactor. h o r i z o n t a l b a f f l i n g provides a l s o the e f f e c t of s t a g i n g the f l u i d bed and l i m i t i n g the formation of gross c i r c u l a t i o n p a t t e r n s w i t h i n the bed. which r e l a x e s the durene c o n s t r a i n t . l e a d i n g to reductions of about 30% i n heat t r a n s f e r area and compressor horsepower.s c a l e Cold Flow Model (CFM). the s i z e of the r e c y c l e c i r c u i t i s reduced and i t becomes more e f f i c i e n t . The development of the HGT. 1983 | doi: 10. However. and v i s u a l o b s e r v a t i o n . i f the r e c y c l e r a t i o i s reduced from 9:1 to 7:1. J. bed expansion a n a l y s i s .acs. For example.org Publication Date: July 28. DC. l o c a l g a s / s o l i d s d i s t r i b u t i o n and bubble s i z e d i s t r i b u t i o n were measured.. Experimental r e s u l t s i n d i c a t e that h o r i z o n t a l b a f f l e s are e f f e c t i v e i n breaking bubbles. This non-reacting model proved very u s e f u l f o r o p t i m i z i n g b a f f l e design and c a t a l y s t c i r c u l a t i o n s t r a t e g i e s . ACS Symposium Series. w i t h most of the c a t a l y s t accumulating above the top b a f f l e s e c t i o n . opens the process v a r i a b l e window c o n s i d e r a b l y . a small f r a c t i o n of "coked" c a t a l y s t w i l l be c o n t i n u o u s l y regenerated and returned to the r e a c t o r . 2012 | http://pubs. h o r i z o n t a l b a f f l e s were s e l e c t e d f o r i n s t a l l a t i o n i n the p i l o t p l a n t . Thus. . S e v e r a l d i f f e r e n t b a f f l e designs — h o r i z o n t a l and v e r t i c a l arrangements (Figure 14) — have been t e s t e d i n the CFM using s e v e r a l experimental techniques: gas t r a c e r . S e v e r a l more advanced fixed-bed process arrangements which reduce processing c o s t s without reducing octane are being considered and subjected to p r e l i m i n a r y screening t e s t s . An o v e r l y r e s t r i c t i v e design can cause a marked d e n s i t y gradient i n the bed.C H E M I C A L R E A C T I O N ENGINEERING Downloaded by UNIV OF ARIZONA on December 2. the octane of the g a s o l i n e product i s reduced by about one number. In the t u r b u l e n t f l u i d i z a t i o n regime. The f i n a l b a f f l e design chosen f o r the 100 B/D p i l o t p l a n t d i d not e x h i b i t t h i s c a t a l y s t segregation phenomenon.1021/bk-1983-0226. et al. In Chemical Reaction Engineering—Plenary Lectures. Future Development The fixed-bed MTG process designed f o r New Zealand represents a simple but h i g h l y r e l i a b l e design concept. Integrated residence time behavior of the bed and q u a n t i t a t i v e . The mechanical design b a s i s of the 100 B/D u n i t has been v e r i f i e d on a f u l l .. capacitance probes. American Chemical Society: Washington. 1983.

DC.Downloaded by UNIV OF ARIZONA on December 2. .. Wei. 1983 | doi: 10.org Publication Date: July 28. ACS Symposium Series. 1983. In Chemical Reaction Engineering—Plenary Lectures. American Chemical Society: Washington.1021/bk-1983-0226..b e d r e a c t o r i n t e r n a l b a f f l e s .acs. 2012 | http://pubs. Methanol-to-Gasoline Process Examples o f f l u i d . et al. Figure Ik.ch002 PENiCK E T A L . J.

I n the g a s o l i n e production mode. By m o d i f i c a t i o n of c a t a l y s t and/or process c o n d i t i o n s . 1983 | doi: 10.ch002 46 CHEMICAL REACTION ENGINEERING The f l u i d . We are l o o k i n g a t c a t a l y s t m o d i f i c a t i o n s both f o r improved y i e l d / o c t a n e c h a r a c t e r i s t i c s and f o r improved steam s t a b i l i t y . We have learned to i n c r e a s e the ethylene y i e l d to about 30 wt% of hydrocarbon. one can operate where the s e l e c t i v i t y t o l i g h t o l e f i n s i s h i g h . This process i s perhaps the most promising new route f o r the production of ethylene from s y n t h e s i s gas. et al.acs.b e d process being developed i n the 100 B/D p i l o t plant has good p o t e n t i a l f o r becoming an important part of our f u t u r e technology. whether the d e s i r e d product i s g a s o l i n e .org Publication Date: July 28. In Chemical Reaction Engineering—Plenary Lectures. f o r i n s t a n c e . In a d d i t i o n t o the production o f g a s o l i n e . improved c a t a l y s t s are an i n t e g r a l part of r e a c t i o n engineering. we have now found good leads f o r y i e l d i n g as much as 75-80% C 2 . R e f e r r i n g back t o Figure 3. 1983. American Chemical Society: Washington. Wei. j e t f u e l o r ethylene f o r petrochemicals. the prospects look promising f o r manufacturing d i e s e l f u e l s and chemicals using r e l a t e d technology. DC. we are operating a t the f a r r i g h t where the g a s o l i n e components dominate. . w i l l provide new o p p o r t u n i t i e s f o r s y n f u e l s i n the coming decades. d i e s e l .1021/bk-1983-0226. In our e x p l o r a t o r y s t u d i e s . As the r e a c t i o n proceeds.. The z e o l i t e . the l i g h t o l e f i n s react f u r t h e r t o form i s o p a r a f f i n s and aromatics. I t has inherent p o t e n t i a l advantages over the fixed-bed process as mentioned e a r l i e r . I t i s b a s i c a l l y f l e x i b l e f o r easy a d a p t a t i o n t o petrochemicals production and b e t t e r c o n t r o l of the a u t o c a t a l y t i c r e a c t i o n .. 2012 | http://pubs. ACS Symposium Series. J. we observe that l i g h t o l e f i n s form f i r s t as intermediate products. Engineering and development s t u d i e s are i n the i n i t i a l phases of e v a l u a t i n g such concepts. i t i s necessary t o c o n t i n u a l l y look f o r improved c a t a l y s t s . ( _ 5 > 6 ) We can now consider the co-production of g a s o l i n e and d i s t i l l a t e from methanol as shown i n Figure 15. I t has been our experience that new. which shows the r e a c t i o n steps i n v o l v e d i n methanol conversion t o hydrocarbons.c a t a l y z e d methanol conversion technology. which i n t u r n can be converted to good q u a l i t y d i s t i l l a t e .C 4 o l e f i n product.Downloaded by UNIV OF ARIZONA on December 2. To keep processes v i t a l and c o m p e t i t i v e .

DC. g a s o l i n e . from . D. 1983.org Publication Date: July 28.1021/bk-1983-0226. J.ch002 2.. In Chemical Reaction Engineering—Plenary Lectures. Washington. PENICK E T A L . P r o d u c t i o n o f e t h y l e n e . Methanol-to-Gasoline Process 47 » Ethylene for Chemicals Methanol Methanol To Olefins çr. and d i s t i l l a t e methanol. American Chemical Society Library 1155 16th St. 1983 | doi: 10.W.acs.Downloaded by UNIV OF ARIZONA on December 2.c = Olefins 4 MTG 371-427°C 172-2068 kPa Gasoline MOGD Distillate 204-316°C 3447-5516 kPa F i g u r e 15. American Chemical Society: Washington.C.Pr. Wei.. et al. N. 20036 ACS Symposium Series.. 2012 | http://pubs.

P. May. Wei. 86-9. Meisel. B. 1981. 1977. T. Η. 10 1983 In Chemical Reaction Engineering—Plenary Lectures.C H E M I C A L REACTION 48 Literature Cited 1.. Utah. D. "Hydrocarbon Conversion and Synthesis Over ZSM-5 Catalysts".org Publication Date: July 28.. 1978. 6. and Silvestri. A. Meisel. An Alternative Route to High Quality Gasoline. DC. "Conversion of C -C Olefins to Higher Olefins Over Synthetic Zeolite ZSM-5. "Methanol-to-Gasoline. CHEMTECH. C. American Chemical Society: Washington. Fitch.. and Meier. 6. Honolulu. McCullough. Chem. 1982.. J. Η.. C. and Weisz. 4. and Weisz. 1976. B. L. Soc.. D. Mtg. 272. W.. Catal. S.ch002 ENGINEERING RECEIVED March 10. F. Kokotailo.. Olson. S. 437-8. Nov.. Μ. Lawton. W. L.. P. J. L. 1983." presented at Am. 249-59. Nevada.. Las Vegas. 47." presented at the International Pacific Conference on Automotive Engineering. Hawaii. 1982. presented at Advances in Catalytic Chemistry II Symposium. B. P. Nature..acs. 5. W. E. Salt Lake City. J. Chang. 1983 | doi: 10. March... G. et al.. 2012 | http://pubs. and Lee. S. 3. Garwood. 2... 2 Downloaded by UNIV OF ARIZONA on December 2. ACS Symposium Series. Lechthaler... .1021/bk-1983-0226. J.

J. ACS Symposium Series. i n t r i g u i n g .1021/bk-1983-0226. N . e s p e c i a l l y Denbigh's. There i s a l o t of j u i c e yet l e f t i n such a succulent subject although i t becomes i n c r e a s i n g l y d i f f i c u l t to t r e a t w i t h o r i g i n a l i t y a t o p i c that has been mouthed by so many.f u l l . DC. 2012 | http://pubs. i n t e r e s t . there were s i x ) . Torrington Place.. The previous s i x I n t e r n a t i o n a l Symposia on CRE have included 56 plenary l e c t u r e s three of which were devoted exc l u s i v e l y to f l u i d i s e d bed r e a c t o r s and a f u r t h e r two were subs t a n t i a l l y concerned w i t h them (1-5). c h a l l e n g i n g . This and Danckwerts c l a s s i c a l paper on residence time d i s t r i b u t i o n s (8) submitted i n 1952.org Publication Date: July 28. et al. He a l s o showed how s e l e c t i v i t y would depend on the order of competing r e a c t i o n s . promising and v e r s a t i l e form of chemical r e a c t o r . U n c h a r a c t e r i s t i c a l l y Octave seems to have overlooked Denbigh's c l a s s i c a l paper (7) submitted i n 1943 i n which Denbigh described and defined the continuous f l o w t u b u l a r r e a c t o r and the 'continuous flow s t i r r e d tank r e a c t o r f o r each of which he showed how to c a l c u l a t e both y i e l d and s i z e of r e a c t o r needed f o r given orders of r e a c t i o n and r e q u i r e d production r a t e s . American Chemical Society: Washington. .3 Fluidized-Bed Reactors P. 1983 | doi: 10. s t a b i l i t y and c o n t r o l and exceeded only be plenary l e c t u r e s concerned w i t h k i n e t i c s ( j u s t exceeded. Two years ago we were t r e a t e d to a n o s t a l g i c account of the coming of age of chemical r e a c t i o n engineering by P r o f e s s o r L e v e n s p i e l who dated i t s b i r t h as 1957 and i t s p o s s i b l e conception as 1947 (6). This i s a l e v e l of i n t e r e s t equalled only by the general subject of o p t i m i s a t i o n . Here we are w i t h yet another t a s t e of t h i s f a s c i n a t i n g . 1983. England This Plenary Lecture surveys the place of fluidised beds within the field of chemical reaction engineering and describes some developments and changes of interest over the last decade. ROWE Downloaded by UNIV OF ARIZONA on December 2.acs. Wei.00/0 © 1983 American Chemical Society In Chemical Reaction Engineering—Plenary Lectures. London WC1E 7JE. he 1 0097-6156/83/0226-0049$06.ch003 University College London. It concludes by suggesting the direction basic research should take in the future. Department of Chemical and Biochemical Engineering. l a i d most o f the founda t i o n s on which chemical r e a c t i o n engineering has since b u i l t .. I t i s an i n t e r e s t i n g experience to re-read these papers. I t i s q u i t e a long paper (22 pages.

Bubbling leads immediately to the concept of two phases w i t h p a r t of the gas f l o w i n g i n t e r s t i t i a l l y amongst c l o s e l y spaced p a r t i c l e s and the r e s t f l o w i n g i n the form of bubbles. w i t h i n the bed and without them the system would behave more or l e s s as a packed bed. I t i s the bubbles that cause p a r t i c l e mixing and b r i n g about the h i g h heat t r a n s f e r r a t e s that can occur between the bed and w a l l s or immersed s u r f a c e s . w i t h the w i l l i n g a i d of modern computational methods.ch003 50 would never get away w i t h that l e n g t h today) and gives an imp r e s s i o n of being r a t h e r tedious and t a k i n g a long time to come to the p o i n t . e s p e c i a l l y of temperature and p a r t i c l e composition.acs.org Publication Date: July 28. To r e t u r n f o r a moment to the t r a d i t i o n a l models. elaborated upon and mixed i n a l l p o s s i b l e (and some impossible) proportions and. In Chemical Reaction Engineering—Plenary Lectures. J. 2012 | http://pubs. These models of the patterns of r e a c t a n t c o n t a c t i n g form the b a s i s f o r much of present day chemical r e a c t i o n engineering. The PFR and CSTR are r e a d i l y imagined and widely a p p l i c a b l e d e s c r i p t i o n s of how r e a l l a r g e s c a l e r e a c t o r s a c t u a l l y behave. Wei. they have been expanded. The bubble flow i s t h e r e f o r e e a s i l y evaluated from Q B = Q - and the f a c t that Qi = Qmf. The reason f o r me reminding you of these foundations i s to draw a t t e n t i o n to the s c a r c i t y of f u r t h e r models beyond these two b a s i c types. The bubbling gas f l u i d i s e d bed i s one of the very few a d d i t i o n a l models a l b e i t a much more complicated one and n e c e s s a r i l y more l i m i t e d i n a p p l i c a t i o n . This i s why i t i s such a f a s c i n a t i n g subject to chemical r e a c t i o n engineers. The heart of h i s i d e a i s the b e a u t i f u l l y l o g i c a l combination of b a s i c laws of chemistry w i t h simple models of how the r e a c t a n t s come i n t o contact w i t h each other. This i s a poignant reminder of how deeply we have accepted h i s ideas and now take f o r granted t h i s imaginative and f r u i t f u l approach. ACS Symposium Series. F o r t u n a t e l y f l u i d i s e d bed r e a c t o r models are s t i l l reasonably c l o s e l y r e l a t e d to what a c t u a l l y happens and by and l a r g e the models can s t i l l be imagined as p h y s i c a l r e a l i t i e s . 1983 | doi: 10. The i n t e r s t i t i a l f l o w remains constant at the minimum f l u i d i s a t i o n value although f i n e powders may expand a l i t t l e and permit a r a t h e r l a r g e r flow. 1983. DC. American Chemical Society: Washington. They are r e s p o n s i b l e f o r the high degree of u n i f o r m i t y .1021/bk-1983-0226. .C H E M I C A L REACTION ENGINEERING Downloaded by UNIV OF ARIZONA on December 2. A l l powders bubble when f l u i d i s e d by gas at v e l o c i t i e s i n excess of a minimum value and look r a t h e r as i n F i g u r e 1 which i s a photograph of a two-dimensional bed sandwiched between glass p l a t e s ... et al. developed to a l e v e l of complexity that i s i n some cases out of touch w i t h r e a l i t y and c e r t a i n l y no longer p h y s i c a l l y imaginable but t h i s process of p a r a l y s i s by a n a l y s i s i s the f a t e of many o r i g i n a l l y simple i d e a s . At t h i s stage I should f o r the b e n e f i t of those l e s s f a m i l i a r w i t h f l u i d i s e d beds spend a few minutes d e s c r i b i n g the p r i n c i p a l features that govern t h e i r behaviour as r e a c t o r s ( 9 ) .

J.acs.org Publication Date: July 28.Fluidized-Bed Reactors Downloaded by UNIV OF ARIZONA on December 2.. et al.1021/bk-1983-0226. ACS Symposium Series. American Chemical Society: Washington. Bubbles i n a two-dimensional f l u i d i z e d bed. In Chemical Reaction Engineering—Plenary Lectures. 2012 | http://pubs.ch003 ROWE Figure 1. .. Wei. 1983 | doi: 10. DC. 1983.

Average bubble s i z e i n creases w i t h height as i n d i c a t e d i n F i g u r e 2. p a r t l y be shear displacement or d r i f t but a l s o by the bulk t r a n s p o r t of p a r t i c l e s i n the bubble wake. There i s . This i s i l l u s t r a t e d i n Figure 5. The slugging bed g e n e r a l l y gives b e t t e r g a s / s o l i d c o n t a c t i n g but must be modelled d i f f e r e n t l y from the bubbling bed and r e q u i r e s greater free-board. A major reason f o r by-passing i n the bubble phase i s the formation of clouds or s p h e r i c a l v o r t i c e s centred on the bubbles. Only that p o r t i o n of the cloud or v o r t e x that extends beyond the bubble i s i n contact w i t h p a r t i c l e s andtherefore able to r e a c t . however. Bubbles may a l s o cause segregation i f there are d i f f e r e n t kinds of p a r t i c l e s present. Chemical r e a c t o r models i n v a r i a b l y s t a r t from the two-phase theory (12). P r o d u c t i o n requirements w i l l determine the r e a c t a n t gas feed r a t e and bed diameter f i x e s v e l o c i t y and thence the bubbling r a t e . a s i t u a t i o n that occurs when bubbles r i s e f a s t e r than i n t e r s t i t i a l gas which i s commonly the case. Gas i s o b l i g e d to f l o w upwards through the bubble because of pressure d i f f e r e n c e but as i t r e .Downloaded by UNIV OF ARIZONA on December 2. P a r t i c l e mixing i s caused by the bubbles. In many r e a l i s t i c s i t u a t i o n s t h i s p r o p o r t i o n can be very s m a l l . i t i s trapped and dragged downwards u n t i l pressure d i f f e r e n c e pushes i t back i n t o the bubble. These simple f a c t s a l l o w an immediate c o n s i d e r a t i o n of r e a c t o r v e s s e l s i z i n g (10). f o r example. 1983 | doi: 10. 2012 | http://pubs. What would be a bubble i n a l a r g e r e a c t o r at a given height and v e l o c i t y would be a s l u g i n a narrow one as Figure 3 i n d i c a t e s . segregation i s i n s e n s i t i v e to p a r t i c l e s i z e d i f f e r e n c e but p a r t i c u l a r l y s e n s i t i v e to d e n s i t y d i f f e r e n c e . There may be some exchange between the two phases and F i g u r e 4 d e p i c t s t h i s k i n d of model.. 1983. Heat t r a n s f e r c o n s i d e r a t i o n s and blower c a p a c i t y are l i k e l y to set l i m i t s to the bed height or aspect r a t i o and bed diameter must accommodate the bubbles. et al. At any i n s t a n t only t h i s proport i o n of the t o t a l cloud i s r e a c t i n g so that the e f f e c t i v e r a t e constant i s reduced. In the past p i l o t p l a n t s have operated i n the slugging regime and reduced performance was experienced when s c a l i n g up simply by i n c r e a s i n g diameter but no one should make that mistake today. Wei. when the f l o w i s f a s t enough.org Publication Date: July 28. U n l i k e other kinds of mixers.ch003 52 C H E M I C A L REACTION ENGINEERING The bubbles coalesce r e a d i l y so that they may be small and numerous at the bottom and large and few at the top w h i l s t maint a i n i n g s u b s t a n t i a l l y constant flow. ACS Symposium Series.1021/bk-1983-0226. This can cause problems i n . J. The whole i s c i r c u l a t i n g as a v o r t e x w i t h In Chemical Reaction Engineering—Plenary Lectures. The i n t e r s t i t i a l f l o w i s assumed to be i n good and continuous contact w i t h s o l i d s w h i l s t some by-passing occurs i n the bubble phase. I n a b i n a r y system of p a r t i c l e s segregation increases approximately as p a r t i c l e d e n s i t y r a t i o to the power 5/2 but w i t h p a r t i c l e s i z e r a t i o only to the power 1/5 (11). very l i t t l e a x i a l or r a d i a l mixing of the gas. DC..acs. . American Chemical Society: Washington. c o a l combustion where char has a markedly lower d e n s i t y than ash and a l s o i n some ore r e d u c t i o n processes using coke.e n t e r s the dense phase ahead i t i s caught i n a stream of p a r t i c l e s f l o w i n g downwards r e l a t i v e to the bubble and.

A bubble i n a l a r g e bed becomes a s l u g i n a s m a l l one. ACS Symposium Series. 1983. . Wei.org Publication Date: July 28. In Chemical Reaction Engineering—Plenary Lectures.. Figure 3.. American Chemical Society: Washington. J. ROWE Fluidized-Bed Reactors 53 Downloaded by UNIV OF ARIZONA on December 2. DC.1021/bk-1983-0226.ch003 g'4 increasing gas flow Ο Ο Ο ο ο ο ^ ο ο » * ° Ο <=> ο ° ο| tut Ο Figure 2. 2012 | http://pubs.acs. Bubbles s i z e increases w i t h bed height and flow r a t e . et al.3. 1983 | doi: 10.

54

C H E M I C A L REACTION

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch003

interstitial

"
exchange

phase

Figure h.

ENGINEERING

bubble
phase

B a s i c two-phase bubble model.

particle

flow

V

induced

Figure 5·
clouds.

gas circulation

P a r t i c l e flow induces gas c i r c u l a t i o n and so forms

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch003

3.

ROWE

Fluidized-Bed Reactors

55

upward v e l o c i t y through the empty space of the bubble of s i m i l a r
magnitude to minimum f l u i d i s a t i o n v e l o c i t y . With f i n e p a r t i c l e s
t h i s i s small so that l i t t l e c i r c u l a t i o n occurs during the r e s i dence time of a bubble i n the bed. This i s the very s i t u a t i o n
where the cloud cannot penetrate f a r i n t o the dense phase so the
o v e r a l l e f f e c t i s poor c o n t a c t i n g o f bubble phase gas w i t h p a r t icles.
Severe by-passing i n the bubble phase and very poor gas
mixing can make the f l u i d i s e d bed an extremely poor chemical
r e a c t o r but a t l e a s t the major reasons f o r t h i s are now understood. The prospects o f success f o r a given process can be
judged a t an e a r l y stage and design can minimize by-passing
u s u a l l y by choosing p a r t i c l e s i z e a p p r o p r i a t e l y .
What development and progress has occurred during the l a s t
ten years or so? Experience has accumulated and a number of
f l u i d i s e d bed processes are operated s u c c e s s f u l l y . I n d u s t r i a l
companies are r e l u c t a n t to d i s c l o s e too many d e t a i l s o f a successf u l and p r o d u c t i v e r e a c t o r but I have seen beds as l a r g e as 17 m
i n diameter very uniformly and s t a b l y f l u i d i s e d which could be
shut down and r e - s t a r t e d without t r o u b l e .
During the l a s t decade much i n t e r e s t has centred on the
behaviour of l a r g e p a r t i c l e s (diameters i n m i l l i m e t e r s r a t h e r
than microns) as r e q u i r e d i n f l u i d i s e d c o a l combustion. The
t o p i c has generated two l a r g e conferences r e c e n t l y i n the U.K.
alone (13, 14) and many more i n the U.S.A. This i s the subject
of the next Plenary Lecture so I w i l l only mention some f e a t u r e s
b r i e f l y . Large p a r t i c l e s are necessary i n t h i s a p p l i c a t i o n
because high f l o w r a t e s are r e q u i r e d since the f l u i d i s i n g a i r i s
a l s o combustion a i r and a high i n t e n s i t y of heat generation i s
aimed f o r . I n order f u l l y t o convert oxygen to C O 2 , c o a l conce n t r a t i o n i n the bed i s low (a few percent) and most of i t i s ash
or a chosen r e f r a c t o r y granular m a t e r i a l such as sand. Limestone
may be a d d i t i o n a l l y included to adsorb S O 2 . These p a r t i c l e s must
be f a i r l y l a r g e t o avoid e l u t r i a t i o n . Furthermore, the bed i s
shallow to minimise the pressure drop the fans are r e q u i r e d to
overcome. There i s l i k e l y t o be a l o t o f heat exchanger surface
w i t h i n the bed. Of course, gas v e l o c i t y and hence the need f o r
l a r g e p a r t i c l e s can be reduced by i n c r e a s i n g absolute pressure.
These c o n d i t i o n s have not been widely studied i n the l a b o r a t o r y because of the obvious d i f f i c u l t i e s of p r o v i d i n g high a i r
v e l o c i t i e s (a few meters/sec) on a s c a l e that i s l a r g e compared
w i t h the s i z e of the p a r t i c l e s . C e r t a i n l y i n t e r s t i t i a l gas f l o w
w i l l f a r exceed bubble r i s e v e l o c i t y and there i s no p o s s i b i l i t y
of cloud formation as shown i n Figure 5. Instead gas w i l l f l o w
s t r a i g h t through the bubbles and the o v e r a l l p a t t e r n w i l l approximate to plug flow. Because o f the l a r g e d i f f e r e n c e i n d e n s i t y
between c o a l char and other bed m a t e r i a l the former w i l l tend to
f l o a t . This i s a c o m p l i c a t i o n imposed upon what would otherwise
be a w e l l mixed p a r t i c l e bed. E f f i c i e n t in-bed combustion
r e q u i r e s uniform d i s p e r s i o n of c o a l but the process of p a r t i c l e

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch003

56

C H E M I C A L REACTION

ENGINEERING

segregation i s q u i t e w e l l understood (15) and the system can be
designed to be reasonably uniform under operating c o n d i t i o n s .
S a t i s f a c t o r y models e x i s t f o r p r e d i c t i o n of combustor performance
although there i s some d i f f i c u l t y i n c o r r e c t l y e s t i m a t i n g the
temperature of a burning c o a l p a r t i c l e . The major design problems are of the broadly mechanical k i n d such as c o a l feeding and
i n i t i a l d i s t r i b u t i o n , heat exchanger design and ash removal.
At the other end of the spectrum there i s c o n t i n u i n g
i n t e r e s t i n the behaviour of f i n e p a r t i c l e s (approximately l e s s
than 100 ym) because c a t a l y s t powders are g e n e r a l l y i n t h i s range.
F l u i d bed c r a c k i n g c a t a l y s t i s the best known example. Geldart
(16) made an important c o n t r i b u t i o n when he proposed a c l a s s i f i c a t i o n of powders and l a b e l l e d t h i s f i n e m a t e r i a l Type A.
The
c h a r a c t e r i s t i c f e a t u r e of them i s that they expand u n i f o r m l y at
v e l o c i t i e s not g r e a t l y i n excess of U f as i l l u s t r a t e d i n F i g u r e
6. Only at some higher v e l o c i t y , U ^ do they begin to bubble.
Values of U b/U £ can be as high as 3 or 4 and the bed volume can
double i n extreme cases before bubbling begins.
I f the dense phase expands t h i s immediately a f f e c t s the
r e a c t o r model because more gas w i l l then flow v i a the favourable
i n t e r s t i t i a l phase. Most models r e a d i l y a l l o w f o r t h i s change
given that the t r u e d i v i s i o n of f l o w can be p r e d i c t e d . Unh a p p i l y i t has so f a r only been p o s s i b l e to measure t h i s d i v i s i o n
experimentally at f a i r l y low flow r a t e s , w e l l below those
employed i n commercial r e a c t o r s . C e r t a i n l y at v e l o c i t i e s up to
about 15 cm/s much more gas flows i n t e r s t i t i a l l y through Geldart
type A powders than minimum f l u i d i s a t i o n f l o w (17).
I n d u s t r i a l r e a c t o r s g e n e r a l l y operate a t very high v e l o c i t i e s
(of order 1 m/s) much i n excess of t e r m i n a l f a l l i n g v e l o c i t y f o r
at l e a s t the f i n e s t powder f r a c t i o n s . Powder i s c o n t i n u a l l y
e l u t r i a t e d and returned to the bed v i a cyclones. Under these
c o n d i t i o n s there i s disagreement as to whether or not bubbles
r e t a i n t h e i r i d e n t i t y and such beds have been described as
" t u r b u l e n t " or " f a s t f l u i d i s e d " . What l i t t l e evidence there i s
supports the continued existence of bubbles but now i n a much
d i s t u r b e d or heterogeneous dense phase and w i t h a l e s s d e f i n i t e
shape. U n t i l more i s known about t h i s p h y s i c a l s i t u a t i o n i t i s
not easy to see how the bubbling bed r e a c t o r models should be
modified c o r r e c t l y to d e s c r i b e t h i s f l o w regime.
I t i s too simple to assume that average p a r t i c l e s i z e i s an
adequate index of powder type i n G e l d a r t s c l a s s i f i c a t i o n .
C e r t a i n l y type A powders depend s t r o n g l y on d i s t r i b u t i o n of s i z e
and p a r t i c u l a r l y on the p r o p o r t i o n at the lowest end of the range.
There i s p l e n t y of i n d u s t r i a l experience to support t h i s view and
p l a n t operators u s u a l l y acknowledge the importance of m a i n t a i n i n g
a c e r t a i n p r o p o r t i o n of f i n e s i n the r e a c t o r . W h i l s t the v i t a l
r o l e of the f i n e s f r a c t i o n has been recognised i t i s a d i f f i c u l t
dependence to study s y t e m a t i c a l l y .
The two-phase bubbling bed model i s capable of many minor
adjustments and has given numerous academics a l o t of fun p l a y i n g
m

m

m

m

1

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

ROWE

Fluidized-Bed Reactors

Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch003

3.

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

57

When an i n s o l u b l e gas enters a l i q u i d p In Chemical Reaction Engineering—Plenary Lectures. P o s s i b l y a j e t could be e s t a b l i s h e d i n a c y l i n d r i c a l bed by e r e c t i n g s u i t a b l e b a f f l e s to hinder p a r t i c l e f l o w but t h i s would have to be a d e l i b e r a t e arrangement.ch003 58 C H E M I C A L REACTION ENGINEERING v a r i a t i o n s on the b a s i c tune. I would l i k e to spend a few minutes over t h i s d e t a i l because i t leads to a simple and s a t i s f y i n g model f o r chemical r e a c t i o n i n the d i s t r i b u t o r zone. 1983 | doi: 10. Although a t t r a c t i v e t h i s model i s q u i t e wrong simply because gas does not form a j e t above the d i s t r i b u t i o n o r i f i c e but enters the bed i n the form of bubbles j u s t as. There i s no such d i f f i c u l t y when p a r t i c l e s can approach w i t h i n the f u l l 360°. In a narrow slab bed p a r t i c l e s can only flow towards the hole over a r e s t r i c t e d r e g i o n and cannot always move f a s t enough to c l o s e the hole p e r i o d i c a l l y . In t h i s l a s t case there i s no observable l a t e r a l p e n e t r a t i o n and bubbles r i s e v e r t i c a l l y from the o r i f i c e . the bubble forms as a near p e r f e c t sphere above the h o l e . J. One reason f o r the p e r s i s t e n c e of a wrong concept of how gas enters i s the f a c t that i t does so d i f f e r e n t l y i n a two-dimensiona l f l u i d i s e d bed. Here I must pause to emphasise the importance of i d e n t i f y i n g c o r r e c t l y the mechanism by which events occur which can o n l y be done by s u i t a b l e e x p e r i mental o b s e r v a t i o n . a i r blown i n t o water (19) . f o r example.. et al. detaches and r i s e s and w i t h i n a very short d i s t a n c e . i f gas enters downwards through a pipe b u r i e d i n the bed or i f gas enters h o r i z o n t a l l y through a hole i n the w a l l . The evidence comes from X-ray ciné photographs taken at 50 frames/s w i t h an exposure time of 1 ms which c o n d i t i o n s a l l o w the very r a p i d events to be c l e a r l y followed. In t h i s case i t i s q u i t e p o s s i b l e to e s t a b l i s h a permanent j e t s t a b i l i s e d by the w a l l s .F i g u r e 7.org Publication Date: July 28. ACS Symposium Series. The d i s t r i b u t o r p l a t e i n a f u l l s c a l e r e a c t o r i s u s u a l l y d r i l l e d w i t h a number of holes s e v e r a l m i l l i m e t e r s i n diameter and the gas v e l o c i t y through these i s h i g h (tens of m/s). American Chemical Society: Washington. Powder could be entrained i n t o the j e t as i n a spouted bed and i t has been imagined that t h i s p o t e n t i a l l y good g a s / s o l i d s c o n t a c t i n g arrangement i s r e s p o n s i b l e for a h i g h r a t e of chemical conversion (18). . As Figure 8 shows. E s s e n t i a l l y the same bubbling occurs i f the hole i s covered with a bubble cap. 2012 | http://pubs. A l l t h i s has been seen w i t h a v a r i e t y of p a r t i c l e s but not very l a r g e ones ( d measured i n mm) where there i s reason to t h i n k behaviour may be d i f f e r e n t . assumes i t s c h a r a c t e r i s t i c shape w i t h an indented base as the wake forms. This mode of entry has been observed at gas v e l o c i t i e s up to 70 m/s and through holes as l a r g e as 16 mm diameter.1021/bk-1983-0226. There are more models than data against which to t e s t them and s u i t a b l e data f o r t h i s purpose are not e a s i l y obtained. 1983.acs. Wei. Whatever the model chosen i t i s commonly observed that the r e a c t i o n r a t e i s unusually h i g h i n the bottom few centimeters of the bed and t h i s i s o f t e n r e f e r r e d to as the distributor effect. I t i s easy to imagine that t h i s produces a spout or j e t of gas above which a stream of bubbles occurs. an arrangement chosen because of the ease of o b s e r v a t i o n .. DC.Downloaded by UNIV OF ARIZONA on December 2.

f l o w i n t e r s t i t i a l l y o r t r a n s f e r between the two.Downloaded by UNIV OF ARIZONA on December 2. Not very much funda- In Chemical Reaction Engineering—Plenary Lectures. During the time that a bubble grows to the s i z e shown i n F i g u r e 9 the gas that produced i t has advanced t o f i l l the volume i n d i c a t ed by the outer broken l i n e . I t i s a f a c t of observation that a t the moment o f detachment bubble s i z e and frequency accounts f o r only about h a l f the o r i f i c e gas flow. The annular r e g i o n above and around the bubble now contains an excess of gas and so the powder v o i d age must increase. J. The other end c o n d i t i o n where the bubbling bed model i s i n a p p r o p r i a t e i s above the bed where there may be r e a c t i o n i n the f r e e board r e g i o n . L a t e r i t may form a cloud as i n F i g u r e 5 w i t h l i m i t e d access t o p a r t i c l e s . ROWE Fluidized-Bed Reactors 59 i t i s no s u r p r i s e that bubbles form because of the i n c o m p a t i b i l i . The l a s t area I wish to mention i s the e f f e c t on f l u i d i s a t i o n of changing temperature and pressure. This i s unstable and as the bubble detaches and r i s e s through the expanded dense phase the powder r e l a x e s and and r e t u r n s the excess gas t o the bubble. Furthermore bubble s i z e and frequency must be equivalent t o the gas flow r a t e . As yet there i s no f l u i d dynamic model that describes i n q u a n t i t a t i v e d e t a i l the bubble formation process but i t i s b a r e l y necessary f o r a r e a c t i o n engineering model. When gas enters a f l u i d i s e d bed the phases are not incompatible because gas may form bubbles. say. Wei. This appears t o be completed by the time i t has r i s e n about one diameter (of order 1/10 second) and t h e r e a f t e r i s of constant volume u n t i l i t coalesces . .* ty of the two phases.acs. one i n i t i a l bubble diameter deep and t h e r e a f t e r forms bubbles.org Publication Date: July 28. American Chemical Society: Washington. Hence the high r e a c t i o n r a t e s a s s o c i a t e d w i t h the process of bubble formation and l i m i t e d to the bottom l a y e r of the bed of thickness up to twice the i n i t i a l bubble diameter . Frequency i s e s s e n t i a l l y independent of f l o w r a t e and constant a t about 8/s. U n l i k e formation i n a l i q u i d the boundary of a f l u i d i s e d bed bubble can only expand by gas f l o w i n g across i t to produce the drag f o r c e that w i l l cause the p a r t i c l e s to move a p p r o p r i a t e l y . 1983. et al. I t i s adequate to assume that e n t e r i n g reactant gas passes i n plug f l o w through the bottom l a y e r of p a r t i c l e s . 2012 | http://pubs. Considering now the consequences f o r chemical r e a c t i o n . much of the reactant gas that u l t i m a t e l y forms a bubble w i l l f i r s t enter the i n t e r s t i t i a l phase and enjoy a b r i e f moment of i n t i m a t e contact w i t h the p a r t i c l e s .ch003 3..a few centimeters a t most. Above t h i s d i s t r i b u t o r l a y e r the two-phase bubble model can be a p p l i e d . With f i n e powders where there i s appreciable e l u t r i a t i o n gas and p a r t i c l e s may remain i n contact w i t h f u r t h e r opportunity f o r r e a c t i o n ..1021/bk-1983-0226. About two bubble diameters higher they have grown i n s i z e and now account f o r a l l the flow. 1983 | doi: 10. I n i t i a l bubble diameter i s r e a d i l y estimated from the known flow through the o r i f i c e and the f a c t that frequency i s about 8/s. This s i t u a t i o n has not a t t r a c t e d the a t t e n t i o n of many modellers but a t l e a s t one model p r e d i c t s that considerable r e a c t i o n can continue under c e r t a i n circumstances (20). ACS Symposium Series. DC.

1021/bk-1983-0226.org Publication Date: July 28. 1983. ACS Symposium Series. Figure 9· Gas flow causes the bubble boundary t o expand. ENGINEERING ski 1 | F i g u r e 8. . 2012 | http://pubs. Wei. DC. American Chemical Society: Washington. et al.Downloaded by UNIV OF ARIZONA on December 2.. x-Ray photograph o f bubble formation at an o r i f i c e .ch003 60 CHEMICAL REACTION F i g u r e 7· Gas enters the bed as a stream o f bubbles.acs.. In Chemical Reaction Engineering—Plenary Lectures. J. 1983 | doi: 10.

heat exchang­ ers and m a t e r i a l s of c o n s t r u c t i o n . I n s p i t e of the i n t e r e s t of f l u i d dynamicists l i t t l e i s known about the r e l a t i o n s h i p between p e r m e a b i l i t y .ch003 m In Chemical Reaction Engineering—Plenary Lectures. Wei. ROWE 61 Fluidized-Bed Reactors mental work has been reported on the former (21. U f = U ^ ) become type A a t q u i t e modest increases i n pressure.1021/bk-1983-0226. DC. bed height and p a r t i c l e s i z e and s i z e d i s t r i b u t i o n .3. This i s good news from a chemical r e a c t i o n engineering point of view and the bubbling bed models continue to apply and only r e q u i r e the changed d i v i s i o n of flow to be q u a n t i f i e d . I t i s evident that p a r t i c l e s i z e and s i z e d i s t r i b u t i o n are f a c t o r s determining p e r m e a b i l i t y and that " f i n e s " are important i n t h i s respect but i t i s d i f f i c u l t to understand why change of absolute pressure should change voidage and p e r m e a b i l i t y . Understanding these things could g r e a t l y improve our a b i l i t y t o engineer f l u i d ­ i s e d bed chemical r e a c t o r s and t h i s should be a major object of b a s i c research. I t i s becoming f a i r l y c l e a r that when compared a t the same s u p e r f i c i a l gas v e l o c i t y . J. .. Powders that normally behave as Geldart type Β ( i . the v a r i a b l e s are very l i m i t e d . The reason f o r t h i s seems t o be that p r o p o r t i o n a t e l y more gas flows i n t e r s t i t i a l l y as pressure increases and bubbles are smaller because the reduced f l o w gives l e s s opportunity f o r growth by coalescence.acs. The f i r s t two are l a r g e l y f i x e d by production r a t e and simple engineering c o n s i d e r a t i o n s and p a r t i c l e s i z e i s about the only t h i n g l e f t to choose. I t u r n f i n a l l y to consider the d i r e c t i o n f u t u r e b a s i c research should take. ACS Symposium Series. Gas d e n s i t y and v i s c o s i t y and p a r t i c l e d e n s i t y w i l l be determined by chemistry and thermodynamics and the only major v a r i a b l e s remaining are gas v e l o c i t y . 1983 | doi: 10. e . Downloaded by UNIV OF ARIZONA on December 2. I f we knew more about how to make t h i s choice our designs might be much improved. Leaving aside d e t a i l s o f mechanical design such as the d i s t r i b u t o r . Bubbles begin to l o s e t h e i r i d e n t i t y and a t q u i t e low gas v e l o c i t i e s the bed takes on the general appearance of a " t u r b u l e n t " o r " f a s t f l u i d i s e d bed". voidage and the flow c o n d i t ­ ions and yet i t i s t h i s that decides the d i v i s i o n of gas between the phases w i t h important consequences f o r chemical r e a c t i o n . 22) but there i s i n c r e a s i n g i n t e r e s t i n the l a t t e r (23-29). b a f f l e s . This again i s advantageous f o r r e a c t i o n engineering but few processes w i l l be r e q u i r e d t o operate a t such high pressures. American Chemical Society: Washington. 2012 | http://pubs.org Publication Date: July 28. This f o r c e depends not only on the gas p r o p e r t i e s and v e l o c i t y but a l s o on the p a r t i c l e spacing and arrangement.. However deep our knowledge of the mechanism of f l u i d i s a t i o n i t i s s a l u t a r y to pause and consider the freedom of choice a chemical r e a c t i o n engineer w i l l have. bubble s i z e decreases as pressure i n c r e a s e s . I t i s fundamental to the s t a t e o f f l u i d i s a t i o n that p a r t i c l e s are supported by the drag of f l o w i n g gas. et al. At pressures greater than about 80 bar some i n t e r e s t i n g hydrodynamic changes occur. 1983.

Trans.H. 133. 12. 1971. 2. Symp. W. ι i n t e r s t i t i a l flow rate minimum f l u i d i s a t i o n flow r a t e U ^ minimum bubbling flow v e l o c i t y U ^ minimum f l u i d i s a t i o n flow v e l o c i t y Literature Cited 1. 50. D. Rowe. Denbigh. 121 et seq. Danckwerts... A9. A. of Energy.G. l .N. 424.org Publication Date: July 28. Dechema: Frankfurt. 2.systems and applications" 1980. Chem. Proc. 9.P. 13. Rowe. D. Academic Press: New York. L. Rowe. Eng. (Editor) "Fluidisation". 11. Science 1980. Faraday Soc. 106.ch003 D Q. Harrison. Elsevier: Amsterdam.W. Wei. 17. Santoro. Series N o . N .. "Fluidised Combustion . ACS Symposium Series. 35. P. P. G . Powder Tech'y 1973.. Chem. 285. P. A . O. 537. "Fluidised Combustion" 1975. 2012 | http://pubs. 4th ISCRE 2. A. Agbim. . London: Institute of Fuel. 1976. Kunii. 14. Pyle. . Trans. J . Yates. 35. 352. Science 1978.L. Powder Tech'y 1978. Chem. 1969. Y . 89. London: Inst.N. Advances in Chemistry Series 72. 40. In Chemical Reaction Engineering—Plenary Lectures.V. 12 1978. P . 193. I.1021/bk-1983-0226. DC. Davidson. Cheung. D. Advances in Chemistry Series 109. Nienow. American Chemical Society: Washington. .F. 10. 3. P. 6. Chem.4. van Swaaij. P. Rudolph. Science 1980. Levenspiel. 15. 1972.L . J. 1972. J.W.N. J . 1983 | doi: 10. 1. 7. John Wiley: New York. Proc. Science 1953. Eng. Eng. 5. Symp. bubble f l o w r a t e r a t e i n t o the bed Downloaded by UNIV OF ARIZONA on December 2. 4. 1978. Chem. : Nienow.. K. 2nd ISCRE. Geldart. O. 1944.. 7.acs. Rowe. Ε 1972. Rowe. 1983. D. 1887. Kunii. 8.. 324.F.62 CHEMC IAL REACTO IN ENGN IEERN IG L i s t of Symbols cL bubble diameter JD D Κ r e a c t o r diameter h bed height Q volumetric flow Q_. "Fluidisation Engineering".M. D. Chemistry & Industry No. P. 16.. 1821. Eng.N. et al. Levenspiel. L . Series No.

J .N. I. Wei. T . H . Eng. 55.U. J . Eds. 50. . J . Yeoman.E. S . Grace. Desai. J . Harrison. Inst. J . DC. Harrison. D. Carvalho. 135. A. I. Series No. Chem. H .. Rowe. IV.1. 26.1021/bk-1983-0226. J. Pulsifer. 137. P. F . 2012 | http://pubs. 45. 1977.. 21.: i b i d . .. . E d . American Chemical Society: Washington. M.A. C l i f t . D . Series No. "Fluidisation".3. King.W. Grace. J . Guedes de. 55. Varadi. 1983. Pyle. 1.acs. E . 22.. 93. Carvalho. J . Downloaded by UNIV OF ARIZONA on December 2. 39. 1974. E . D.. Chem. ROWE Fluidized-Bed Reactors 63 Zenz. Fund. 1968. 18. M . D. Powder Tech'y 1977. M . 143. Matsen. . 57. 1983 | doi: 10. 136.R. "Fluidisation". 1980. . "Fluidization". Y. M . P. .. Trans. 201. Trans. C l i f t . 19. 1983 In Chemical Reaction Engineering—Plenary Lectures. Harrison. 29.. . R . et al. 1979. F . Kikukawa. Series 4. E. RECEIVED April 27. M. C. 20. Rowe. J. Symp. Guedes de. 27. J. J . Grace. R .30. J . 194.. Ind.. Trans. 1975. 28.H. F. B1. de Kock.. J . Cheesman. R . F .F. Chem. R. 1961.N. J . L . P. 23.P.: 1978. Yates. Α. Chem. Chem. . . 59.ch003 24. B o t t e r i l l . G . 1980. P i r i e . Plenum Press: New York. MacGillivray. of Fuel Symp. D . ACS Symposium Series. I. I.N. Inst. Davidson. Subzwari. of Energy Symp. . Rowe. H . MacGillivray. 25.. . : i b i d . J. Weber. . R. E. R . D . 16.org Publication Date: July 28.P.

This page intentionally left blank .

bed temperature. American Chemical Society: Washington. Department of Chemical Engineering. some w i t h over 40. heat transfer. 0097-615 6/83/0226-0065$10. . w i t h over 200 u n i t s i n use i n the l a t t e r . DC. 2012 | http://pubs.000 hours o f o p e r a t i o n a l experience (2). MA 02139 The factors controlling the performance of atmospheric-pressure fluidized-bed combustors (AFBC's) are illustrated by order-of-magnitude calculations of the design and operating variables for a hypothetical 100 MW boiler. and the development of atmosphericpressure and p r e s s u r i z e d f l u i d i z e d . Wei.acs. suspension f i r i n g of p u l v e r i z e d c o a l and the burning of lump c o a l on s t o k e r s . 2_. Bed height. fluidizing velocity and coal feed size are selected by consideration of the fluids mechanics. i s that i t i s able to handle coals o f w i d e l y v a r y i n g composition. and kinetics of the governing gas-solid reactions.p o w e r generation i s being pursued at a p i l o t s c a l e l e v e l (4_. _3 ). I t s advantages over a l t e r n a t i v e methods o f d i r e c t c o a l u t i l i z a t i o n . The fluid mechanics and heat transfer in AFBC's are shown to be differ distinctly from those in more traditional fluidized bed reactors. et al. At present s e v e r a l firms o f f e r designs of AFBC's f o r i n d u s t r i a l steam generation. Small (<3MW) u n i t s are i n commercial s e r v i c e i n both the United Kingdom (1) and the People's Republic of China. ACS Symposium Series... i n c l u d i n g low-grade coals w i t h high ash content.. 5). 1983 | doi: 10. e.4 Fluidized-Bed Coal Combustion: Controlling Parameters A D E L F. sorbent feed size and rate. Consideration i n t h i s paper w i l l be r e s t r i c t ed to u n i t s operated at atmospheric pressure (AFBC's) s i n c e these are o f greater current commercial i n t e r e s t . immersed heat-transfer surface area. bed cross-sectional area. and i t provides a c a p a b i l i t y of in-bed s u l f u r capture. 1983. The development of the technology of AFBC's has been pursued v i g o r o u s l y s i n c e the e a r l y s i x t i e s . t F l u i d i z e d bed combustion provides one option f o r u t i l i z i n g some of our l a r g e c o a l reserves f o r purposes of energy generation. SAROFIM Downloaded by CORNELL UNIV on December 2.1021/bk-1983-0226.g. Larger demonstration u n i t s (>20MW) have been constructed and operated (1. Cambridge.org Publication Date: July 28. J.ch004 Massachusetts Institute of Technology.b e d combustors f o r c e n t r a l s t a t i o n e l e c t r i c .00/0 © 1983 American Chemical Society In Chemical Reaction Engineering—Plenary Lectures.

t y p i c a l l y about 50 jJm. Wei. The r e a c t i o n s of importance i n f l u i d i z e d beds i n c l u d e those r e l a t i n g to c o a l combustion. 1983.r i s e v e l o c i t y exceeds the gas v e l o c i t y i n the dense phase (u f/c £) over a bed's depth. c o a l ->• char + v o l a t i l e s ( i n c l u d i n g NH^ + v o l a t i l e + 0 + C0 + H 0 ' 2C + 0 + 2C0 + NO + S 0 C + C0 + 2C0 CO + 1/2 0 •> C0 2 2 H S) 2 2 2 2 2 2 2 Downloaded by CORNELL UNIV on December 2.org Publication Date: July 28. be d i s t i n g u i s h e d from those i n f l u i d i z e d c a t a l y t i c r e a c t o r s such as f l u i d i z e d c a t a l y t i c crackers (FCCs) because the p a r t i c l e s i z e i n an AFBC. 1983 | doi: 10. the FCC s operate i n the s o . CaC0 CaO + CaS0 S0 + CaS0 3 3 2 3 + CaO S0 •> + 1/2 1/2 0 + 1/2 2 2 + C0 CaS0 0 + CaS0 -> S 0 0 -> CaS0 2 3 2 4 3 2 4 and to n i t r i c oxide formation and d e s t r u c t i o n ..ch004 to s u l f u r capture.1021/bk-1983-0226. By contrast. 2012 | http://pubs. however. a f a c t often overlooked because t h e i r primary purpose i s t o generate steam and e l e c t r i c i t y .. t y p i c a l l y about 1 mm i n diameter.acs.c a l l e d f a s t bubble regime to be e l a b o r a t ed on l a t e r .66 C H E M I C A L REACTION ENGINEERING F l u i d i z e d . DC. ACS Symposium Series. c o n s i d e r a t i o n of which must be part of any attempt to r e a l i s t i c a l l y model bed performance. Minimum v e l o c i t y of f l u i d i z a t i o n ( f ) i n an FCC i s so low that the b u b b l e . et al. The consequences of t h i s d i f f e r e n c e i n p a r t i c l e s i z e i s i l l u s t r a t e d i n Table 1. The f l u i d mechanics and heat t r a n s f e r i n an AFBC must.the b u b b l e . i s more than an order of magnitude l a r g e r than that u t i l i z e d i n FCC s. The performance of a f l u i d i z e d bed combustor i s s t r o n g l y i n f l u e n c e d by the f l u i d mechanics and heat t r a n s f e r i n the bed. . P a r t i c l e Reynolds number i n an FCC i s much s m a l l e r than u n i t y so that viscous forces dominate whereas f o r an AFBC the p a r t i c l e Reynolds number i s of order u n i t y and the e f f e c t of i n e r t i a l forces become n o t i c e a b l e .b e d combustors are complex chemical r e a c t o r s . J.r i s e v e l o c i t y i n an AFBC may be slower or f a s t e r than the gas-phase v e l o c i t y i n the emulsion f u m m m T In Chemical Reaction Engineering—Plenary Lectures. 2NH + 3/2 0 -> 2N0 + 3/2 H 0 NH + NO + 1/4 0 -> N + 3/2 H 0 NO + C •> 1/2 N + CO 3 2 2 3 2 2 2 2 N 0 + C 0 1 / 2 N + C ^îïî 2 °2 NO + CaS0 + CaS0 + 1/2 3 4 N 2 From t h i s p a r t i a l l i s t i n g one can f i n d r e a c t i o n s belonging to many of the important c l a s s e s of homogeneous and heterogeneous reactions . American Chemical Society: Washington.

0 3 OQ ( 2°)Q. 1 0 0 kJ/kg* and ten percent ash by weight. 1983. In order t o help focus the d i s c u s s i o n .t r a n s f e r s u r f a c e s .4.acs.e ) h s (1) where ε and h are the v o i d f r a c t i o n and height of the unexpanded bed. D i f f e r e n c e s i n F l u i d i z a t i o n and Heat Transfer o f AFBC's and F l u i d i z e d C a t a l y t i c Reactors (e. shown s c h e m a t i c a l l y i n Figure 1 . c o a l feed s i z e . J. the c h a r a c t e r i s t i c h e a t i n g times are long compared t o the p a r t i c l e residence time a t the w a l l and the p a r t i c l e s can be t r e a t e d as being a t the b u l k temperature f o r purposes o f heat t r a n s f e r c a l c u l a t i o n s (7). c o a l feed l o c a t i o n . et al. immersed h e a t . freeboard h e i g h t .. and a i r flow r a t e g In Chemical Reaction Engineering—Plenary Lectures.ch004 T particle(s) heating phase. The paper w i l l consider the parameters c o n t r o l l i n g the design and operation of an AFBC. The a d d i t i o n a l pressure drop across the d i s t r i b u t o r p l a t e w i l l here be taken t o be one t h i r d that across the bed. Wei. and p i s the d e n s i t y o f the bed s o l i d s . The fan work. DC. FCC s) T FCC AFBC Ρ Downloaded by CORNELL UNIV on December 2.org Publication Date: July 28. Fluidized-Bed Coal Combustion SAROFiM 67 Table I . order-of-magnitude c a l c u l a t i o n s w i l l be performed f o r the conceptual design of a b o i l e r designed t o produce 1 0 0 MW of steam a t 644 K. sorbent s i z e and feed r a t e . l e a d i n g t o operation i n e i t h e r the slow or f a s t bubble regime. f i r e d w i t h a c o a l of elemental composition C H Q ^ S O Q N Q . The pressure drop across the bed i s simply the weight of the bed. American Chemical Society: Washington.. 1983 | doi: 10.g. For an AFBC.07» 8 value of 2 9 . The b o i l e r w i l l be operated w i t h 2 0 percent excess a i r . ΔΡ = P g ( l . bed temperature and f l u i d i z i n g v e l o c i t y .1021/bk-1983-0226. . 2012 | http://pubs. The questions to be addressed are what are the f a c t o r s t h a t guide the s e l e c t i o n of bed h e i g h t . Q 2 H A N E A T I N Pressure Drop Across Bed (Bed Height S e l e c t i o n ) The bed height i s determined by c o n s i d e r a t i o n of the work r e q u i r e d t o overcome the pressure drop across the bed and d i s t r i b ­ utor p l a t e . F i n a l l y the c h a r a c t e r i s t i c h e a t i n g time of p a r t i c l e s i n an FCC i s s m a l l r e l a t i v e t o the residence time o f s o l i d s near a tube surface and the heat t r a n s f e r r a t e i s then c o n t r o l l e d by the p e n e t r a t i o n o f a thermal waves i n t o the s o l i d s as f i r s t proposed by M i c k l e y and Fairbanks ( 6 ) . ACS Symposium Series.

ch004 CHEMICAL SPENT SORBENT REACTION ENGINEERING COAL Figure 1. 2012 | http://pubs. Wei. In Chemical Reaction Engineering—Plenary Lectures.Downloaded by CORNELL UNIV on December 2. Schematic o f atmospheric pressure f l u i d i z e d bed combustor.org Publication Date: July 28. ACS Symposium Series.acs. . 1983.. 1983 | doi: 10.. J.1021/bk-1983-0226. et al. American Chemical Society: Washington. DC.

3. S u l f u r Capture ( S e l e c t i o n o f Bed Temperature and P a r t i c l e S i z e ) The s u l f u r sorbent that has r e c e i v e d the most a t t e n t i o n i s limestone because o f i t s widespread a v a i l a b i l i t y and low cost. t h i s can pose problems o f ensuring uniform f u e l d i s t r i b u t i o n over the bed. American Chemical Society: Washington.4. . et al. Inasmuch as the fan power l o s s i s p r o p o r t i o n a l t o the v o l u m e t r i c a i r requirement v ^ per u n i t mass of f u e l (Eq. A consequence of t h i s c o n s t r a i n t on maximum bed height i s that f l u i d i z e d bed c r o s s . the fan e f f i c i e n c y . For r e a l i s t i c values o f the c o e f f i c i e n t s : p = 2400 Kg/m .5 m /Kg c o a l . 1983 | doi: 10.7 m i s o f t e n s e l e c t e d to keep the energy l o s s f o r fan power t o 2 percent o f the f u e l ' s h e a t i n g value.ch004 3 e f a -:— = 0.5. s e 3 o Downloaded by CORNELL UNIV on December 2. and i t can be r e a d i l y shown (<3) that f o r p a r t i c l e s that do not permit v o l u m e t r i c expansion on r e a c t i o n the maximum conversion a t t a i n a b l e i s about 59 percent (the value i s dependent on the s p e c i f i c volumes of reactant and product). 2012 | http://pubs. the bed height cor­ responding t o a given Δπι-ρ/τη-ρ i s p r o p o r t i o n a l to pressure so that p r e s s u r i z e d FBC's may be operated w i t h deep beds and much s m a l l e r c r o s s . 1983.6. as w i l l be discussed l a t e r . r e s u l t i n g i n bed widths much l a r g e r than bed depth f o r l a r g e r u n i t s . given the v o l u m e t r i c a i r requirement v per mass o f f u e l . J.028 h *F (3) where the bed height h i s i n meters.. SAROFiM Fluidized-Bed Coal Combustion 69 i s the product o f the v o l u m e t r i c a i r flow r a t e and the pressure drop.1021/bk-1983-0226. may be expressed as an e q u i v a l e n t amount of f u e l Διη„. The unexpanded bed height needs to be kept low i n order to minimize pumping energy l o s s e s . Wei. t ) = 0. ACS Symposium Series.s e c t i o n a l areas than AFBC's. This c o n s t r a i n t can be avoided by use of dolomite. The above conclusions f o l l o w from c o n s i d e r a t i o n o f the s t o i c h i o m e t r i c r e l a ­ tions : In Chemical Reaction Engineering—Plenary Lectures. n = 0. and a value of about 0.. DC. 2 ) . The f r a c t i o n of the f u e l flow rate m needed t o supply the energy t o d r i v e the fans i s r e a d i l y shown to be a F ~ζΓ 3 (-AH )n n c e v> f where -ΔΗ^ i s the heat o f combustion. but a t the expense of an added weight o f sorbent and added energy requirement f o r c a l c i n a t i o n . Unfortunately the conversion o f limestone to calcium s u l f a t e r e s u l t s i n a v o l u m e t r i c i n c r e a s e . v = 24. s i n c e the MgO i s not s u l f a t e d and the v o i d volume produced by the decomposition of MgCO^ and CaCO^ i s s u f f i c i e n t t o permit complete calcium u t i l i z a t i o n . and r) the e f f i c i e n c y o f conversion of thermal t o e l e c t r i c a l energy.org Publication Date: July 28.s e c t i o n a l area i s p r o p o r t i o n a l to the c a p a c i t y of a b o i l e r .acs.e= 0.

(16) have observed Downloaded by CORNELL UNIV on December 2. f o r s e v e r a l p a r t i c l e s s i z e s . The models have been found to d e s c r i b e experiment a l data f o r many limestones (13) by a d j u s t i n g the constants i n the model.MgC0 3 2 3 + 1/2 + S0 0 2 + o 2 + 1/2 CaSO. The rate of s u l f a t i o n i s seen to de­ crease w i t h extent of s u l f a t i o n approaching zero at a maximum s u l f a t i o n m · Both the r a t e constant K„ at a given s u l f a t i o n and oo S the maximum s u l f a t i o n m decrease w i t h i n c r e a s i n g p a r t i c l e s i z e . 1 2 ) and the pore-plugging model (13. Allowance can be made f o r a f i n i t e rate of the C a 0 / S 0 r e a c t i o n ( 1 2 ) .. + 4 0 C0 o ΔΗ = -325 kj/mole 2 + Mg0. In the pore-plugging model the c a l c i n e d limestone i s assumed to c o n s i s t of calcium oxide p e r f o r a t e d by c y l i n d r i c a l holes of uniform diameter. The r a t e of r e a c t i o n i s c o n t r o l l e d by the d i f f u s i o n of S 0 through the porous m a t r i x and the product CaSO^ l a y e r formed on each g r a i n (11). In the g r a i n model.2 1 0 kJ/mole (5) The r a t e constant f o r s u l f a t i o n of a limestone i s shown as a f u n c t i o n of the f r a c t i o n a l s u l f a t i o n m of calcium. As a consequence the r e a c t i o n r a t e f a l l s to very low values as the pore mouth plugs. 1983 | doi: 10. The S 0 d i f f u s e s through the pore and the product CaSO^ to unreacted CaO. can be e x p l a i n e d by models which assume that the r e a c t i o n i s retarded by a product l a y e r of CaSO^ of low p o r o s i t y through which the SO2 must d i f f u s e i n order to reach the unreacted CaO.ch004 œ 1 g 2 2 2 2 2 2 2 In Chemical Reaction Engineering—Plenary Lectures. taken from the measurements of F i e l d e s and Davidson (9).C H E M I C A L REACTION ENGINEERING 70 CaC0 o 3 + S0 o CaC0 .acs. 14) are the most n o t a b l e . As w i t h the g r a i n model. J. This o b s e r v a t i o n . Because of the increase i n volume on r e a c t i o n . most n o t a b l y the d i f f u s i v i t y through the product l a y e r . Such a hypothesis has formed the b a s i s f o r the development of s e v e r a l models to q u a n t i t a t i v e l y f i t s u l f a t i o n data. a c o r r e l a t i o n which has proved u s e f u l i n developing models of s u l f u r capture f o r AFBC s (10). of which the g r a i n model ( 1 1 .1021/bk-1983-0226. 2012 | http://pubs. DC. .CaS0 2 4 + 2C0 (4) 2 ΔΗ = . 1983. The model has been developed without (14) and w i t h (15) allowance f o r a k i n e t i c r e s i s t a n c e due to the C a 0 / S 0 r e a c t i o n . American Chemical Society: Washington. i t i s assumed that the CaO c o n s i s t s of s p h e r i c a l grains of uniform s i z e d i s t r i b u t e d i n a porous matrix. The maximum s u l f a t i o n observed i s c o n s i d e r a b l y s m a l l e r than the t h e o r e t i c a l l i m i t of 59 percent. i n Figure 2 . together w i t h the decrease i n r a t e constant K w i t h extent of s u l f a t i o n . The r e a c t i o n of S 0 w i t h c a l c i n e d limestone i s found to be f i r s t order w i t h respect to S 0 but the dependence on 0 concent r a t i o n i s more complicated.org Publication Date: July 28. the pore diameter decreases w i t h a maximum decrease at the opening where the d i f f u s i o n path i s s h o r t e s t . Wei. the data may be c o r r e l a t e d by one curve when p l o t t e d versus m/m^. et al. F i e l d e s et a l . the pore-mouth plugging model can adequately describe the decrease i n r e a c t i o n r a t e w i t h i n c r e a s i n g extent of r e a c t i o n and w i t h decreasing p a r t i c l e s i z e by appropriate adjustment of the d i f f i s u v i t y through the product layer.. ACS Symposium Series.

1021/bk-1983-0226. In Chemical Reaction Engineering—Plenary Lectures. American Chemical Society: Washington. DC. and m/m» .acs.Downloaded by CORNELL UNIV on December 2. ACS Symposium Series. 2012 | http://pubs.). the f r a c t i o n a l s u l f a t i o n . SAROFiM Fluidized-Bed Coal Combustion m/m oo Figure 2 .org Publication Date: July 28. Wei.. 1983 | doi: 10. 1983.ch004 4. the f r a c t i o n a l s u l f a t i o n normalized w i t h i t s asymptotic value (9. J. et al. Rate constant f o r the r e a c t i o n o f S O 2 w i t h c a l c i n e d limestone as a f u n c t i o n o f m.. 71 .

f o r example. et al.235 the c o a l feed r a t e . They a t t r i b u t e d t h i s decrease t o an i n c r e a s e i n SO^ concentration w i t h i n c r e a s i n g oxygen.ch004 œ 1 2 F l u i d Mechanics (Determination of Bed C r o s s . DC. c o a l type.345 that of the c o a l feed and the flow r a t e of the p a r t i a l l y s u l f a t e d spent sorbent i s 0.3. The In Chemical Reaction Engineering—Plenary Lectures. CaSO^ decomposes a t temperature i n excess o f 1500 K. The Ca/S r a t i o cor­ responds t o a maximum s u l f a t i o n of about 0. 18).. 1983 | doi: 10. i s at lower temperatures. Because the s i n g l e p a r t i c l e behavior i s so complex. ACS Symposium Series.s e c t i o n a l Area and Flow Regime The f l u i d i z i n g v e l o c i t y i n a bed i s bounded by the minimum fluidizing velocity u and the t e r m i n a l v e l o c i t y u (27). f i t s o f s i n g l e p a r t i c l e behavior determined. In order to p r e d i c t emissions from AFBC s i t i s necessary t o couple a model of the s u l f u r capture of i n d i v i d u a l p a r t i c l e s i n t o a system's model which takes i n t o account the S 0 formation. s i n c e the rate of r e a c t i o n of SO. The e x p l a n a t i o n f o r the peaking i n s u l f u r capture a t temperatures below that at which CaSO^ decomposes has not been d e f i n i t e l y e s t a b l i s h e d . The bed temperature s e l e c t i o n i s based on the admittedly shaky evidence that t h i s i s where the maximum s u l f a t i o n peaks. . w i t h CaO i s high the SO. 21. 22) use s i m p l i f i e d . 2 2 Downloaded by CORNELL UNIV on December 2. and t r a n s p o r t . u s u a l l y e m p i r i c a l . A p l a u s i b l e argument f o r the decrease i n r e a c t i v i t y w i t h i n c r e a s i n g tempera­ ture i s that s i n t e r i n g o f grains i s a c c e l e r a t e d a t higher tempera­ tures and that the maximum s u l f a t i o n t h e r e f o r e decreases as a consequence of the increased g r a i n s i z e .72 C H E M I C A L REACTION ENGINEERING t h a t the maximum s u l f a t i o n m of a v a r i e t y of limestones 00 decreased J w i t h i n c r e a s i n g oxygen c o n c e n t r a t i o n . most such models (10.acs. and a Ca/S r a t i o of about 3. The maximum s u l f a t i o n m i s reported as o c c u r i n g around 1120 Κ (17. a sorbent p a r t i c l e of 1 mm. from thermogravimetric a n a l y s i s . Promising areas f o r research are on reducing g r a i n s i z e by minimizing g r a i n growth (23. 1983. The optimum c o n d i t i o n s needed to achieve the d e s i r e d s u l f u r capture e f f i c i e n c y (90 percent) i s dependent on sorbent type.1021/bk-1983-0226. Wei. 2012 | http://pubs. Representative c o n d i t i o n s are a bed temperature of 1116 K. f o r the l e v e l s o f S 0 and 0 found i n combustion products. The p a r t i c l e s i z e s e l e c t i o n i s a compromise between a d e s i r e t o use high gas v e l o c i t i e s and the observed decrease i n s u l f a t i o n w i t h i n c r e a s i n g s i z e (Figure 2). r e ­ moval. American Chemical Society: Washington.w i l l react p r e f e r e n t i a l l y a t the moutn of a pore and l e a d to the pore plugging. 20.. The maximum s u l f a t i o n m i s expected t o pass through a peak as temperature i s i n c r e a s e d s i n c e .. For these condi­ t i o n s the mass feed r a t e of a limestone sorbent i s 0.org Publication Date: July 28. and f l u i d i z e d bed design. The maximum observed. Examples of the i n c r e a s e i n g r a i n s i z e (19) and the decrease i n maximum s u l f a t i o n (9) w i t h i n c r e a s i n g temperature are shown i n Figure 3. i n c r e a s i n g limestone u t i l i z a ­ t i o n through p a r t i a l h y d r a t i o n (25) and the development o f r e ­ generative sorbents (26). however. J. This provides the b a s i s f o r the current s e l e c t i o n of optimum bed temperature. C l e a r l y there i s an i n c e n t i v e f o r reducing the amount of sorbent. 24).

American Chemical Society: Washington. Data from Refs.ch004 4.1021/bk-1983-0226.acs. 1983 | doi: 10. J. Wei. 2012 | http://pubs. E f f e c t o f bed temperature on g r a i n s i z e and asymptotic f r a c t i o n a l s u l f a t i o n o f limestone.org Publication Date: July 28. 1983. 9 and 19. SAROFiM Fluidized-Bed Coal Combustion 1050 1100 1150 73 1200 Temperature (°K) Figure 3..Downloaded by CORNELL UNIV on December 2.. ACS Symposium Series. In Chemical Reaction Engineering—Plenary Lectures. et al. DC. .

From F i g u r e 4. b e i n g given by the v o l u m e t r i c f l o w r a t e r e q u i r e d f o r combustion m v d i v i d e d by the f l u i d i z i n g v e l o c i t y U . E l u t r i a t i o n r a t e s i n c r e a s e approximately i n p r o p o r t i o n to the e x p o n e n t i a l of the r a t i o u /u^_ of the f l u i d i z i n g to t e r m i n a l v e l o c i t y .ch004 74 CHEMICAL REACTION ENGINEERING c o r r e l a t i o n s f o r the bounding curves are given i n Figure 4 where the dimensional coordinates are f o r the c o n d i t i o n s i n an AFBC (using a s p h e r i c i t y f a c t o r φ = 0. From c o n s i ­ d e r a t i o n o f the t r a d e . which provides a u s e f u l . 31) view of bubble flow. p a r t i c l e s w i t h diameters below 350 ym once e n t r a i n e d from the bed w i l l be c a r r i e d over t o the p a r t i c u l a t e c o l l e c t i o n devices s i n c e t h e i r t e r m i n a l v e l o c i t i e s w i l l be exceeded by the f l u i d i z i n g v e l o c i t y . For FBC's. When the emulsion v e l o c i t y i s f a s t r e l a t i v e t o the bubble r i s e v e l o c i t y the bubbles are s a i d to be slow or c l o u d ­ l e s s and the emulsion gas uses the bubble as a by-pass (see Figure 5). J.5. 1983 | doi: 10. According t o the two-phase theory o f f l u i d i z a t i o n (29). the bed c r o s s s e c t i o n area i s f i x e d . i t i s d e s i r a b l e t o operate a t as h i g h a v e l o c i t y above the minimum f l u i d i z i n g v e l o c i t y as i s p r a c t i c a l . From a viewpoint of m i n i m i z i n g the c r o s s . The t r a n s i t i o n from slow t o f a s t bubble depends upon the 1 F a q 1 Q m m In Chemical Reaction Engineering—Plenary Lectures.s e c t i o n a l area of a bed.1 MW thermal output per square meter of bed area.7l/gd^ (29) i s slow or f a s t r e l a t i v e t o the gas v e l o c i t y i n the emulsion phase ( u f / e f ) .1021/bk-1983-0226. t h i s s i z e i s found t o correspond t o a minimum f l u i d i z i n g v e l o c i t y of 0. DC. The b u b b l i n g behavior o f a bed i s a l s o determined by the f l u i d i z i n g v e l o c i t y u . the p a r t i c l e s i z e s are about 1. At t h i s v e l o c i t y . the excess v e l o c i t y over that r e q u i r e d f o r minimum f l u i d i z a t i o n passes through the bed i n bubbles. At low v e l o c i t i e s the slopes approach two as would be expected f o r v i s c o u s flow.o f f s between decreased bed c r o s s . the bubbles are s a i d to be f a s t o r clouded and the gas c i r c u l a t e s through a cloud s u r ­ rounding the bubble as shown s c h e m a t i c a l l y i n F i g u r e 5 (adapted from Ref. as may be seen from F i g u r e 4.0 mm. American Chemical Society: Washington.s e c t i o n and i n c r e a s e d e l u t r i a t i o n r a t e s a v e l o c i t y o f about 2 m/s i s o f t e n s e l e c t e d as the nominal o p e r a t i n g v e l o c i t y i n AFBC s.. For our t e s t case o f 100 MW ^hernial output. When the bubble r i s e v e l o c i t y exceeds the emulsion v e l o c i t y . et al.org Publication Date: July 28.Downloaded by CORNELL UNIV on December 2. although o v e r s i m p l i f i e d (30. ACS Symposium Series. Wei. The gas flow through the bubbles depends on whether the bub­ b l e r i s e v e l o c i t y .4m/s. 1983. Once the f l u i d i z i n g v e l o c i t y i s s e l e c t e d . The upper l i m i t on f l u i d i z i n g v e l o c i t y i s imposed i n part by the i n c r e a s e i n amount of e l u t r i a t e d m a t e r i a l w i t h i n c r e a s i n g v e l o c i t y . . 0. 32). and a t the h i g h e r v e l o c i t i e s at which i n e r t i a l forces are dominant.acs. 2012 | http://pubs. the c r o s s s e c t i o n a l area o f the bed i s 87 m .6).. a c c o r d i n g to one of tfie a v a i l a b l e e m p i r i c a l c o r r e l a t i o n s (28). The approximate c r o s s s e c t i o n a l area of AFBC s may be estimated by n o t i n g that the v e l o c i t y c o n s t r a i n t of 2 m/s corresponds approximately t o 1. the slopes approach 0. the approximate t r a n s i t i o n p o i n t to the regime i n which i n e r t i a l forces b e g i n to become appreciable.

C o r r e l a t i o n s f o r the minimum f l u i d i z i n g v e l o c i t y u ^ and p a r t i c l e t e r m i n a l v e l o c i t y u. SAROFiM Fluidized-Bed Coal Combustion 75 Downloaded by CORNELL UNIV on December 2. American Chemical Society: Washington. .. 2012 | http://pubs. 1983 | doi: 10. DC.4.1021/bk-1983-0226. ACS Symposium Series.org Publication Date: July 28. J.acs.. as a f u n c t i o n o f p a r t i c l e s i z e . In Chemical Reaction Engineering—Plenary Lectures. Wei.ch004 dp (/im) Figure h. 1983. et al.

Wei.ch004 76 C H E M I C A L REACTION ENGINEERING d (m) B Figure 5.Downloaded by CORNELL UNIV on December 2. .. ACS Symposium Series. American Chemical Society: Washington.acs.org Publication Date: July 28. et al. 2012 | http://pubs. J. 1983 | doi: 10. DC.1021/bk-1983-0226. The dependence o f the t r a n s i t i o n from the slow t o f a s t bubble regime on bubble diameter d^ and minimum f l u i d i z a t i o n velocity u In Chemical Reaction Engineering—Plenary Lectures. 1983..

and a reasonable value f o r α o f 0. I f we n e g l e c t temporarily the c r o s s .u ^ ) . The bubbles are.4 m/s and a bubble-cap p l a t e w i t h A = 2. For an assumed r a t i o of wake t o bubble volume. J.s e c t i o n o f the bed occupied by the bubbles and the a s s o c i a t e d s o l i d s moving upwards. American Chemical Society: Washington. . The simple c r i t e r i a f o r gas r e ­ c i r c u l a t i o n . the s o l i d c i r c u l a t i o n time i s found to be about 3 t o 6 seconds which i s slow enough compared t o limestone r e a c t i o n times (see above) o r char burnout times (see below) that the bed s o l i d s can be t r e a t e d as being well-mixed.4m/s.1 1 ^ ) 0 1 . the v o l u m e t r i c c i r c u l a t i o n r a t e of s o l i d s per u n i t c r o s s . equals the emulsion v e l o c i t y . ( 3 3 ) .13m. expected t o s t a r t i n the slow o r c l o u d l e s s bubble regime but a c c e l e r a t e i n t o the f r e e bubble regime a t an e l e v a t i o n o f 0. The s o l i d c i r c u l a t i o n time i s then equal to h/(u .org Publication Date: July 28. u^f = 0.1 t o 0. As the bed p a r t i c l e diameter i n c r e a s e s . which may be estimated from the simple r e l a t i o n developed from the theory f o r bubble growth due t o coalescence by Darton e t a l .4.2 and e = 0.079 m a t the d i s ­ t r i b u t o r p l a t e t o a value of 1 m a t the top o f the bed (1 m). and i s the value encountered a t a height o f 0. ACS Symposium Series.71/gdb.5 χ 10" m . 1983 | doi: 10. as a consequence o f the entrainment o f s o l i d s i n the bubble wake. 0. mf mf T N E A S (7) + For values of α o f 0. Wei. i s then Q Q 2 m f 2 Q Downloaded by CORNELL UNIV on December 2. Whether the gas can be t r e a t e d as being well-mixed o r i n p l u g flow depends upon the v e l o c i t y o f the downward f l o w i n g s o l i d s r e l a t i v e t o the minimum f l u i d i z i n g v e l o c i t y (34). For the values U = 2m/s.2 (34). DC. When t h i s v e l o c i t y exceeds the i n s t e r t i t i a l gas v e l o c i t y o f f/ f* 8 i s r e c i r c u l a t e d w i t h the s o l i d s . h = lm.ch004 i s m 1 0 m q u m e m -U2->l _±_ u ^ αε .acs.s e c t i o n a l area o r a i ^ .. The bubble motion w i l l a l s o determine the s o l i d c i r c u l a t i o n i n the bed.1 to 0. For u = 2 m/s and u = 0.54 b (u -u o m f ) (h + 4 / T ) 2 / 5 4 / 5 /g (6) 1 / 5 where A i s the area o f d i s t r i b u t o r p l a t e per o r i f i c e and h i s the height o f the bubble above the p l a t e .5 we f i n d that the t r a n s i t i o n from a p l u g flow t o well-mixed gas occurs a t a value of m f In Chemical Reaction Engineering—Plenary Lectures.1m above the d i s t r i b u t i o n p l a t e . the bubbles i n c r e a s e i n diameter from a value of 0. 0. u ^ / ε ^ .u f ) a . developed i n a more general form by K u n i i and L e v e n s p i e l ( 3 4 ) . SAROFiM Fluidized-Bed Coal Combustion 77 minimum f l u i d i z i n g v e l o c i t y and the bubble diameter d^. u f increases and the f r a c t i o n of the bed that i s i n the slow bubble mode w i l l i n c r e a s e . The bubble diameter at which the bubble v e l o c i t y .1021/bk-1983-0226..1m. the v e l o c i t y o f the s o l i d s f l o w i n g downwards i s then determined by t h e i r v o l u m e t r i c flow r a t e per u n i t c r o s s . Whereas FCC's operate p r i m a r i l y i n the f a s t bubble regime AFBC s operate i n the t r a n s i t i o n of the f a s t t o slow bubble regimes. d = 0. 1983.s e c t i o n a l area of bed i s equal t o ( u . 2012 | http://pubs. et al. t h e r e f o r e .

8 f a l l s r a p i d l y but compensation i s provided by the i n c r e a s e d convection c o n t r i b u t i o n given by the second term. convection from gases f l o w i n g past the tube. The heat t r a n s f e r coef­ f i c i e n t from the p a r t i c l e s i s then governed by conduction across the gap s e p a r a t i n g the p a r t i c l e s from the w a l l . . For the considions here. From the expanded bed h e i g h t ..V 4 .78 CHEMICAL REACTION ENGINEERING u / u f i n the range of 10 to 20. The above e x p r e s s i o n i s f o r a tube surface i n the emulsion phase. The con­ t r i b u t i o n s to the heat t r a n s f e r by the above mechanisms i s shown i n Figure 6. so that the t o t a l passes through a minimum. et al.ch004 ? Heat Transfer ( S e l e c t i o n of Tube Area) The heat t r a n s f e r to the immersed tubes i s by a combination of r a d i a t i o n . and sorbent feed r a t e . w i t h the f i r s t term represent­ ing the conduction from the p a r t i c l e s and the second the augmenta­ t i o n of the f l u x by convection. and once again we f i n d a d i f f e r ­ ence between the regime of operation of an FCC which operate w i t h U Q / U J J J ^ >20 and AFBC which t y p i c a l l y operate w i t h u / t ^ f below the transition point.1021/bk-1983-0226. I l/ε . corresponding to an expanded bed h e i g h t of about lm..[12 + 0. 2012 | http://pubs. 0 m Downloaded by CORNELL UNIV on December 2. and ε^ i s the e f f e c t i v e emm i s s i v i t y of a plane formed by the s p h e r i c a l p a r t i c l e s .1 b w 9 <> where ε i s the tube w a l l e m m i s i v i t y . DC. 34).acs. American Chemical Society: Washington. the temperature of the p a r t i c l e s near the w a l l does not depart ap­ p r e c i a b l y from the mean bed temperature. The sum of the conductive and convective f l u x e s can be c a l c u l a t e d from the expression derived by Decker and Glicksman (7_) : ^ .Ι/ε. i t can be r e a d i l y shown that the mean residence time of the limestone i n the bed i s about 20 hours.3 i s assumed. As p a r t i c l e diameter increases the conduction con­ t r i b u t i o n given by the f i r s t term i n Eq. An other important e f f e c t of bubbles i s to cause the bed to expand. since In Chemical Reaction Engineering—Plenary Lectures. The bed expansion i s a consequence of the bubble h o l d up i n the bed and can be c a l c u l a t e d from the bubble flow r a t e and the bubble r i s e v e l o c i t y (29.org Publication Date: July 28. The r a d i a t i v e heat t r a n s f e r c o n t r i b u t i o n can be adequately approximated by the f l u x between two i n f i n i t e p a r a l l e l gray p l a t e s 4 h r ( T b . J. 1983 | doi: 10.05 (1 + 2 0 ) ( ^ d p ) P r ] (8) where 6 i s the bed v o i d volume. and t r a n s f e r from p a r t i c l e s i n the v i c i n i t y of the tube s u r f a c e . Wei. ACS Symposium Series. bed c r o s s s e c t i o n a l a r e a . Since the p a r t i c l e residence time near the tube w a l l s i s s m a l l r e l a t i v e to t h e i r thermal r e l a x a t i o n times (see Table 1 ) . The e f f e c t i v e heat t r a n s f e r c o e f f i c i e n t to the tubes w i l l be s l i g h t l y lower than that given by Equations 8 and 9. a bubble v o i d f r a c t i o n of 0. 1983.

1983 | doi: 10.acs. SAROFiM Fluidized-Bed Coal Combustion Figure 6.Downloaded by CORNELL UNIV on December 2. et al.. J. American Chemical Society: Washington.org Publication Date: July 28.ch004 4. C o n t r i b u t i o n s o f the convective and r a d i a t i v e t i o n s t o heat t r a n s f e r on p a r t i c l e diameter. 1983. DC. 79 contribu- . Wei. ACS Symposium Series. 2012 | http://pubs.1021/bk-1983-0226.. In Chemical Reaction Engineering—Plenary Lectures.

Downloaded by CORNELL UNIV on December 2. e i t h e r the heat t r a n s f e r c o e f f i c i e n t o r immersed tube area must be v a r i e d correspondingly.8 MW w i t h the stack gases ( f o r an exhaust temperature of 450 K) and 1. Given a r e c y c l e o f 13 MW t o the bed as a i r preheat. m~l p a r t i c l e radius. The governing population balance f o r the carbon i n the bed i s : . The area of the tubes immersed i n the bed i s then determined from energy balances on the FBC (Figure 7). J.org Publication Date: July 28. tubes w i t h a h o r i z o n t a l p i t c h o f 150 mm and a v e r t i c a l p i t c h o f 125 mm.1021/bk-1983-0226. The tube area needed t o achieve t h i s i s 515 m^. An energy i n p u t w i t h the c o a l of 111 MW i s needed to provide the d e s i r e d thermal output of 100 MW and the l o s s e s o f 9. kg t o t a l s o l i d s i n bed. e . 1983. p ( R ) = ô(R-R^). C o n t r o l o f bed temperature provides some s p e c i a l challenges. Wei. ACS Symposium Series. et al.ch004 80 CHEMICAL REACTION ENGINEERING the tubes w i l l be s h i e l d e d p e r i o d i c a l l y from contact w i t h the dense phase by bubbles. American Chemical Society: Washington. 2012 | http://pubs. m r a t e o f change o f p a r t i c l e r a d i u s .. In order t o evaluate the carbon l o s s e s i t i s d e s i r a b l e t o consider a balance on the carbon i n the bed (34). m/s carbon l o a d i n g . kg/s s o l i d s withdrawal r a t e . provided for example by s i x rows o f 50 mm O. f o r n e g l i g i b l e l o s s o f carbon by e l u t r i a t i o n and Q In Chemical Reaction Engineering—Plenary Lectures. s" f r a c t i o n of mass of c o a l i n s i z e range R t o R + dR.acs. 1983 | doi: 10.πΓ p(R) f o r feed stream. Carbon Combustion E f f i c i e n c y ( S e l e c t i o n o f Coal Feed Diameter) The p r i n c i p a l l o s s o f combustible from the bed i s by l o s s of unburned carbon e i t h e r e l u t r i a t e d from the bed o r withdrawn w i t h the bed s o l i d s . . kg For the s p e c i a l case o f a feed o f constant s i z e R-^. DC.3 MW w i t h the spent bed solids (assuming no recovery of the s e n s i b l e h e a t ) . This may be achieved over a moderate load change by v a r y i n g the area o f tubes immersed i n the bed by v a r y i n g the h e i g h t o f the bed. To s i m p l i f y the a n a l y s i s we w i l l f i r s t approximate c o a l as carbon. As the load i s v a r i e d . W F ρ (R) = o o = W K(R)p(R) r input c s o l i d s withdrawal d[p(R)R] c dR net shrinkage out o f s i z e range where F F^ K(R) p(R) p (R) R R W W Q Q c t = = = = = = = = = elutriation 3W p(R)R c (10) R growth w i t h i n s i z e range c o a l feed. 73 MW must be e x t r a c t e d by c o i l s immersed i n the bed i n order t o maintain the bed temperature a t 1116 K. i ..D. kg/s e l u t r i a t i o n constant f o r p a r t i c l e s o f s i z e R.

4.. American Chemical Society: Washington.2 S MW 50. SAROFiM 81 Fluidized-Bed Coal Combustion 23. 1983. J. tube w i t h a h o r i z o n t a l p i t c h of 150 mm and a v e r t i c a l p i t c h o f 125 mm.1021/bk-1983-0226. et al. e.org Publication Date: July 28. o 0..3 MW BED SOLIDS I3MW 589K 298 Κ AIR PREHEAT 9.8 MW = 515 m 2 h(T -Tw> B _ L .D.4 MW t III MW QF Q =73 C MW ^ -T =644 Τ «ΙΙΙ6Κ Κ B w Θ 1. .125 m T'b 0 J ( 5 m Ο ^Ο ο ο 0 Figure Τ· Energy balance on a h y p o t h e t i c a l 100 MW^ b o i l e r and t h e in-bed heat t r a n s f e r area r e q u i r e d t o m a i n t a i n the bed temperature at 1116 K. 1983 | doi: 10. DC.ch004 Qc*27.g. Wei. In Chemical Reaction Engineering—Plenary Lectures.acs.. 6 rows o f 50 mm O. ACS Symposium Series. 2012 | http://pubs.2 MW Downloaded by CORNELL UNIV on December 2.

org Publication Date: July 28. I t i s a v a r i a b l e of major impor­ tance because i t determines the carbon l o s s from the bed and a l s o has an important impact on the emissions of n i t r o g e n oxides. and C the oxygen concentration i n the emulsion phase. Eq.6 Re 1 / 2 Sc 1 / 3 ] (14) The oxygen concentration C w i l l depend upon the excess a i r .C H E M I C A L REACTION ENGINEERING 82 w i t h the s o l i d s withdrawn from the bed [K(R) = Ί?ι = 0 ] .ch004 W c F c R o l 2 -*Γ- = ÔShPC^ where t ^ i s the burning 2 ( 1 2 ) . 1983. expressed as a f r a c t i o n of the s t o i c h i o m e t r i c a i r . Estimates of the carbon l o a d i n g can be obtained by e v a l u a t i n g t ^ from the r e l a t i o n f o r a s h r i n k i n g sphere model of a d i f f u s i o n l i m i t e d o x i d a t i o n of carbon. f o r p a r t i c l e s of density p and i n i t i a l diameter c U b 48ShPC ( 1 3 ) p where Sh i s the Sherwood Number. V the oxygen d i f f u s i v i t y . ACS Symposium Series. 2012 | http://pubs. Assuming that n e g l i g i b l e amounts of oxygen by-pass the bed i n bubbles. Thus p m Sh * ε[2 +0. p the carbon d e n s i t y . American Chemical Society: Washington. DC. Although some controversy e x i s t s on the c o r r e l a t i o n of Sherwood Number a p p l i c a b l e to f l u i d i z e d beds. C the t o t a l molar gas c o n c e n t r a t i o n . 10 can be solved f o r the p a r t i c l e s i z e d i s t r i b u t i o n ρ(R) and the carbon l o a d i n g . where V i s the oxygen d i f f u s i v i t y ..1021/bk-1983-0226. and y the oxygen mole f r a c t i o n ) .d e f i n e d combus­ t i o n experiments support the use of the Ranz and M a r s h a l l (35) or F r o s s l i n g (36) c o r r e l a t i o n w i t h an approximate c o r r e c t i o n of e f to allow f o r the o b s t r u c t i o n to d i f f u s i o n by the i n e r t p a r t i c l e s surrounding the burning char p a r t i c l e s (37). the oxygen concentration C i n the bed can be r e l a t e d to the i n l e t oxygen concentration C and excess a i r by p p Q In Chemical Reaction Engineering—Plenary Lectures. and f o r a d i f f u s i o n l i m i t e d carbon burning to C O 2 (R = -6ShPC^yQ /p R.f Vb time of p a r t i c l e s of i n i t i a l radius R-^. . I t i s r e a d i l y shown t h a t . Wei. The carbon l o a d i n g i s found to be p r o p o r t i o n a l to coal feed rate and p a r t i c l e burning time.acs.. 1983 | doi: 10. J. and the f l u i d mechanics. w e l l . et al. The s o l u t i o n s are c T c 0 \ ψο 2 γ and P Downloaded by CORNELL UNIV on December 2.

) s (17) K ± / J £ ο the p r e v i o u s l y determined values of h = 0. and the f r a c t i o n (W /W ) of the bed s o l i d s i n the form o f carbon: s c s g C T m m W c. 12. an excess a i r e of 0.83 Kg/s f o r 111 MW thermal i n p u t ) and burning time i n t o Eq.org Publication Date: July 28.acs.5. and 67 seconds f o r plug flow.2. and are then blown out of the bed.1021/bk-1983-0226. . 1983 | doi: 10. In Chemical Reaction Engineering—Plenary Lectures. one i s i n a p o s i t i o n t o evaluate the carbon l o s s from the bed. American Chemical Society: Washington. J. the p a r t i c l e s i z e d i s t r i b u t i o n p(R) of carbon i n the bed. The f r a c t i o n m /m-p o f the carbon feed l o s s w i t h spent solids i s determined by the rate m o f spent s o l i d w i t h d r a w a l . 2012 | http://pubs. The carbon l o a d i n g i n the bed i s then determined by s u b s t i t u t i n g the c o a l feed r a t e (3.ch004 T W W = W T 9 Ahp (l. and the carbon l o a d i n g W (Eq. Wei. The f r a c t i o n o f the t o t a l bed weight which i s i n the form o f carbon i s s m a l l . e l u t r i a t i o n o f carbon that has burned down t o an e l u t r i a b l e s i z e range.. A carbon l o a d i n g o f 103 Kg i s obtained f o r the case o f p l u g f l o w i n the gase phase. A = 87 m and the density of limestone ( p = 2400 Kg/m^). SAROFiM Fluidized-Bed Coal Combustion 83 f o r a w e l l .s _ s ^ ^ ( 1 8 ) Τ The f r a c t i o n m /m l o s t by e l u t r i a t i o n i s determined by the e l u t r i a t i o n r a t e constant K ( R ) . ACS Symposium Series.3Γ * 2. With carbon l o a d i n g determined.4. and e f of 0. DC.14 percent o f the t o t a l bed weight. a bed temperature o f 1116 K.7 m.s t i r r e d emulsion gas.. With char p a r t i c l e s 1mm i n diameter. For t h i s simple model c e F c 9 Z m F = (~) * (0. A f i r s t approximation f o r t h i s l o s s may be obtained by assuming that that p a r t i c l e s of feed diameter d^ s h r i n k t o an e l u t r i a b l e s i z e d approximately 300 ym from Figure 4. The three p r i n c i p a l sources are carbon withdrawn from the bed w i t h spent s o l i d s . The lower times are more p e r t i n e n t t o AFBC s i n which the gas i s approximately i n p l u g flow. 10). This mechanism f o r a t t r i t i o n has been s t u d i e d by M a s s i m i l l a and coworkers (38-41). and C p = ( 1 6 ) (l+e)£n(l+l/e) f o r p l u g flow. et al. S u b s t i t u t i n g i n t o m Downloaded by CORNELL UNIV on December 2. 1983. we f i n d that the carbon accounts f o r only 0. the burning times are 185 seconds f o r a w e l l . and the e l u t r i a t i o n o f f i n e s produced by a t t r i t i o n .7 χ 10 i (19) d Another source o f e l u t r i a t e d carbon are the f i n e s produced by the a t t r i t i o n of the carbon surface by a b r a s i o n .s t i r r e d gas.

and t h e r e f o r e carbon combustion e f f i c i e n c y . The above s i m p l i f i e d a n a l y s i s was intended to provide a f e e l f o r the r e l a t i v e importance of the processes that govern carbon l o a d i n g . and a l s o on the model assumptions.u c a ο mf) n _ 3k (u -u -) a ο mf . Wei.. The r a t e of the carbon surface r e g r e s s i o n due to a t t r i t i o n i s approximately given by Q R (20) where k i s about 3. the optimum depends upon o p e r a t i n g c o n d i t i o n s . 1983 | doi: 10. As c o a l p a r t i c l e feed s i z e increases the a t t r i t t e d carbon increases (note t ^ i n Eq. J.1x10 The above c a l c u l a t i o n s show a carbon l o s s of about 4 percent of the c o a l feed. ACS Symposium Series.p equals 1. Carbon l o s s e s can t h e r e f o r e be minimized by the j u d i c i o u s choice of c o a l feed s i z e . and that i t i s much higher during o x i d a t i o n than p y r o l y s i s . The f i n e s e l u t r i a t e d from the bed are u s u a l l y captured i n a cyclone and r e c y c l e d to the bed.C H E M I C A L REACTION 84 ENGINEERING They f i n d that the r a t e of a t t r i t i o n i s p r o p o r t i o n a l to the energy d i s s i p a t i o n r a t e i n the bed.1021/bk-1983-0226.5x10"^. p r i m a r i l y as f i n e s produced by carbon a t t r i t i o n or by the shrinkage of the c o a l feed. being considered. The r a t e of feed carbon l o s s due to the e l u t r i a t i o n of a t t r i t e d carbon i s then given by Downloaded by CORNELL UNIV on December 2. m /m. The s i m p l i f i e d model presented above y i e l d s the f o l l o w i n g expression f o r the optimum s i z e : c a 1/4 3 d ( i>opt 48ShPCp(d*) ρ k (u -u .org Publication Date: July 28.ch004 a d /2 ± 3p(R)Wk ( u . American Chemical Society: Washington. 22 i s 1. which i s p r o p o r t i o n a l to u . 2012 | http://pubs. 19) decreases. (21) For the c o n d i t i o n s we have s e l e c t e d .u ^ f .) c a ο mf (22) For the t e s t case. More com­ p l e t e treatments of AFBC s are a v a i l a b l e which consider the d e t a i l e d population balance equations f o r the char p a r t i c l e s coupled w i t h an oxygen balance (41-50). C l e a r l y . et al. These treatments have given r e s u l t s which p a r a l l e l observations on o p e r a t i n g AFBC*s but 1 In Chemical Reaction Engineering—Plenary Lectures. so that high combustion e f ­ f i c i e n c i e s are achievable w i t h AFBC's. DC. B e t t e r understanding of the residence time of f i n e s i n a bed i s needed i n order to deter­ mine the r e c y c l e r a t e . the optimum c o a l feed s i z e given by Eq.acs. They p o s t u l a t e that a s p e r i t i e s are produced on the surface of the char during combustion and that these are abraded by c o l l i s i o n s w i t h the bed s o l i d s .. 1983. .6mm. 21 i s p r o p o r t i o n a l to d^) but the e l u t r i a t e d carbon (Eq.

Studies o f the r e a c t i o n o f oxygen w i t h carbon a t temperatures o f i n t e r e s t f o r AFBC's suggest that i t i s near zero order i n oxygen (62).acs. Most models have been based on an assumed f i r s t order r e a c t i o n but they can be r e a d i l y m o d i f i e d t o accommodate the more r e a l i s t i c lower r e a c t i o n order (63. E x t e r n a l D i f f u s i o n vs. These show that f o r p a r t i c l e s o f 1 mm diameter 1116 K. As expected. A g e n e r a l i z e d treatment of the carbon o x i d a t i o n r e a c t i o n s a l l o w i n g f o r the two g a s i f i c a t i o n r e a c t i o n s . 1983. The refinements that can be made t o the model f o r c o a l char o x i d a t i o n are seemingly endless (51). Dominant Oxidant. The c o r r e c t i o n f o r order o f r e a c t i o n w i l l be most important f o r the p r e d i c t i o n of the combustion of r e c y c l e d f i n e s which are i n the s i z e range i n which chemical k i n e t i c s dominate and f o r p r e d i c t i n g the performance o f p r e s s u r i z e d f l u i d i z e d beds. et al. 64).f i l m model f o r char o x i d a t i o n . Carbon g a s i f i c a t i o n i n f l u i d i z e d bed combustors can occur by both the C O 2 / C and the O 2 / C r e a c t i o n s : Downloaded by CORNELL UNIV on December 2.4. In Chemical Reaction Engineering—Plenary Lectures.. CO i s then converted t o C O 2 as i t d i f f u s e s from the p a r t i c l e surface. i n which C O 2 reacts w i t h carbon a t the surface t o form CO w i t h the CO b e i n g o x i d i z e d i n a d i f f u s i o n flame enveloping the p a r t i c l e . 85 Fluidized-Bed Coal Combustion SAROFiM are q u a l i f i e d by u n c e r t a i n t i e s i n the flow models and mass t r a n s f e r models which are used t o c a l c u l a t e the t r a n s f e r o f oxygen t o the dense phase and by d i f f e r e n c e s i n assumptions concerning the comb u s t i o n of the char.x ) C 0 2 (24) Avedasian and Davidson (37) i n t h e i r p i o n e e r i n g work on the modelling of char o x i d a t i o n i n f l u i d i z e d beds assumed a t w o .|) 0 (23) 2C0 2 + C = xCO + (1 . L a t e r s t u d i e s (52) showed that the C O 2 / C r e a c t i o n was too slow a t f l u i d i z e d bed temperatures t o c o n t r i b u t e s i g n i f i c a n t l y t o the carbon g a s i f i c a t i o n r a t e . A few o f these w i l l be discussed b r i e f l y . E a r l y c a l c u l a t i o n s by Borghi e t a l (59) determined the c o n t r i b u t i o n s of k i n e t i c s and e x t e r n a l d i f f u s i o n as a f u n c t i o n of bed temperature. Reaction Order. 1983 | doi: 10. 23 and 24.org Publication Date: July 28. c o n d i t i o n s t y p i c a l o f commercial p r a c t i c e . American Chemical Society: Washington. ACS Symposium Series. Eqs. based on molecu l a r beam s t u d i e s on graphite (53).. DC. Wei. the rate of carbon o x i d a t i o n i s determined by the combination o f e x t e r n a l d i f f u s i o n and the k i n e t i c s o f the carbon o x i d a t i o n . The primary product o f the C / O 2 r e a c t i o n i s b e l i e v e d to be CO. and the carbon monoxide o x i d a t i o n i n the boundary l a y e r has been presented by Amundson and coworkers (54-58).ch004 C0 (1 2 + C= . p a r t i c l e s i z e . Experimental support f o r these p r e d i c t i o n s i s provided by Ross and Davidson (60. and oxygen concentrations. J. . 2012 | http://pubs.1021/bk-1983-0226. 61). Chemical K i n e t i c s . the d i f f u s i o n and k i n e t i c r e s i s t a n c e s are of equal importance.

and v a r i a t i o n i n pore s i z e w i t h i n c r e a s i n g extent of r e a c t i o n . The importance of these at AFBC c o n d i t i o n s i s u n c e r t a i n .ch004 86 C H E M I C A L R E A C T I O N ENGINEERING Pore S t r u c t u r e . From the theory one can a l s o c a l c u l a t e that CO w i l l burn near the surface of a p a r t i c l e f o r l a r g e p a r t i c l e s but w i l l react outside the boundary l a y e r f o r s m a l l p a r t i c l e s . J. The chars produced from coals are h i g h l y porous. s i n c e the t h e o r e t i c a l c a l c u l a t i o n s . American Chemical Society: Washington. Carbon Monoxide Oxidation.1021/bk-1983-0226. i n q u a l i t a t i v e agreement w i t h experimental observations. This expectation i s supported by s t u d i e s of combustion of propane i n f l u i d i z e d beds. DC. w i t h i n t e r n a l surface areas of 100 to 1000 m^/g. In Chemical Reaction Engineering—Plenary Lectures. since the e x t e r n a l r e s i s t a n c e c o n s t i t u t e s a s i g n i f i c a n t f r a c t i o n of the t o t a l r e s i s t a n c e . and pore r a d i i ranging from nanometer to micron i n s i z e . A n a l y s i s of the carbon monoxide o x i d a t i o n i n the boundary l a y e r of a char p a r t i c l e shows the pos­ s i b i l i t y f o r the existence of m u l t i p l e steady s t a t e s (54-58). where i t was observed that i g n i t i o n and combustion took place p r i m a r i l y i n the bubble phase (74). I t i s determined i n p a r t by the heat r e l e a s e d at the p a r t i c l e surface due to r e a c t i o n and i n part to the a d d i t i o n a l heat released by carbon monoxide o x i d a t i o n near the p a r t i c l e surface (54-58). Models of i n c r e a s i n g s o p h i s t i c a t i o n have been developed to describe the r e a c t i o n i n porous chars (65-71) which a l l o w f o r d i f f u s i o n and chemical r e a c t i o n . The temperature of the burn­ ing char p a r t i c l e s w i l l run h o t t e r than that of the bed by amounts that depend upon p a r t i c l e s i z e . et al. are based on the use of g l o b a l k i n e t i c s f o r CO o x i d a t i o n . Wei.org Publication Date: July 28. d e s i r a b l e when examining d e t a i l s of secondary r e a c t i o n s such as those that i n f l u e n c e p o l l u t a n t forma­ t i o n which occur w i t h i n the pores.. I t i s therefore expected that the CO o x i d a t i o n rates i n the dense phase of f l u i d ­ i z e d beds w i l l be suppressed to l e v e l s considerably below those i n the bubble phase.2 m i l l i m e t e r s i z e coke p a r t i c l e s burning i n a f l u i d i z e d band of sand at 1173 Κ increased from the bed temp­ erature at low oxygen concentrations to values 150 to 200 Κ above the bed temperature f o r oxygen concentrations approaching that of a i r (72). More a t t e n t i o n needs to be given to the e f f e c t of bed s o l i d s on gas phase r e a c t i o n s occuring i n f l u i d i z e d r e a c t o r s . Use of such models are. Q u a n t i t a t i v e agreement w i t h theory would not be expected.. 2012 | http://pubs.Downloaded by CORNELL UNIV on December 2. 1983 | doi: 10. . Hydroxyl r a d i c a l s are the p r i n c i p a l oxidant f o r carbon monoxide and i t can be shown (73) that t h e i r concentration i s lowered by r a d i c a l r e ­ combination on surfaces w i t h i n a f l u i d i z e d bed. bed temperature. however. ACS Symposium Series. E s t i m a t i o n of t h i s temperature r i s e i s important f o r purposes of e v a l u a t i n g the NO/C r e a c t i o n and a l s o f o r p r e d i c t i o n of the burnout times of f i n e s . or i n e v a l u a t i n g the e f f e c t of pore s t r u c t u r e on a t t r i t i o n and fragmentation r a t e s . P a r t i c l e Temperature Overshoot. 1983. pore s i z e d i s t r i b u t i o n .acs. Measurements f o r 1. r e a c t i v i t y . The added refinements are not needed f o r purposes of c a l c u l a t i n g char burnout times f o r most of the carbon i n AFBC's.8 to 3.

the near dominance o f the e x t e r n a l d i f f u s i o n r e s u l t s i n good agreement being obtained between the p r e d i c t i o n s o f burning times obtained using r e l a t i v e l y simple models and experimental r e s u l t s . however^ of major importance t o the operation o f AFBC s s i n c e the c o a l must be d i s t r i b u t e d throughout a bed i n a manner that ensures t h a t the v o l a t i l e s w i l l have access t o s u f f i c i e n t a i r f o r t h e i r complete oxidation. c o a l contains on the average about 10 percent by weight of m i n e r a l c o n s t i t u e n t s . In p r i n c i p l e . Estimates of the v o l a t i l e r e l e a s e r a t e may be obtained from the e x t e n s i v e l i t e r a t u r e on c o a l p y r o l y s i s (76). DC. These y i e l d an ash during combustion which tends t o accumulate on the surface of the receding char. I n d i r e c t evidence f o r fragmentation of various chars during combustion was a l s o provided by Campbell and Davidson (75) who a t t r i b u t e d the d e v i a t i o n of the p a r t i c l e s i z e d i s t r i b u t i o n during the combustion of char p a r t i c l e s of uniform i n i t i a l s i z e from the p r e d i c t e d s i z e d i s t r i b u t i o n given by Eq. i n f l u e n c e the l a t t e r stages of combustion and the achievement of h i g h carbon burnout.S. such as the importance of h i g h i n t e r n a l CO concentrations on the augmentation of the reduction of NO by char. the ash e i t h e r f l a k e s o f f as the carbon surface recedes or forms a h i g h l y porous. such as pore s t r u c t u r e and chemical parameters. The d e t a i l e d models w i l l prove u s e f u l i n r e s o l v i n g i s s u e s that cannot be addressed by simpler models. which determines the y i e l d of the char. p a r t i c l e s i z e . V o l a t i l e E v o l u t i o n (Coal Feed L o c a t i o n ) Most models o f f l u i d i z e d . on the e f f e c t o f e v o l v i n g pore s t r u c t u r e on a t t r i t i o n and fragmentation. . Although a complete model f o r s i n g l e p a r t i c l e burning requires d e t a i l e d i n f o r m a t i o n on p h y s i c a l parameters.s i n t e r e d .ch004 T P a r t i c l e Fragmentation. Wei. M a s s i m i l l a and coworkers (41) have measured the c o a l fragments produced during p y r o l y s i s .4.. American Chemical Society: Washington. have t r e a t e d the v o l a t i l e e v o l u t i o n as being e i t h e r instantaneous o r uniformly d i s t r i b u t e d throughout the f l u i d i z e d bed. Since AFBC s operate below the f u s i o n temperature of ash.acs. ACS Symposium Series.D i f f u s i o n C o n t r o l . 1983. Downloaded by CORNELL UNIV on December 2. A U. I t may. i t s p o r o s i t y . 11 as b e i n g due t o fragmentation. the ash l a y e r should r e t a r d the r a t e of char combustion (34) but the experimental evidence t o date suggests that i t s e f f e c t i s s m a l l i n determining o v e r . however. and p a r t i c l e number. An added complication i n the modell i n g of c o a l combustion i s provided by the d e v o l a t i l i z a t i o n step. such as i n t r i n s i c r e a c t i v i t i e s o f char/ oxygen.1021/bk-1983-0226.b e d combustors have been developed for chars on cokes w i t h n e g l i g i b l e v o l a t i l e content o r . J. l o o s e l y .org Publication Date: July 28. i f address i n g c o a l s . et al. The c o a l d e v o l a t i l i z a t i o n step i s . the assumption of uniform v o l a t i l e r e l e a s e would be j u s t i f i e d . SAROFiM Fluidized-Bed Coal Combustion 87 A s h . f r i a b l e cage about the char. and on where CO combustion occurs.a l l burning r a t e s . T In Chemical Reaction Engineering—Plenary Lectures. 2012 | http://pubs. I f the v o l a t i l e r e l e a s e r a t e i s slow r e l a t i v e t o the rate of s o l i d c i r c u l a t i o n .. 1983 | doi: 10.

C H E M I C A L REACTION ENGINEERING Downloaded by CORNELL UNIV on December 2. Coal p a r t i c l e s i n j e c t e d a t the bottom of the bed are convected upward and d i f f u s e r a d i a l l y as a consequence of bubble motion. Park et a l (42) recognized the importance of modeling the v o l a t i l e release i n AFBC s and developed a plume model based on the instantaneous r e l e a s e of v o l a t i l e s and l a t e r a l d i f f u s i o n using a d i f f u s i v i t y based on t r a c e r d i s p e r s i o n . .s e c t i o n over which the v o l a t i l e s are r e leased i s determined by the s o l i d d i f f u s i v i t y P . 1983 | doi: 10. depending upon p a r t i c l e s i z e and bed temperature. 9. Wei. DC. ACS Symposium Series.org Publication Date: July 28. The v o l a t i l e r e l e a s e time i s therefore comparable to the s o l i d c i r c u l a t i o n time and n e i t h e r the model of instantaneous or distributed v o l a t i l e release i s v a l i d .ch004 88 Using the data of Howard and coworkers (77) Borghi et a l (59) have modeled the v o l a t i l e r e l e a s e rate f o r AFBC c o n d i t i o n s .. Stubingdon and Davidson (79) however showed that the combustion of hydrocarbons. i s governed by molecular d i f f u s i o n which i s considerably lower than the r a d i a l d i f f u s i o n obtained from t r a c e r s t u d i e s . 1983. which presents the c a l c u l a t e d ( s o l i d l i n e ) and measured (data p o i n t s ) weight l o s s of 3 m i l l i m e t e r p a r t i c l e s burned i n 5 percent oxygen stream i n a f l u i d i z e d bed maintained a t 1173 K. The radius r of the c r o s s . 26 represents only a f i r s t approximation. J. For 1 mm p a r t i c l e s the time f o r d e v o l a t i l i z a t i o n i s under 1 second.1021/bk-1983-0226. The mechanism for r a d i a l d i s p e r s i o n i s due to s o l i d and not gas d i f f u s i o n . The i n i t i a l steep drop i n weight i s due to v o l a t i l e e v o l u t i o n . For In Chemical Reaction Engineering—Plenary Lectures.acs. To a f i r s t approximation 1 g r = ifuZt (25) The c o r r e l a t i o n proposed by K u n i i and L e v e n s p i e l (34) w i l l be here used to obtain an estimate f o r f} 3 (26) The mechanism of s o l i d d i s p e r s i o n i s complex and p o o r l y understood so that Eq. 2012 | http://pubs. Their pred i c t i o n f o r both the duration of a v o l a t i l e flame and the subsequent char burnout times have been confirmed by the experimental measurements of Andrei (78). American Chemical Society: Washington. T h i r t y percent of the weight of coal i s l o s t i n a p e r i o d of a l i t t l e under 4 seconds for the 3 mm p a r t i c l e . which are a v a l i d surrogate f o r c o a l v o l a t i l e s . and i t i s followed by the slower char burnout stage. A s l i g h t v a r i a n t on the plume model of Park et a l (42) i s shown i n F i g . (The t r a c e r s t u d i e s apparently provide a measure of the meandering of a laminar stream without mixing at the molecular l e v e l needed f o r r e a c t i o n ) . Their model succeeded i n showing the major importance of l a t e r a l d i f f u s i o n w i t h i n AFBC*s i n determining feed p o i n t l o c a t i o n .. et al. Sample r e s u l t s are shown i n Figure 8. V o l a t i l e s w i l l be r e l e a s e d at a decaying r a t e f o r s e v e r a l seconds. These times can be compared w i t h the estimates of the s o l i d c i r c u l a t i o n time of 3 to 6 seconds obtained above.

Wei. S o l i d l i n e c a l c u l a t e d from t h e o r y . data p o i n t s experimental. ACS Symposium Series. American Chemical Society: Washington.. 1983 | doi: 10.ch004 4. Time-resolved values o f the f r a c t i o n a l weight r e t e n t i o n o f c o a l p a r t i c l e s i n i t i a l l y 3 mm i n diameter burned i n a f l u i d i z e d bed at 1173 Κ and an oxygen c o n c e n t r a t i o n o f 5 percent. J. DC. .org Publication Date: July 28.Downloaded by CORNELL UNIV on December 2. 2012 | http://pubs. SAROFiM Fluidized-Bed Coal Combustion 89 Figure 8. F i g u r e 9· Schematic e l e v a t i o n and p l a n views o f v o l a t i l e plume formed by c o a l i n j e c t e d at base o f bed.acs. In Chemical Reaction Engineering—Plenary Lectures..1021/bk-1983-0226. et al. 1983.

0.3. DC.4. .4 to 2.1 m.C H E M I C A L REACTION ENGINEERING 90 a v o i d volume δ of 0. 1983. 79 80). This importance of the NII3/NO r e a c t i o n and i t s p a r t i a l suppression by bed s o l i d s has been demonstrated by the i n j e c t i o n of N H 3 i n t o In Chemical Reaction Engineering—Plenary Lectures..5. The NO concentration then decays as a consequence of both heterogeneous and homogeneous reactions.org Publication Date: July 28. Consequently r . American Chemical Society: Washington. ACS Symposium Series. Wei.5 to 3 second.8 to 4 MW. a mean bubble diameter of 0. The spacing Β of c o a l feed p o i n t s (Figure 9) should be such that the a i r f l o w i n g i n the c r o s s . A t y p i c a l value f o r f i s about 0.1 of the s t o i c h i o m e t r i c a i r i s used to t r a n s p o r t the c o a l . AFBC's operate i n the temperature regime i n which ammonia reacts s e l e c t i v e l y w i t h NO i n the presence of oxygen (84): NH 3 + NO + 1/4 ° = 2 N + 2 3 / 2 H 2° 28> ( * Ammonia i s evolved w i t h the c o a l v o l a t i l e s and may be t h e r e f o r e p a r t i a l l y r e s p o n s i b l e f o r the reduction of NO that occurs i n AFBC's. Methods of overcoming the problem of m u l t i p l e feed p o i n t s i n c l u d e the use of a spreaders t o k e r to d i s t r i b u t e the c o a l evenly over the surface of the bed or the promotion of l a t e r a l mixing by r e c i r c u l a t i n g bed s o l i d s . The oxygen requirements of the v o l a t i l e s i s then s a t i s f i e d when v Downloaded by CORNELL UNIV on December 2.ch004 y v a 2 f -f Trr _ y a 2~ 1+e π (27) B For the values s e l e c t e d above Β i s 1.s e c t i o n ïïr^ of the v o l a t i l e plume should be s u f f i c i e n t to o x i d i z e the v o l a t i l e s . 83). J. 2012 | http://pubs. or approximately 25 to 55 feed p o i n t s . The f r a c t i o n f of the s t o i c h i o m e t r i c a i r requirement needed to consume the v o l a t i l e s w i l l depend upon the v o l a t i l e y i e l d and composition (76. the value of Vs = 0. A f r a c t i o n f of about 0.6 m.1021/bk-1983-0226. For our t e s t case. 1 Emissions of Nitrogen Oxides (Staging of A i r A d d i t i o n ) 1 One of the advantages of AFBC s i s that t h e i r emissions of n i t r o g e n oxides can be c o n s i d e r a b l y lower than corresponding values from p u l v e r i z e d c o a l f i r e d b o i l e r s . 1983 | doi: 10. This estimate agrees w i t h current commercial p r a c t i c e of spacing feed p o i n t s at i n t e r v a l s of 1 to 3 m.acs.. t h i s corresponds to one c o a l feed p o i n t f o r every 1.4 to 0. The n i t r o g e n oxides are produced p r i m a r i l y by the o x i d a t i o n of n i t r o g e n o r g a n i c a l l y bound i n the c o a l (82. The requirement f o r a l a r g e number of feedpoints i s one of the shortcomings of AFBC s. et al. The time f o r the bubble to r i s e to the surface we have p r e v i o u s l y shown to be of the order of 1. Rapid conversion of the f u e l bound n i t r o g e n occurs near the d i s t r i b u t o r place w i t h peak l e v e l s of 1000 ppm NO and higher being observed. Because of the i n h i b i t i o n of f r e e r a d i c a l r e a c t i o n s w i t h ­ i n the bed t h i s r e a c t i o n i s expected to be most important i n bub­ b l e s and i n the s o l i d disengaging height above the bed.03 m^/s.

Carbon w i l l reduce NO d i r e c t l y : (1 . SAROFiM 91 Fluidized-Bed Coal Combustion d i f f e r e n t p o s i t i o n s w i t h i n a f l u i d i z e d bed combustor (85). c o n s i s t e n t w i t h the greater strength o f the NO bond than that i n 0 . i t has been observed that the r e a c t i o n i s a c c e l e r a t e d i n the presence o f oxygen (91).c o n t a i n i n g . ( i i ) the k i n e t i c s o f formation o f NO by the o x i d a t i o n of the products o f d e v o l a t i l i z a t i o n . depending upon the knowledge of the (1) d e v o l a t i l i z a t i o n chemistry and k i n e t i c s of f u e l n i t r o g e n which determines the d i s t r i b u t i o n of n i t r o g e n between char n i t r o g e n .acs. This l a t t e r r e s u l t may be a consequence o f the increase i n the CO concentration w i t h ­ i n a char p a r t i c l e as the 0 concentration i s r a i s e d .ch004 2 2 2 CaS0 + NO = CaS0 + 1/2 N 3 4 (30) £ T A complete modeling of NO formation i n AFBC s i s a formidable task. CO. At low temperatures (850 Κ ) . C. 1983 | doi: 10. and CaS0 . the NO reduction by char can be a c c e l e r ­ ated by i n c r e a s i n g the carbon l o a d i n g i n the bed by s t a g i n g the a i r a d d i t i o n (99-100). 1983. a s t a b l e chemisorbed oxygen compled (86) forms and i n h i b i t s the r e a c t i o n . For example. Because o f the many chemical r e a c t i o n s i n v o l v e d .γ)NO + C = 1/2 N 2 + xCO + ( l .1021/bk-1983-0226. Downloaded by CORNELL UNIV on December 2. 87). In order t o solve f o r the NO concentration one needs t o a l s o determine the concentration of C. and CaSO^ i n the bed and f o r the temperature overshoot by the carbon.x ) C 0 (29) 2 The r a t e o f the r e a c t i o n (86-90) i s about two orders of magnitude slower than the O2/C r e a c t i o n . DC. Wei.. Because the O2/C r e a c t i o n i s so much f a s t e r than the NO/C o r the carbon c a t a l y z e d CO/NO r e a c t i o n (86. The C0/C0 r a t i o i n the products of the r e a c t i o n increases w i t h i n c r e a s i n g temperature (86.org Publication Date: July 28. These experiments showed that the NO r e d u c t i o n was most e f f e c t i v e when the ammonia was i n j e c t e d d i r e c t l y above the bed. CO. 91). p a r t i a l l y s u l f a t e d limestone (93). the s i t u a t i o n e x i s t s i n which the e f f e c t i v e n e s s f a c t o r f o r the O2/C r e a c t i o n i s s m a l l and l i t t l e O 2 p e n e t r a t i o n i n t o char occurs a t a time when the e f f e c t i v e n e s s f a c t o r f o r the NO reduction r e a c t i o n s are near u n i t y . Several have been developed which adequately c o r r e l a t e a v a i l a b l e experimental data (94-98) but t h e i r p r e d i c t i v e c a p a b i l i t y i s yet to be proven. American Chemical Society: Washington. ammonia.4. 2012 | http://pubs. . and the a d d i t i o n a l complexity introduced by the f l u i d mechanics. ACS Symposium Series. however. guide the s e l e c t i o n of appropriate c o n t r o l s t r a t e g y .92) and the reduction of NO by s u l f i t e .. A d d i t i o n a l NO reduction r e a c t i o n s that may occur are the CO/NO r e a c t i o n c a t a l y z e d by bed s o l i d s (90 . J. so that the reduction i n NO may be a t the expense of an increase i n carbon l o s s o r an increase i n r e c y c l e of t i n e s . Several heterogeneous r e a c t i o n s c o n t r i b u t e t o the r e d u c t i o n of NO i n AFBC's. At AFBC temperatures. et al. 3 3 In Chemical Reaction Engineering—Plenary Lectures. But s t a g i n g the oxygen w i l l increase the carbon l o a d i n g and correspondingly the formation o f carbon f i n e s . ( i i i ) the k i n e t i c s of reduction of NO by NH . The understanding o f the dominant mechanism f o r NO formation and r e d u c t i o n can. however. and other s p e c i e s . models of NO formation i n beds are only p a r t i a l .

ACS Symposium Series. Reactions of p a r t i c u l a r importance are those between NO and char. Wei. A number of the c o r r e l a t i o n s used were derived from the l i t e r a t u r e on b u b b l i n g beds of f i n e p a r t i c l e s .2 m/s (estimated from u . The net consequence of t h i s would be to i n c r e a s e the importance of the slow or c l o u d l e s s bubble regime (see Figure 4 ) .ch004 0 m Impact of Immersed Tubes on Flow Regimes In the above attempt to provide an order-of-magnitude e s t i mate of the f a c t o r s c o n t r o l l i n g the design and operation of AFBC s gross approximations were made. I t i s of i n t e r e s t to n o t e . For a bubble r i s e v e l o c i t y of 3. presumably due to a r e d u c t i o n i n the s i z e of the bubbles. DC. American Chemical Society: Washington.7l/gd^ (29) and a bubble diameter of 0. The e a r l y s t u d i e s of flow i n coarse p a r t i c l e systems was f o r beds without immersed tubes (107. 1983 | doi: 10.1021/bk-1983-0226. 108). The s o l i d concentration i n the freeboard i s s u f f i c i e n t l y h i g h to c o n t r i b u t e s i g n i f i c a n t l y to the r e a c t i o n s occuring i n AFBC's.3 m. 1983. however. I t must be emphasized that the flow regimes i n beds of coarse p a r t i c l e s d i f f e r from those i n beds of f i n e p a r t i c l e s (105. a t y p i c a l h e i g h t s e l e c t e d f o r the freeboard. and the combustion of the r e c y c l e d f i n e s . J. p a r t i c u l a r l y i n e s t i m a t i n g some of the flow and mixing parameters. the burnout of carbon monoxide. The data of F i t z g e r a l d .5 m). L e v e n s p i e l and co-workers (109) show that the impact of tubes i s to reduce the d i s p e r s i o n of gas due to the meandering of a t r a c e r gas plume but to increase the d i f f u s i o n due to t u r b u l e n t mixing.u f + 0. that the e l u t r i a t i o n r a t e of l a r g e r p a r t i c l e s has been found to be g r e a t l y augmented by the concentration of f i n e s (103) i n a bed.. T In Chemical Reaction Engineering—Plenary Lectures. Downloaded by CORNELL UNIV on December 2. 106) and that t h i s must be taken i n t o c o n s i d e r a t i o n i n the s e l e c t i o n of the most r e l e v a n t models.org Publication Date: July 28. so that the r e c y c l e of f i n e s may i n f l u e n c e bed behavior i n an unobvious manner. The e f f e c t of tubes i n the bed i s t o decrease the pressure f l u c t u a t i o n s .acs.. The i n i t i a l v e l o c i t y of the s o l i d s that splash i n t o the freeboard i s 4 to 8 times the bubble r i s e v e l o c i t y (100) and the freeboard height i s determined by the k i n e t i c energy of the l a r g e r p a r t i c l e s f o r which drag forces are r e l a t i v e l y unimportant. Space i s not a v a i l a b l e to cover the s u b j e c t adequately and the reader i s r e f e r r e d to s e l e c t e d l i t e r a t u r e on the subject (101-104).C H E M I C A L REACTION 92 ENGINEERING Freeboard Reactions (Determination of Freeboard Height) A height of three to four meters above the bed i s r e q u i r e d to a l l o w s o l i d s e n t r a i n e d by the bubble wakes i n t o the freeboard to r e t u r n to the bed s u r f a c e . the maximum h e i g h t obtained by a p a r t i c l e w i t h an i n i t i a l v e l o c i t y s i x times the bubble r i s e v e l o c i t y i s 4. This augmentation of mixing by the tubes should be taken i n t o account i n the modeling of v o l a t i l e combustion. More recent s t u d i e s have shown that the f l u i d mechanics and gas and s o l i d mixing can be considerably i n f l u e n c e d by the presence of tubes i n the bed (109114). . et al. 2012 | http://pubs.

American Chemical Society: Washington. and changing heat l o a d without v a r y i n g bed temperature. DC. There i s c l e a r l y a need f o r a b e t t e r understanding o f the processes that govern ( i ) par­ t i c l e c i r c u l a t i o n and e l u t r i a t i o n i n l a r g e p a r t i c l e systems. ra Q Cp i n l e t oxygen c o n c e n t r a t i o n . reducing the number of c o a l feed p o i n t s . ( i i i ) the generation and burnout o f f i n e carbon p a r t i c l e s . the carbon monoxide i n f l u e n c e s the carbon p a r t i c l e temperature overshoot and a l s o p a r t i c i p a t e s i n the surface c a t a ­ l y z e d r e d u c t i o n o f NO. SAROFiM 93 Fluidized-Bed Coal Combustion Although general treatments o f the flow i n f l u i d i z e d beds o f coarse p a r t i c l e s . there have been some promising developments. 1983 | doi: 10. For example. p r e s s u r i z e d beds. J. i n view of the d i f f i c u l t y o f the problem. There i s c l e a r l y opportunity f o r improvement.org Publication Date: July 28. 113.ch004 1 X Legend of Symbols ο A 0 Β C bed c r o s s e c t i o n a l area. ( i i ) g r a i n growth f o r purposes o f improving stone u t i l i z a t i o n . and has already been commercialized. the order o f magnitude e s t i ­ mates of many o f the parameters i n the bed was intended t o i n d i c a t e which processes were important. 1983. The f a s t .4. mole/m 3 Continued on next page In Chemical Reaction Engineering—Plenary Lectures. A number o f f l u i d i z e d bed combustors o f advanced design have been developed o r are under i n v e s t i g a t i o n . Wei. w i l l only evolve s l o w l y . . These i n c l u d e the success achieved i n c o r r e l a t i n g heat t r a n s f e r data (7_. m u l t i . These i n c l u d e f a s t f l u i d i z e d beds.f l u i d i z e d r e ­ c i r c u l a t i n g bed i s f u r t h e s t developed of those advanced concepts. Downloaded by CORNELL UNIV on December 2. An attempt was made i n the p r e s e n t a t i o n t o show the complex i n t e r a c t i o n between the d i f f e r e n t processes occuring i n the bed.. the carbon f i n e s i n f l u e n c e the e l u t r i a t i o n r a t e s of coarser p a r t i c l e s . 2012 | http://pubs. 1 Concluding Comments The above c o n s i d e r a t i o n o f the f a c t o r s that govern the design and operation o f the f i r s t generation of AFBC s provide an a p p r e c i a t i o n f o r the parameters t h a t c o n s t r a i n t h e i r perform­ ance. Such i n t e r a c t i o n s add t o the challenges of modeling t h i s c l a s s o f chemical r e a c t o r s . ACS Symposium Series. 114) and the development o f s c a l i n g parameters t h a t permit the use o f c o l d flow models t o study many of the c h a r a c t e r ­ i s t i c s o f AFBC s (114. mole/m 3 average oxygen concentration i n emulsion phase. From a fundamental standpoint.1021/bk-1983-0226.s t a g e beds. et al.115). m spacing between c o a l feed p o i n t s . p a r t i c u l a r l y w i t h respect t o reducing the amounts o f sorbent used f o r s u l f u r capture.. reducing the l o s s o f carbon f i n e s . sorbent u t i l i z a t i o n may a f f e c t N 0 through the formation o f CaSO^ and bed pressure drop through the dependence of s o l i d d e n s i t y on extent of s u l f a t i o n .acs. c i r c u l a t i n g beds. and r o t a t i n g beds. carbon burning times deter­ mine the carbon l o a d i n g i n the bed which i n turn governs both the amount of f i n e char p a r t i c l e generation and the r e d u c t i o n of NO.

e. s Κ r a t e constant f o r the S0 /Ca0 r e a c t i o n . m d* diameter of p a r t i c l e s w i t h t e r m i n a l v e l o c i t y lower than fluidizing velocity. m h convective heat t r a n s f e r c o e f f i c i e n t i n Equation 8. 1983.. dimension­ less e l u t r i a t i o n constant f o r p a r t i c l e s of s i z e R. by e l u t r i a t i o n . Kg/s.acs. Kg/s s o l i d s withdrawal r a t e . American Chemical Society: Washington. m ο gas-phase d i f f u s i v i t y . and by a t t r i t i o n r e s p e c t i v e l y In Chemical Reaction Engineering—Plenary Lectures. and a r e f e r t o l o s s w i t h s o l i d s w i t h d r a w a l .94 C H E M I C A L R E A C T I O N ENGINEERING Legend o f Symbols—Continued Downloaded by CORNELL UNIV on December 2. m d^ i n i t i a l diameter of char p a r t i c l e . 1983 | doi: 10.1021/bk-1983-0226. S u b s c r i p t s s.. J/Kg c o e f f i c i e n t of a t t r i t i o n defined by Equation 20. m dp bed p a r t i c l e diameter. J. m /s V V s e excess a i r .W/(m )(°C) -ΔΗ^ k K(R) heat of combustion. W/(m )(°C) 2 2 h^ r a d i a t i v e heat t r a n s f e r coefficient. ACS Symposium Series. m/s h height of bed. . s 2 o 9 cm/s m f r a c t i o n of calcium converted t o the s u l f a t e m^ value of m approached a s y m p t o t i c a l l y a t l o n g times m rate of carbon l o s s from the bed. 2012 | http://pubs. et al. f r a c t i o n of s t o i c h i o m e t r i c f f r a c t i o n of s t o i c h i o m e t r i c coal feed f oxygen requirement to completely combust the v o l a t i l e s . Kg/s 2 g grativational acceleration. Wei.ch004 3 C t o t a l gas-phase molal c o n c e n t r a t i o n mole/m d^ bubble diameter. f r a c t i o n o f s t o i c h i o m e t r i c a i r requirement F q F^ a i r requirement a i r used as c a r r i e r gas f o r c o a l feed r a t e . m /s 2 d i f f u s i o n c o e f f i c i e n t s f o r s o l i d s i n emulsion phase.org Publication Date: July 28. DC.

m /Kg carbon mass i n the bed. °K. m/s Sc Schmidt number Sh t t Τ Sherwood number residence time. m R p a r t i c l e radius. s p a r t i c l e burnout time.org Publication Date: July 28. S u b s c r i p t s b. et al. 2012 | http://pubs. ACS Symposium Series.ch004 ρ (R) p(R) f o r c o a l feed stream. m/s t p a r t i c l e t e r m i n a l v e l o c i t y .4. m ^ 2 ΔΡ pressure drop across bed. J. 1983. m/s 3 ν a W v o l u m e t r i c a i r supply per u n i t mass o f c o a l . Kg/s Γ Δτη c o a l feed r a t e needed t o supply power f o r a i r fans. m/s mr u Q f l u i d i z i n g v e l o c i t y . DC.acs.. Kg/s Γ m r a t e of s o l i d s withdrawal from bed. r e s p e c t i v e l y u^ bubble r i s e v e l o c i t y . Kg/s p(R) f r a c t i o n o f mass of c o a l i n s i z e range R t o R + dR. N/m r radius of v o l a t i l e plume. m ^~ g Downloaded by CORNELL UNIV on December 2. s absolute temperature. w r e f e r t o bed and tube w a l l temperature. American Chemical Society: Washington. . Kg ^2 mole f r a c t i o n of oxygen α r a t i o of wake to bubble volume δ f r a c t i o n of bed volume occupied by bubbles In Chemical Reaction Engineering—Plenary Lectures. Kg c W t o t a l mass o f the bed.1021/bk-1983-0226. SAROFiM Fluidized-Bed Coal Combustion 95 Legend o f Symbols—Continued m c o a l feed r a t e . 1983 | doi: 10. m/s b u U £ u m f / £ m f i n emulsion phase minimum f l u i d i z i n g v e l o c i t y . m Re Reynolds number based on v e l o c i t y R r a t e of change of p a r t i c l e r a d i u s . Wei. m R^ p a r t i c l e r a d i u s o f monodisperse feed..

C h r i s t o s Georgakis. R. N. Jack. High. Zheng. R.Y. Ind. S c i . 1978. 10. Wei. Eng. 6th Int. Eng.L. AIChE J 1955. 9.. 1983 | doi: 10.. pp 1152-1158 Hartman. 8. Ind. and Leon R. on Fluidized Bed Combustion 1980. . S c i . Develop. Hartman. Proc. DC. 13. 13. 23-29. Smith D. Mickley. on Fluidized Bed Combustion 1980. 59. W i l l i s . Coughlin. 1970. R . Conf. 11. . 12. 2. 1974. 1982. 4. F .A. Glicksman whose views are r e f l e c t e d . J . American Chemical Society: Washington. Develop. Proc. M. . 36-40. 22. on Fluidized Bed Combustion 1980. G . Conf. B . 6th Int. Proc. Eng. H . s Acknowledgments The above overview has drawn on background developed as p a r t of an i n t e r d i s c i p l i n a r y program on f l u i d i z e d bed combustion a t MIT funded by DOE. 167-174. P. 7. 307-317. Proc. Chem. i n the paper. Kg/m 3 C ρ Downloaded by CORNELL UNIV on December 2. E. M.N. Environ. 6. .. Fieldes.F. Zhang. a l b e i t through a g l a s s d a r k l y . on Fluidized Bed Combustion 1980. Estimation of Kinetic Data from a Batch Experiment" AIChE 71st Annual Meeting. Conf. 248-253. Borgwardt. L .W.R. 6th Int. w i t h p a r t i a l support from Stone and Webster E n g i ­ n e e r i n g Corp. 3. 1983. . . R . J . Glicksman. Kg/m s τ 2 4 Stefan-Boltzmann constant. Wright.acs. M. on Fluidized Bed Combustion 1980. 1. Rowe. Fairbanks. Beer.96 CHEMICAL REACTION ENGINEERING Legend o f Symbols—Continued ε e bed v o i d f r a c t i o n mf n e n f v o i d f r a c t i o n a t minimum f l u i d i z i n g v e l o c i t y f r a c t i o n a l e f f i c i e n c y o f conversion of thermal t o e l e c t r i c a l energy fan e f f i c i e n c y 3 ρ carbon d e n s i t y .. on Fluidized Bed Combustion 1980. S .D. Carls. L . 4.L.1021/bk-1983-0226. R. R. D. R . 6th Int. Process Des.H. Conf. W/(m )(°K ) c h a r a c t e r i s t i c h e a t i n g time o f p a r t i c l e s . . III. 12 85-91. "Reactions of SO with Limestone in a Fluidized Bed. Literature Cited 1. Chem. 374. M . J. Decker. et al. J . 2012 | http://pubs. 6th Int. I I . Sliger. Pigford. Yates. I. 5.M. ACS Symposium Series. Technol. Conf. AIChE J 1976.. Process Des. 37. 41-44.W. S .. Chem. 225-239. Kaden.org Publication Date: July 28. I. 6th Int. G. .. Davidson. J. X. D. I. Proc. The authors i s indebted t o h i s students and c o l ­ leagues f o r h i s education on many aspects o f the problem especially to Janos M. Coughlin. 2 In Chemical Reaction Engineering—Plenary Lectures. 1973. I I . A.ch004 σ bed s o l i d d e n s i t y . 490-498. Proc. Gamble.

C. Morgan. 1963. Smith. 137 1973.B.. 1 1975. P.. Massimilla. p. Russo. Donsi. 21. H. M. Myles. Sci. R. Gill.. P. R.E. Highley. J. 27. England.. Conf. Combust. Gerlands Beitr. J. R.B. 30. 41. Hartman. Series No. 1973. 32. 1980. J. B. G. W.. Donsi.. Massimilla L.. R. 642-649... 21.. Thesis in Mechanical Engineering. J. In Chemical Reaction Engineering—Plenary Lectures.Κ.V. 6th Proc.F. 41. Haas. 1. Yang.I. 12. N. Chrostowski. Eng. AIChE J. 33.. O. ACS Symposium Series 1978. D.A.. Johnson. AIChE J.D. Vogel.B.R. 1967. 35. 1983 | doi: 10. Geophys.. Wei. 56. 40. Pillai. 24. Series No.J. Κ.1021/bk-1983-0226. G. Fieldes. T. W. L. Ramaswami. L. Beacham.org Publication Date: July 28. AIChE Symp.. R. 1189-1194. Fuel 1977. Sci. J. Kunii. Anastasia. 1979.4. 14. Ranz. Darton.. J. Grace.D. Miccio. II.R. G. Harrison. Stantan. Russo.. Eng. Α.R. R. John Wiley and Sons. American Chemical Society: Washington.W. Shearer. L. Glasson. G. 1983. 52.. M. Donsi.. 17. 25. 57.. 2012 | http://pubs.W. G.C. 276-280. Green.. 1979. Jarry. D. P. 22. 16. Int. 1015-1026. 401-412. Smith J. 28. Lee. on Fluidized Bed Combustion 1980. London. D. Chem. R. 517-22.A. 31. Miccio.. W. Flame 1981. O. Georgakis. 141-146. C. Trans. I Chem. 57-69. Vargo. La Nauze. Seventeenth Symposium (International) on Combustion 1979. Argonne National Laboratory Annual Report ANL/ES-CEN-1004 1971. Massimilla. Chem. Lord. D. Bethell.. M. Avedasian. J.M. Fuel 1973. New York. SAROFIM Fluidized-Bed Coal Combustion 97 Ramachandran. Comb.P..N. 327.acs.J. C. 19. ACS Symposium Series.. Wilkins. W. J. Inst. Proc. Inst. Battcock. Davidson. 1981. M-S... Fuel.P. Saxena.E. 41. 1977. Massimila. "Fluidized Particles" Cambridge University Press. 6th Int. N. 51.. 353.. 34. 35. DC. Eng. 29. Fluid.. 23. Appl. M. 1983.. 225-237. J. . R.G. Marshall. D. S. 170-216.D. "Fluidization Engineering". Fluidized Combustion: Systems and Applications 2nd Int.....V. 366-378. Hoy..R. Schoffstoll.E. 52.. J. B.R. 23. W.. G. 20.. Proc. L.. AIChE J. 5th International Conference on Fluidized Bed Combustion 1977. Combust. Stecconi. J. D4-1 to D4-11.F.. A.C. Ρ 25. 55 274-279. Trans. 39. Eng.T. Prog. J. Trnka.. D. Moulton. L.W. Cammarota. 1969.. Fuel Symp. Sci. and Stecconi. 25. Davidson.M.M.S. Pavlik. Conf.205. M.M.K.. Merrick. Davidson. Harrison.C. 1938. P.. Chem. Chem. F.. Chirone. 48. M. 37. Ε 1977. 173-180. Technol. Glasson. Chen. 1973. 29. 1952.T... D. Downloaded by CORNELL UNIV on December 2. 1.R. 17.B. pp 25-33.. Smyk. 65.. Burdett. 121-131. R. Clift.. 1980.. III. 27. 38. D. Conf. 26... G. D... Levenspiel. G. M. Inst. 91-96. Sc. on Thermal Anal. 811-819. 1980.ch004 18. Α. Davidson.. La Nauze.Α. Chem. W. 15. et al. 70. Frössling. J. I. D. E.. Trans I Chem Ε 1979. D'Amore. Shing. Georgakis. 36. Roberts. Swift. D. O'Neill. Jonke..

.G. Chem. Ross. Chem. 45. 36. S c i .. F . Sundaresan. Chem.. P . Yagi. Beér. Bukur. 51. . R. Kunii. J . Conf.B. Eng. 57. Ε.A. American Chemical Society: Washington. 1983..... Mon. S . Wiley-Interscience: New York. Chapter 19. 17. 1981.R.1021/bk-1983-0226. C . F . G. 179-187. 2nd Suppl. Froberg. 12391256. Seventeenth Symposium (Inter­ national) on Combustion 1979. D. N.ch004 47. Sarofim. A . P . 3. Mon. 58. Inst. . Massimilla.W. 1978. Proc. 57. Amundson. 312-321. 1980. Fuel 1972. 61. J . 1981. S. Fundam.R.acs. pp 231-244. Thesis.. N. 36. Downloaded by CORNELL UNIV on December 2. Amundson. 171-181. 4 1980. Fuel Symp. S . Chem.org Publication Date: July 28. I . N. D. Fitzgerald. Chem. 1138-1149... S c i . M . Essenhigh. R. Ε. et al. J . 1981. 60. 60. Trans. Amundson.W. Horio. H . 6th Int. Trans I Chem Ε 1979. H .R.W. Amundson. pp 1213-1220. J . Fundam. 1977. and N. Tyler. A. 408. 1980. C. Jung. 919-929. . J . University of Cambridge. Calleja. L. AIChE Symp. C. 1981. 1972. Eng. A . I. Patel. Beér. Conf. 2012 | http://pubs. J. 19. Borghi. Stanmore.. Ross. Trans.R. 57. Ind. Chem. Sarofim. Ind. 344-351. R. 773-783. C. D. F . M. 73. Inst. A . 63. 16. Sickhaus. S.. Georgakis. 48. Ser. England. B. Cambridge. 1979.D. . Wei. "Chemistry of Coal Utilization". S c i . V o l . J . 53. Sarofim. Inst. Ind. 1983 | doi: 10. Olander. . Proc.M. Amundson. Smith. Eng. . F .R. 313-314. ACS Symposium Series. .S.. E l l i o t t . 1982... N.. Fuel 1981. Congalidis. Fundam. Davidson. Wells. J . Fundam.Y. G . 50. 31. 1976.. 108. M. 64.. D. 19.R. Fluidized Bed Combustion 1980. 54. E d . Amundson. Chem. Caram. on Fluidized Bed Combustion 1980.. 66-68. Davidson. Georgakis. Saxena. Eng. Phys. 1163-1178. No. S c i . 65. 59. I. Combust. J .98 42. 55.R. 46. Fundam. 215. 6th Int. Amundson. 43. Rehmat. . 51. R.. 313-321. W. Schwarz.P. Eng. .. I . Chem. Wen. B . Krishnan. N. M. A . 243-250. J . Sundaresan. 1976. 49. Chem. 52.. Ind. 1529-1546. Flame 1971. . Park. 295-306. 17. N. In Chemical Reaction Engineering—Plenary Lectures. IV (5).L. . T . Chem. Eng. Gordon. Ser. B a l l . A. K. 66. R .R. J. 351-357. 56. DC. S. Eng. 1980. C H E M I C A L REACTION ENGINEERING Nineteenth Symposium (International) on Combustion 1983. Essenhigh. S .W. 19. Ph. 62. Levenspiel. . 58. No. .R. Jones.. B . Fifth Symposium (International) on Combustion. Eng. 36. R . 161 1978. J. Smith. Chem. F . Ind. 9-21. 1-10. 1980. 60. Eng. 44.. Chem. Eng. AIChE 10th Annual Meeting. New York. . Eng.

Schoffstoll. 1980. 31. Ph.. Combustion Institute. Kin. Chem. Thesis.K. American Chemical Society: Washington. Fifteenth Symposium (International) on Combustion 1975. 1983. 2012 | http://pubs. 76..G... 93. Skopp. Kunii. Sci.1021/bk-1983-0226. Ibid pp 131-140. M. 19. Beér. J. 88. E. A. Gavalas. Sixth Members Conference. de Soete. H. 1977.D. Eng.F. Beér. pp 111-120. 1980.S.. 73. I. G. Fuel Symp..M. Gibbs.B.P. .. Ind. Ross. 1982. J. 1975. Argonne National Laboratory Annual Report ANL/ES-CEN-1001. Hottel. 196. Meissner. Suuberg. 21. Sci. 2... 315-318.S.. J. 577-536. J. G. 70. Pereira. "ΝO Formation and Control in Fluidized-Bed Coal Combustion Processes" ASME Winter Ann. Ser. 77.. Gibbs.R. Sarofim. T. 1981. 1981.. Seventeenth Symposium (International) on Combustion. T.. Inst. Carls.ch004 74. M. Hammons.9.C. 87. Kunii. MIT. 1983. 1983. AIChE J 1980. E.. Elliott.T. Fifteenth Symposium (International) on Combustion 1975. 170-177. Int.. 91. ACS Symposium Series 1982. Combust. E. Vol. 293-244. Murphy. 1976. 35.. D. R..acs..B. Kunii. Oguma. Downloaded by CORNELL UNIV on December 2. R.K. W.Α. 299.M. Chem. 71. L. 84. A. 1982 Dennis. G. L. Chem. Nineteenth Symposium (International) on Combustion. 19. G. K. S. J. P.... J. Patel. 1980. J. Nineteenth Symposium (International) on Combustion.B.L.. C. 83-88. 69. N. T. Mackey. J. J.. Eng.F.K. pp 1067-1084. G. P. 1979. Fundam.L. Campbell. M. 24 197-210.M. Α.. B.R.4. Stubington.B.1-A2. pp 1253-1262. 1981.. Combust. Hayhurst. 63. Wiley-Interscience : New York.. Wei.R. T. M... J. Eighteen Symposium (International) on Combustion 1981. Sci. SAROFIM Fluidized-Bed Coal Combustion 99 Simons. AIChE 1981.. M. J. Amundson. Howard. Simons. Furasawa. Eng. Haas. 82.N. Meeting. 2nd Suppl. Yamada. Beér. Chaung. Davidson. G. Thesis.M. Gavalas. 1983 | doi: 10. D. D. Levy. 1979.A. 545. D. Zygourakis. 85.A..F. Arri. B. pp 1303-1316. 20. pp 1205-1212. Α. H.G. L. 89..A. 26. pp 117-128. 347-357.. 1979. Furusawa. Solomon. 59-65. ACS Symposium Series. Eng.F.. K.M. Chan. International Flame Research Foundation 1980. Hedley. 59. 90. Davidson. Cambridge.. 72. J. 79.B.M.. Technol.F. 1.A.F. 80. DC. I. 2nd Specialists Meeting on Oxidation. Howard. A. Walsh. R. 1-12. 67. E.. Tsunoda. de Soete. Jonke. J. Howard.R. J.M.F.B. 86. 78.K. "Chemistry of Coal Utilization". G. Wu. 8. 27. Sarofim. Chem. x In Chemical Reaction Engineering—Plenary Lectures.A.G. Anthony. 227-235.. Lyon. Nineteenth Symposium (Inter­ national) on Combustion 1983. Peters. et al.Z. Revue Générale de Thermique. Hampartsoumian. 92. Andrei. J..B. A. Davidson. W. Technol. Ed.B. Int. Chapter 12.. Chan. 1.. A. pp 32-36. MA..org Publication Date: July 28. 1971. 83.M. Furasawa.. MIT. pp 1149-1155. 1969. Trans.. 75. Cambridge. A2. Chem.M.. Jarry. Colket. MA. Inst. M..

137-142... Chem. Wei. 99. L. M.D. Conf.W. AIChE Symposium Series Vol. Trans. I. on Fluidized Bed Combustion 1980.J. .J..M. 104. N. Wen.. pp 1281-1289. Cranfield.R.J. T. Proceeding of Fifth International Conference on Fluidized Bed Combustion 1977. 38-47. H. Grace. 106. and Wood. Wells.. 176. Ball. 57. N.. RECEIVED May 2.. 1974. Chem. Pereira.R.. Chaung. on Fluidized Bed Combustion 1982. 2012 | http://pubs. 112.. F. George. Fitzgerald. 27-37. N. F. 67-74. DC.. D. 1980. Dutta.. Mc Grath.. Levenspiel. Nineteenth Symposium (International) on Combustion. Eng. McLaughlin..W. 114.. J. Jovanovic. Chen. J... Streatfield. B. Jovanovic. Lee. Conf. Conf. Beér. pp 325-332.W. Energy 1981. Krishnan. J. 269-275. C..J. 97. J. Α.. T. AIChE Symposium Series No. 1977.. No.1021/bk-1983-0226. ρ 339. 176 1978.F. Fitzgerald. 55. 115. 1983 In Chemical Reaction Engineering—Plenary Lectures.. on Fluidized Bed Combustion 1977. J.Z.N. 54 111. P. A. 95. Sarofim. Crane. III.N. Grace. Staub. T.... Mori S. and Jovanovic. J. pp 773-783.R. 54. J.N.M. Engrs. D. II.Y. G.. 105.ch004 94. Matsen.. Georghiades.org Publication Date: July 28... G.J. III. F. Geldart. J. Plenum. Beér. S. 70-79. Rowe.M.. 108. American Chemical Society: Washington. J. Bar-Cohen. Trans. Proc. 1983. Horio. Eds. G. AIChE Symposium Series 1978. Eng. Cranfield.. 1978. A. G. "Fluidization" Grace. Α.acs.. T.H. Martens. 24.C. 100. Beér.. 101.M.N. et al. AIChE J. 28. Yates. Ku... S..M. J.. Sixteenth Symposium (International) on Combustion 1977.G. M.J.100 C H E M I C A L REACTION ENGINEERING Downloaded by CORNELL UNIV on December 2. AIChE J 1978. pp 225-234.R. 117-128. Fitzgerald. Staub.J. Plenum.. Gibbs. 96. 784-790. 1983. G. 935-947. Glicksman. 6th Int. T. T. Eds.. 110.. Catipovic. J. F. Beér. 1980. S. Walsh... L.E. R. Conf. 543-546. R. 1054. 29. 1982.H. Catipovic. Catipovic. J.. Jovanovic. 113. J.R.M.. Y. J..P. ACS Symposium Series. 135-152.W. 5th FBC Conference 1977. Muchi. D. II. 74. R.F. Proc 5th Int. Trans. Gilvray.. Kuwata. III. pp 815-820b. I Chem. Matsen. 1983 | doi: 10. 103. N. 458-471 107.M. 74. Ibid. F.M. Chem. pp 461-472. 6th Int. Canada. 102. 7th Int. 109. 49. Fitzgerald. Sarofim. Inst. 176 (74). E 1979.. Cullinan. Catipovic. 98. 2nd European Symposium on Combustion 1975. on Fluidized Bed Combustion 1980..J.. "Fluidization". A. Fitzgerald.. C..J. A.S. Sci. PP 605-623. M. O. R.J. 1971.M. Proc. O. Inst. R. P. R. III.M. Van Koppen. S. Op den Brouw. Hughes. Levenspiel... Inst. Geldart.J.M. L.Y.. Pope. D. Pereira.T.E.

DC. ACS Symposium Series. American Chemical Society: Washington. In this survey.1021/bk-1983-0226. A survey of the recent literature indicates a strong upsurge of interest in these problems. 1983. Madison. an introduction to some of the key design d i f f i c u l t i e s is followed by several specific examples i l l u s t r a t ing some of the intriguing and exotic phenomena arising routinely in polymerization reactors. The u l t i m a t e use of these products ranges from s y n t h e t i c c l o t h i n g t o l a t e x p a i n t s . HARMON R A Y Downloaded by UNIV OF ARIZONA on December 2.acs. e t c .ch005 University of Wisconsin. h i g h q u a l i t y (and value) polymers are f i n d ing that t h e i r c o m p e t i t i v e edge comes from a deeper understanding of the r e l a t i o n s h i p between p o l y m e r i z a t i o n c o n d i t i o n s and product quality. However.. Department of Chemical Engineering. polymers were l a r g e l y s p e c i a l i t y m a t e r i a l s . J. more uniform product and the use of continuous r e a c t o r s . The t o t a l world sales of the raw polymer i s now approaching $100 b i l l i o n / y e a r and the s a l e s of the f i n a l product a f t e r p r o c e s s i n g .org Publication Date: July 28. C u r r e n t l y some 200 b i l l i o n l b s (~100 m i l l i o n m e t r i c tons) per year of s y n t h e t i c polymers a r e produced i n the world i n a wide v a r i e t y of p o l y m e r i z a t i o n r e a c t o r s .25/0 © 1983 American Chemical Society In Chemical Reaction Engineering—Plenary Lectures.5 Current Problems in Polymerization Reaction Engineering W.. 1983 | doi: 10. compounding. molding. more e f f i c i e n t p o l y m e r i z a t i o n methods have been r e q u i r e d . WI 53706 Polymerization reaction engineering is an important area in the process industry with many diverse and challenging design problems. manufactured i n batch r e a c t o r s from f a i t h f u l l y f o l l o w e d r e c i p e s scaled up from the chemists beaker. Manufacturers of h i g h volume polymers are now moving t o fewer product l i n e s . et al. w i t h the growth of demand and increased p r i c e competition ( p a r t i c u l a r l y f o r h i g h volume commodity polymers). Thus the f i e l d of p o l y m e r i z a t i o n r e a c t i o n engineering i s of s i g n i f i c a n t economic importance. i s many times t h i s f i g u r e . . Up u n t i l a decade or two ago. producers of r e l a t i v e l y low volume. S i m i l a r l y . Although t h i s change from t r a d i t i o n a l p o l y m e r i z a t i o n methods r e q u i r e s a much b e t t e r understanding of the p h y s i c a l and chemical 0097-6156/83/0226-0101$09. 2012 | http://pubs. The world c a p a c i t y and expected r a t e of growth of the 10 l a r g e s t volume polymers i s shown i n Table I . Wei.

000-50. 2012 | http://pubs.634 17. new processes f o r l i n e a r lowdensity polyethylene (such as the continuous f l u i d i z e d bed process of Union Carbide (2_)) present a t t r a c t i v e a l t e r n a t i v e s to the t r a d i t i o n a l high pressure processes. millions Downloaded by UNIV OF ARIZONA on December 2. These.9 6 10 P o l y e t h y l e n e . provide good d e t a i l e d coverage of the e s s e n t i a l s of the f i e l d .071 26. l i n e a r low-density 8. f l u o r o p o l y m e r s .626 16.359 164.006 7.6 8 8 Isocyanates 4.430 8.0% 2 1 Polyvinyl chloride 35.123 8.374 6.4 9 7 Polyols* 4.ch005 1980s 1981 Resin Mid-1980s of l b per yr.. 1983 | doi: 10. p h e n o l i c s .102 C H E M I C A L REACTION ENGINEERING Table I.6 Other 5 TOTAL a polyesters 8. American Chemical Society: Washington.702 20.9 3 3 Polyethylene. World Capacity and Expected Growth of Largest Volume P l a s t i c s (1_) Rank Capacity. phenomena i n the polymerizing medium.809 15. low-density 38. b includes a c r y l i c s . Wei. i t seems probable that many other t r a d i t i o n a l polymerization processes can be comparably improved through the a p p l i c a t i o n of polymerization r e a c t i o n engineering. more w e l l e s t a b l i s h e d technology. polyphenylene o x i d e .8 7 6 Acrylonitrile-butadiene-styrene 4. Table II). DC. J.339 32.631 13.9 5 4 Polystyrene 17.669 202.1021/bk-1983-0226.528 140. extensive delegation of d e t a i l w i l l be made to these surveys.org Publication Date: July 28.acs. the economic b e n e f i t s from such improved engineering can be enormous. Because polymerization r e a c t i o n engineering i s a r e l a t i v e l y new f i e l d . (and t h i s r e q u i r e s the s e r v i c e s of more w e l l .000 p s i g and thus can reduce the plant c a p i t a l expenditure by 50% and energy consumption by 25%. t h e r e f o r e .7 4 5 Polypropylene 17. high-density 22.4% a Used as i n d i c a t o r s f o r d e r i v a t i v e polyurethanes. s t y r e n e .491 6. Foremost In Chemical Reaction Engineering—Plenary Lectures.895 18.516 0.270 3.047 31. c e l l u l o s i c s . As only one example.538 3.. 1983. p o l y c a r b o n a t e s . In preparing t h i s review of p o l y m e r i z a t i o n r e a c t i o n engineering the author i s f o r t u n a t e that there have been so many books and survey a r t i c l e s to appear i n the l i t e r a t u r e r e c e n t l y ( c f .246 0. ACS Symposium Series. p o l y a c e t a l s .a c r y l o n i t r i l e . These new processes can operate at 300-1000 p s i g rather than the t r a d i t i o n a l 30.t r a i n e d p o l y m e r i z a t i o n r e a c t o r engineers). 1981 Change 1 2 P o l y e t h y l e n e .255 4. taken together. This type of new low density p o l y ethylene process i s making s i g n i f i c a n t progress against the o l d e r .081 2.8 17. . et al.2 10 9 Unsaturated 3. amino r e s i n s .662 4.

Just r e c e n t l y Gerrens has summarized t h i s review i n a superb d i s c u s s i o n of p o l y m e r i z a t i o n r e a c t o r s (17. 1983 | doi: 10. . volume) 3 4 5 6 7 8 9 10 P o l y m e r i z a t i o n Reaction Engineering Continuous Emulsion P o l y m e r i z a t i o n 11 12 P o l y m e r i z a t i o n Processes 13 P o l y m e r i z a t i o n Reactors (ed.A a s s e r and Vanderhoff (1982) Sebastian and Biesenberger Quirk (1983) (ed. as w e l l as the experienced p o l y m e r i z a t i o n r e a c t i o n engineer. ACS Symposium Series. i o n i c and c o o r d i n a t i o n . This has been updated and expanded i n the recent chapter on polymerizat i o n technology (16) which has n e a r l y 500 r e f e r e n c e s .. values) (ed..acs. 2012 | http://pubs. volume) 14 O l e f i n Polymerization P o l y m e r i z a t i o n Technology 15 16-18 Polymerization Kinetics P o l y m e r i z a t i o n Reactor Dynamics Emulsion P o l y m e r i z a t i o n (ed. 1 P o l y m e r i z a t i o n K i n e t i c s and Reactor Design Much has been w r i t t e n about p o l y m e r i z a t i o n k i n e t i c s and the e s s e n t i a l steps a r e shown i n Table I I I f o r the three p r i n c i p a l types of mechanisms ( f r e e r a d i c a l . J. 1982 ) Odian (1981) Ray (19 81) Bassett and Hamielec (1982) Piirma (1982) E l .1021/bk-1983-0226. w i l l both f i n d Gerrens surveys p r o f i t a b l e reading. volume) 19 20 21 Emulsion P o l y m e r i z a t i o n Emulsion P o l y m e r i z a t i o n 22 23 (ed. RAY 103 Polymerization Reaction Engineering Table I I . we s h a l l f i r s t provide a broad brush p e r s p e c t i v e of the f i e l d and then focus on some i n t e r e s t i n g unsolved problems which a r e the subject of current research. Wei.org Publication Date: July 28.ch005 Author(s) T o P Reference i c Keane (1972) Ray (1972) K e i i (1972) A l b r i g h t (1974) Min and Ray (1974) Gerrens (1976) Bouton and Chappelear (1976) S i n g l e Phase P o l y m e r i z a t i o n Mathematical M o d e l l i n g Ziegler-Natta Polymerization Polymerization Processes (Monograph) Emulsion P o l y m e r i z a t i o n P o l y m e r i z a t i o n Reactions and Reactors Continuous Reactors (ed. The novice j u s t beginning work i n t h i s area. American Chemical Society: Washington. et al.18) . In t h i s paper. 1983. volume) Piirma Emulsion P o l y m e r i z a t i o n and Gardon (1976) Ray and Laurence (1977) Poehlein and Dougherty (1977) Schildknecht and S k e i s t (1977) Henderson and Bouton (1979) Boor (1979) Gerrens (1980. DC. 1981. and In Chemical Reaction Engineering—Plenary Lectures. volume) P o l y m e r i z a t i o n Engineering 24 Ziegler-Natta Polymerization 25 (1983) among these a r e the recent reviews of Gerrens beginning w i t h h i s outstanding plenary l e c t u r e of the 1976 ISCRE meeting ( 8 ) . Some Recent Books and Survey A r t i c l e s on Polymerization Reaction Engineering Downloaded by UNIV OF ARIZONA on December 2. volume) (ed.5.

there i s not comprehensive understanding of the k i n e t i c s . To i l l u s t r a t e some of the c h a l l e n g i n g problems of polymeriza- In Chemical Reaction Engineering—Plenary Lectures. coordination) I + M Ρ initiation ι P n + M P îÇ* n+l propagation (sometimes chain transfer or termination mechanisms also occur) H. crosslinkLng) P n + m 1Ç n4m P P propagation condensation p o l y m e r i z a t i o n ) .org Publication Date: July 28. o f even these simple polymerizations. DC. The reader should cons u l t the surveys of Table I I f o r a d i s c u s s i o n of the remaining i n t e r e s t i n g problems i n k i n e t i c s . ACS Symposium Series. As important as k i n e t i c mechanism are the phase changes that occur i n p o l y m e r i z a t i o n . Only a small f r a c t i o n of polymerizat i o n s are c a r r i e d out only i n one phase.acs. and the k i n e t i c s of the phase change i t s e l f a l l play a r o l e i n determining the p r o p e r t i e s of the product polymer. 2012 | http://pubs. Free Radical — * • 2R I 1 \ kd R + M p T î initiation 1 i 1 Downloaded by UNIV OF ARIZONA on December 2. However. thus thermodynamics. American Chemical Society: Washington.. Major Classes of Polymerization Reactions Monomer Addition: A. heat and mass t r a n s f e r . J. . et al. cationic. Wei. Each of these c l a s s e s of systems has i t s own p e c u l i a r problems so that p o l y m e r i z a t i o n r e a c t o r design can o f t e n be much more c h a l l e n g i n g than the design of r e a c t o r s f o r short chain molecules. 1983 | doi: 10. p a r t i c u l a r l y w i t h heterogeneous systems. Polymer Coupling (polycondensation.. combination (sometimes chain branching reactions also occur) Ionic (anionic. Table IV i n d i c a t e s the p r i n c i p a l types of k i n e t i c mechanisms and r e a c t i o n media which a r i s e i n polymerizat i o n r e a c t o r s . 1983.ch005 P + M n P 7~+ +1 *P P +A —• Ρ n k P P^g^tion n n + χ +M f ^ M ^t^*»* chain transfer n + M^ disproportionate ) R P m ^ Vtermination k tc — " M_.104 C H E M I C A L REACTION ENGINEERING Table I I I .1021/bk-1983-0226.

PVC) V i n y l polymers ( S t y r e n e . polypropylene) Polyolefins with soluble catalyst (ethylenepropylene copolymers) Coord i n a t i o n Catalysis I N P O L Y M E R I Z A T I O N REACTORS Ionic Kinetic REACTION MEDIA EMPLOYED TABLE IV Downloaded by UNIV OF ARIZONA on December 2. Nylon) Polyethers (Ethylene ox i d e) Polyacetals (formaldehyde) Vinyls (iso-butylene-buty1 rubber) Condensation mechanism Polyolef ins with insoluble catalyst ( L i q u i d and gas p h a s e processes f o r HDPE. LDPE) Free P o l y a m i d es (Nylon interfac i a l poly .acs. E m u l s i o n 1. L L D P E .In Chemical Reaction Engineering—Plenary Lectures. 1983 | doi: 10.. medium 2. Polyamides (PET. ) Polyesters. J. DC. 2012 | http://pubs. PVC) V i n y l polymers (Styrene.1021/bk-1983-0226. American Chemical Society: Washington.org Publication Date: July 28. Wei. H o m o g e n e o u s ( b u l k and s o l u t i o n ) Reaction K I N E T I C MECHANISMS AND radical Vinyl (PVC) polymers V i n y l polymers ( S t y r e n e .ch005 .. 1983. et al. P r e c i p i t a t i o n ( b u l k and solution) b. Heterogeneous a. Suspension c. ACS Symposium Series.

1983.Most polymerizations r e l e a s e l a r g e amounts of heat as monomer i s converted to polymer ( c f . the r e a c t i o n medium begins as a low v i s c o s i t y l i q u i d .7. 1983 | doi: 10. et al.5 -17.4 In Chemical Reaction Engineering—Plenary Lectures. d i s a s t r o u s r e a c t o r runaway i s an ever present p o t e n t i a l hazard because of these heat removal d i f f i c u l t i e s .. which i s i n s o l u b l e i n the monomer.2 -18.4 . p r e c i p i t a t e s ) .acs. heat t r a n s f e r surface f o u l i n g . becomes a paste as the monomer disappears and f i n i s h e s as a s o l i d powder. l e t us l i s t some of the issues which must be faced: 1.6 -16. ACS Symposium Series. Often a large amount of mechanical energy i s required f o r mixing and conveying. Table V). In a d d i t i o n . Wei. 2. 2012 | http://pubs. progresses to a s l u r r y (the PVC polymer.2 -18.7 -22. there can be serious n o n .Downloaded by UNIV OF ARIZONA on December 2. some polymerizations go through s e v e r a l phase changes i n the course of the r e a c t i o n . . however. As might be expected. K i n e t i c s and Phase Behavior . M a t e r i a l Mixing and Conveying . the mechanical energy required f o r mixing may be converted to heat under h i g h l y viscous c o n d i t i o n s . TABLE V HEATS OF POLYMERIZATION FOR SOME COMMON MONOMERS cal/mole at 25°C Ethylene Propylene Butadiene Styrene Vinyl chloride Vinylidene chloride V i n y l acetate Methyl a c r y l a t e Methyl methacrylate Acrylonitrile Formaldehyde -21.2 -19.. DC. s t i c k i n g and f o u l i n g of the r e a c t o r surfaces by polymer i s a d i f f i c u l t design problem. Sometimes.ch005 106 CHEMICAL REACTION ENGINEERING t i o n r e a c t o r design. This presents a great challenge to the process c o n t r o l engineer as w e l l as to the r e a c t o r designer. Heat Removal . modelling the k i n e t i c s of the r e a c t i o n i n such a s i t u a t i o n i s not a simple exercise.With such a v a r i e t y of morphologies. and change of phase during r e a c t i o n . In many i n d u s t r i a l s i t u a t i o n s .org Publication Date: July 28.5 -13. i n the bulk polymeri z a t i o n of PVC. 3.i d e a l i t i e s i n micromixing and macromixing.Table IV represents a s i m p l i f i e d p i c t u r e of the s i t u a t i o n . For example. Removal of t h i s heat i s o f t e n d i f f i c u l t f o r high conversion p o l y m e r i z a t i o n because of high v i s c o s i t y . p a r t i c u l a r l y at high conv e r s i o n s . American Chemical Society: Washington.1021/bk-1983-0226.0 -21.9 -18. J.

13. e t c . American Chemical Society: Washington. only very recent work on p o l y m e r i z a t i o n r e a c t i o n engineering w i l l be provided here as a supplement.org Publication Date: July 28. 1983. examples w i l l be used t o i l l u s t r a t e some of the design c o n s i d e r a t i o n s l i s t e d here. suspension. J. T In Chemical Reaction Engineering—Plenary Lectures. c o n t r o l of polymeri z a t i o n r e a c t o r s i s a s p e c i a l challenge. degree of chain branching. Because of the l a c k of o n . crack r e s i s t a n c e . ACS Symposium Series. taken from Gerrens review provides an i n d i c a t i o n o f the v a r i e t y of r e a c t o r c o n f i g u r a t i o n s found i n i n d u s t r i a l p r a c t i c e . and s t e r e o r e g u l a r i t y . For example. Table VI summarizes both types of q u a l i t y c o n t r o l measures.11.1021/bk-1983-0226. temperature s t a b i l i t y . and p r e c i p i t a t i o n p o l y m e r i z a t i o n can be a c r u c i a l product s p e c i f i c a t i o n . This i s c a t e g o r i z e d by t o p i c i n Table V I I I . . can a l t e r c r i t i c a l molecular p r o p e r t i e s such as molecular weight d i s t r i b u t i o n . I n a d d i t i o n . polymer composition d i s t r i b u t i o n . Q u a l i t y of Polymer Product . In subsequent s e c t i o n s . 2012 | http://pubs. the p a r t i c l e s i z e d i s t r i b u t i o n i n emulsion. r e a c t o r temperature.16-18) provide a treatment of p o l y m e r i z a t i o n r e a c t o r s and processes i n i n d u s t r i a l use.g.ch005 5. One of the greatest d i f f i c u l t i e s i n a c h i e v i n g q u a l i t y c o n t r o l of the polymer product i s that the a c t u a l customer s p e c i f i c a t i o n s may be i n terms of non-molecular parameters such as t e n s i l e s t r e n g t h . mixing. Although a number of the surveys l i s t e d i n Table I I (e. 6. c o l o r or c l a r i t y . e t c .. Wei. et al. 1983 | doi: 10..Product q u a l i t y i s a much more complex i s s u e i n p o l y m e r i z a t i o n than i n more conventional short chain r e a c t i o n s . upsets i n feed c o n d i t i o n s .l i n e measurements f o r most of these product q u a l i t y v a r i a b l e s (molecular or otherwise). DC.Downloaded by UNIV OF ARIZONA on December 2.acs. Because the molecular a r c h i t e c t u r e of the polymer i s so s e n s i t i v e to r e a c t o r operating c o n d i t i o n s . The q u a n t i t a t i v e r e l a t i o n s h i p between these product q u a l i t y parameters and r e a c t o r operating c o n d i t i o n s may be the l e a s t understood area of p o l y m e r i z a t i o n r e a c t i o n engineering. This l a r g e amount of l i t e r a t u r e (which i s not exhaustive) over the l a s t 18 months i s i n d i c a t i v e of the recent e x p l o s i o n of i n t e r e s t i n these problems. chain sequence d i s t r i b u t i o n . the morphological form of the polymer i s o f t e n a key q u a l i t y v a r i a b l e . Because the s t a t e of the l i t e r a t u r e through 1980 i s so w e l l covered by the surveys l i s t e d i n Table I I . Table V I I . RAY Polymerization Reaction Engineering 107 4. Gerrens has provided an outstanding summary of t h i s i n f o r m a t i o n i n h i s recent survey (18). a b s o r p t i o n c a p a c i t y f o r p l a s t i c i z e r ..

Molding. I A Atactic: A I -c-c-c-c-c-c-c- I I i A A A Average P a r t i c l e Size D i s t r i b u t i o n A Size P a r t i a l P o r o s i t y and Surface Area In Chemical Reaction Engineering—Plenary Lectures. Isotactic: -C-C-C-C-C-C-C- I A b. American Chemical Society: Washington.1021/bk-1983-0226. et al. ) Strength S t r e s s Crack Resistance Downloaded by UNIV OF ARIZONA on December 2.. e t c . Some Measures of Polymer Product Q u a l i t y END USE PROPERTIES Flow P r o p e r t i e s ( F i l m Blowing..acs. Linear: I II !! I -c-c-c-c-c-c- I IIII I •Impact Resistance b.C H E M I C A L REACTION ENGINEERING Table VI.) MW Polymer Composition and Composition Distribution nlOO •Melting P o i n t •Corrosion Resistance •Abrasion Resistance Chain Sequence Distribution Degree of Chain Branching • Density -A-A-B-A-A-A-B-Ba.ch005 •Color. etc. I A I A I A Syndiotactic: A I -c-c-c-c-c- I A c.org Publication Date: July 28. . 2012 | http://pubs. J. •Temperature Stability Branched : -C-C-C-C-C-C- •Swellability • P l a s t i c i z e r Uptake •Spray Drying Characteristics •Coating and Adhesion P r o p e r t i e s Stereoregularity (Tacticity) a. 1983. ACS Symposium Series. DC. 1983 | doi: 10. C l a r i t y MOLECULAR ARCHITECTURE Average M o l e c u l a r Weight and Molecular Weight D i s t r i b u t i o n (or Melt Index. Viscosity. Wei.

J. ACS Symposium Series. ο Bead polymerization ρ < JJ Solution polymerization Polymerization reactions Reactor C o n f i g u r a t i o n s Found i n I n d u s t r i a l Downloaded by UNIV OF ARIZONA on December 2..9 buted bead w 19 2-Component mixer + mold 20 16 Batch stirred tank + autoclave with gate paddle nuscer 17 15 Batch stirred tank + filter press Ik <u 13 j Η u BR Piston 12 8 6 2 Semibatch 11 10 9 7 5 k 3 1 Practice. 1983 | doi: 10.In Chemical Reaction Engineering—Plenary Lectures.acs. Wei.. American Chemical Society: Washington.ch005 Batch stirred tank . Stirred tank + tower 29 28 Π) Tower or tower cascade 27 26 25 Extruder 2k 23 Mixer + conveyor 22 21 Continuous tube 18 Continuous tube with distri. 1983.org Publication Date: July 28. y ο Ρ· α ι p Emulsion polymerization Solution polymerization Precipitation polymeri zation §. 2012 | http://pubs. et al. DC. £ | Precipitation polymerization Solid-phase polycondensation Interfacial polycondensation Solution or melt-polycondensation p. 38 37 36 ho 39 Fluidized bed ^ Continuous stirred tank (Double) Loop 35 Rotating ring disc 3k g CO 33 32 31 30 Stirred tank cascade Table V I I .1021/bk-1983-0226.

1021/bk-1983-0226. T i r r e l l (167-184) Process Dynamics. Ugelstad. Zakharov (95-124) Kinetics of High Pressure (Low Density) Ethylene Polymerization Ehrlich.acs. Pino. Vanderhoff (21-23_. Fan. Ray. Middleman. Nigam. Wei.~T42-143. Kumar. O'Driscoll. Jovanovich. Hogan. Ray. Loft. Johnson. Nomura. MacGregor. 160. Johnson. TTff-TBT) in Free Radical Polymerization Copolymerization In Chemical Reaction Engineering—Plenary Lectures. American Chemical Society: Washington. Kaneko. Ito. Kamal. Yamamoto (125-135) CSTR for Polymerization Chen.ch005 Table V I I I . Laurence. T i r r e l l (26-48) Biesenberger. Reichert. Ray (136-147) Tubular Polymerization Reactors Janssen. 246) Reaction Injection Molding (RIM) Gogos. Ray. Some Very Recent Work i n Polymerization Reaction Engineering Topic Principal Research Groups References Gel or Trommsdorf Effect Hamielec. T i r r e l l (49-60) (61-94) Polycondensation Gajewski.org Publication Date: July 28. ACS Symposium Series. Joosten. Ottino. 1983. T i r r e l l l3"5"-l39~. Optimization. Sundberg. DC. 2012 | http://pubs. 50-54. Piirma. 1983 | doi: 10. Kiparissides. Mashelkar. Ï8T-2uD Suspension Polymerization Reichert (206-217) Emulsion Polymerization Bassett. . J. Brockneier. Meira. Brooks. Sundberg. 201-205. Throne. Rafler Olefin Polymerization with Coordination Catalysts Bohm. Ottino. et al.110 C H E M I C A L REACTION ENGINEERING Downloaded by UNIV OF ARIZONA on December 2.. (20. and Control Chen. Hamielec. Guillot. Gupta. Keii.. Î4T-I4T. Macosko. Ray (148-166.

The p r a c t i c a l consequence of t h i s f o r the i n d u s t r i a l r e a c t o r i s that even with p e r f e c t temperature c o n t r o l (an u n l i k e l y event a f t e r i g n i t i o n has occurred). RAY Polymerization Reaction Engineering Some Current 111 Research Problems To provide an i l l u s t r a t i o n of some of the challenges of polymerization r e a c t i o n engineering. Recent studies of CSTR s f o r bulk or s o l u t i o n f r e e r a d i c a l polymerization i n d i c a t e the p o s s i b i l i t y of m u l t i p l e steady s t a t e s (e. Figure 1). Note that the model p r e d i c t i o n s and the steady s t a t e experiments agree that there i s i g n i t i o n to a high conversion.145-147). are s u c c e s s f u l l y employed to d e s c r i b e these r e a c t o r s .. The f a c t that t h i s occurs should not be s u r p r i s i n g given the l a r g e heat e v o l u t i o n and d i f f i c u l t heat t r a n s f e r c h a r a c t e r i s t i c of polymerization r e a c t o r s . they may not. CSTR models. The upper steady s t a t e i s inoperable due to the extremely high v i s c o s i t i e s at such high conversions. the r e a c t o r w i l l i g n i t e i n t o a "runaway" c o n d i t i o n f o r c e r t a i n combinations of solvent concentration and r e a c t o r residence time.137-139. J. I f only temperature measurements are being taken. Downloaded by UNIV OF ARIZONA on December 2. . perhaps with some allowance f o r imperfect micromixing. Thus the behavior of the CSTR i s of great p r a c t i c a l i n t e r e s t . In the laboratory. 1 In Chemical Reaction Engineering—Plenary Lectures. 2012 | http://pubs. DC. steady s t a t e at a c e r t a i n residence time f o r solvent f r a c t i o n s l e s s than ~40%. et al. have the appearance of a CSTR ( c f . there are dramatic new t w i s t s to these phenomena even i n simple s o l u t i o n polymerization. the operator would not be aware of the runaway u n t i l the a g i t a t o r motor blew a fuse. Although many polymerizat i o n reactors i n use by industry have the residence time d i s t r i bution of a CSTR. 1983. at f i r s t glance. Wei. However. These examples r e f l e c t the author s own i n t e r e s t and are s e l e c t e d from research p r o j e c t s c u r r e n t l y underway at the U n i v e r s i t y of Wisconsin. a u t o c a t a l y t i c k i n e t i c s lead to the existence of m u l t i p l e steady states even under isothermal reactor c o n d i t i o n s . For example. ACS Symposium Series. 1983 | doi: 10.. 20. American Chemical Society: Washington.org Publication Date: July 28. we s h a l l discuss here a few i n t r i g u i n g but p r a c t i c a l l y important research problems which a r i s e i n the design of polymerization r e a c t o r s . Nevertheless.acs. i g n i t i o n which was allowed to proceed to t h i s upper steady s t a t e r e s u l t e d i n a reactor f i l l e d with s o l i d polymer.g. or the g r e a t l y increased r a t e of r e a c t i o n exceeded the c o o l i n g system capacity and caused a sharp increase i n temperature and pressure i n the r e a c t o r .ch005 f S o l u t i o n Polymerization i n a CSTR. inoperable.5.. Figure 2 (taken from (145)) i l l u s t r a t e s t h i s f o r the case of methyl methacrylate polymerizat i o n i n e t h y l acetate solvent c a r r i e d out at the b o i l i n g point of the r e a c t i n g l i q u i d .1021/bk-1983-0226.

et al. American Chemical Society: Washington. J.org Publication Date: July 28..acs. Catalyst ethylene Polymer powder Gaseous monomer Monomer Catalyst CSTR (Double) Loop Fluidized bed ("gas phase") F i g u r e 1. 1983 | doi: 10. Wei.ch005 112 C H E M I C A L REACTION ENGINEERING [1 El m m m m flf m m Έ3ϋ Stirred tank cascade Tower cascade 11 1 Η Ring disc Stirred tank-tower combination Polymer Catalyst solvent . 2012 | http://pubs.1021/bk-1983-0226.. ACS Symposium Series. DC. In Chemical Reaction Engineering—Plenary Lectures. Continuous s t i r r e d tank r e a c t o r types i n use by i n d u s t r y (l8).Downloaded by UNIV OF ARIZONA on December 2. 1983. .

ACS Symposium Series.0 —ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—r E X P E C T E D ERROR Downloaded by UNIV OF ARIZONA on December 2.Oj 1 20 30 20 1 J 40 1 ι I 60 Ί 1 ι L 80 Γ 40 100 50 ι I I I I j RESIDENCE TIME (MIN.) . Steady-state con­ v e r s i o n v s . 1983. I. b. c.org Publication Date: July 28.ch005 1 S' S' g δ* > .. 2012 | http://pubs. a. J. Co) non-steady s t a t e s . 1983 | doi: 10.) 10 B O U N D S «-J"* 1.1021/bk-1983-0226. CSTR residence time f o r s o l v e n t f r a c t i o n o f 50%. RESIDENCE TIME (MIN. r e a c t o r residence time f o r t h e s o l u t i o n p o l y m e r i z a t i o n o f MMA. American Chemical Society: Washington. Steady-state and dynamic experiments f o r the i s o t h e r m a l s o l u ­ t i o n p o l y m e r i z a t i o n o f MMA i n e t h y l acetate ( s o l v e n t f r a c t i o n 0 Λ) (·) steady s t a t e s . RESIDENCE TIME (MIN.. i n e t h y l acetate a t 86 °C. Wei.acs. Isothermal p o l y m e r i z a t i o n o f methyl methacrylate i n a CSTR (1U5).) 10 β φ «(Χ3 η—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι 20 30 40 50 F i g u r e 2. et al. P r e d i c t e d steady-state monomer conver­ s i o n v s . DC.In Chemical Reaction Engineering—Plenary Lectures.

found by Schork.ch005 114 C H E M I C A L REACTION ENGINEERING In r e a l i t y . It i s c l e a r that the reactor designer would need to consider t h i s isothermal m u l t i p l i c i t y i n s e l e c t i n g the d e s i r e d reactor operating c o n d i t i o n s . Note that high conversions can be achieved at long residence times ( l a r g e r e a c t o r s ) on the S-shaped m u l t i p l i c i t y branch or a l t e r n a t i v e l y at short residence times (small reactors) on the i s o l a t e d branch. For example. These model p r e d i c t i o n s have been v e r i f i e d by experiment f o r the polymerization of methyl methacrylate and f o r the polymerization of v i n y l acetate (147). multiphase r e a c t o r a l s o shows m u l t i p l e steady states under isothermal c o n d i t i o n s . Wei. J. 1983. monomer conversion i n the r e a c t o r . These m u l t i p l i c i t i e s occur f o r any polymerization having the Trommsdorf e f f e c t . This complex. et a l . et al. Figure 4 (taken from (147)) provides a d e t a i l e d comparison of model p r e d i c t i o n and experiment f o r v i n y l acetate polymerization.org Publication Date: July 28. these i s o l a t e d steady s t a t e s r e q u i r e s p e c i a l start-up procedures and r e l i a b l e c o n t r o l systems to prevent e x t i n c t i o n of the r e a c t i o n . which are the locus of r e a c t i o n . 2012 | http://pubs. The i s o l a t e d branch has the advantage that high conversion polymerization may be c a r r i e d out with a reactor only 10% the s i z e required f o r the same conversion on the continuous branch of steady s t a t e s .5 ym) polymer p a r t i c l e s . (204).1021/bk-1983-0226. Emulsion Polymerization i n a CSTR. Another exotic feature of emulsion polymerization i n a CSTR i s that sustained o s c i l l a t i o n s are f r e q u e n t l y observed i n In Chemical Reaction Engineering—Plenary Lectures..acs. there i s l i m i t e d heat removal capacity f o r i n d u s t r i a l r e a c t o r s . are shown i n Figure 7 where experimental steady s t a t e measurements are compared with model p r e d i c t i o n s . ACS Symposium Series. Figure 6 (taken from r e f .Downloaded by UNIV OF ARIZONA on December 2. so that heat e v o l u t i o n due to r e a c t i o n i s an a d d i t i o n a l source of a u t o c a t a l y t i c behavior. Emulsion polymerization i s u s u a l l y c a r r i e d out i s o t h e r m a l l y i n batch or continuous s t i r r e d tank r e a c t o r s .. The i n t e r s e c t i o n of R with m m ^ f ^ s a t i s f i e s the m a t e r i a l balance and determines τ the r e a c t o r steady s t a t e s . are suspended i n a continuous aqueous medium as shown i n Figure 5. Gerrens and coworkers at BASF seem to be the f i r s t to report these phenomena both computationally and experimentally. (253)) p l o t s the a u t o c a t a l y t i c behavior of the r e a c t i o n r a t e f o r styrene polymeri­ z a t i o n vs. . Note that e x t i n c t i o n i s indeed observed at both ends of the i s o l a . Temperature c o n t r o l i s much e a s i e r than f o r bulk or s o l u t i o n polymerization because the small (~. 1983 | doi: 10. DC. Including these temperature e f f e c t s produces even more i n t e r e s t i n g types of m u l t i p l e steady s t a t e behavior. American Chemical Society: Washington. Figure 3 (taken from (147)) i l l u s t r a t e s the types of steady s t a t e behavior which a r i s e f o r methyl methacrylate polymerization when the solvent volume f r a c t i o n i s high enough that isothermal m u l t i p l i c i t y i s not p o s s i b l e and high conversion steady s t a t e s are f e a s i b l e operating c o n d i t i o n s f o r the CSTR. m u l t i ­ p l i c i t i e s f o r methyl methacrylate polymerization. However.

.1021/bk-1983-0226. 1983 | doi: 10. . Wei. DC.org Publication Date: July 28..acs. 1983.ch005 5.888 45Θ 688 758 9Θ8 1858 188.θ 1858 RESIDENCE TIME Figure 3. U f In Chemical Reaction Engineering—Plenary Lectures. J. 23 C 21 °C .Downloaded by UNIV OF ARIZONA on December 2. RAY 115 Polymerization Reaction Engineering 8.8 Τ Ε η ρ Ε R 58. 2012 | http://pubs.8Η fi Τ U R ε θ. E f f e c t o f feed temperature on steady-state o p e r a t i o n f o r MMA p o l y m e r i z a t i o n (lV7_) • Base case. American Chemical Society: Washington. et al. ACS Symposium Series. and T = 25 °c .

org Publication Date: July 28. = 0. ACS Symposium Series..ch005 1 θ 8. I = O. . 1983.OUlT m o l e / l i t . J. 1983 | doi: 10. T~ = 20 °C.116 C H E M I C A L REACTION ENGINEERING Downloaded by UNIV OF ARIZONA on December 2.unstable transient. Q f In Chemical Reaction Engineering—Plenary Lectures. and 0 .5H θ. American Chemical Society: Washington.acs.. 2012 | http://pubs.θ I I I '0| 25 I I I ! [ 1 1 I 1 j I ϊ 1 ι 58 75 I > I I 1ΘΘ I j I I I I 125 158 188· &Qv^O J rj^^è 58 H Ά è 1 -JÛ_ I I I j I I I I [ I I 1 I j ι » ι ι I I I I I j I I I I 25 50 75 108 125 150 RESIOENCE TIME ( M I N ) Figure U.50. Wei. T = 25 °C. 0 . DC. et al. A comparison o f the steady-state v i n y l acetate model and experimental data (1U7).1021/bk-1983-0226.s t a b l e steady s t a t e .

org Publication Date: July 28. 1983. s t i r r e d tank emulstion p o l y m e r i z a t i o n In Chemical Reaction Engineering—Plenary Lectures. DC.acs. 2012 | http://pubs. ACS Symposium Series.1021/bk-1983-0226.ch005 Emulsifier Initiator Polymerizing Emulsion Figure 5· A continuous reactor.. . 1983 | doi: 10. Wei.5. RAY Polymerization Reaction Engineering 111 Monomer H2O Downloaded by UNIV OF ARIZONA on December 2. J. et al. American Chemical Society: Washington..

American Chemical Society: Washington.org Publication Date: July 28.. 253. ACS Symposium Series. . M u l t i p l e steady s t a t e s i n the emulsion p o l y m e r i z a t i o n o f styrene i n a CSTR.ch005 118 C H E M I C A L REACTION ENGINEERING (Μ) ς S t y r o i / g Latex K)0 80 Π&0 40 20 % Conversion 0 Figure 6. Wei. 1983.1021/bk-1983-0226. Copyright 1971. V e r l a g Chemie. DC. (Reproduced w i t h permission from Ref. GMBH.. 2012 | http://pubs.) In Chemical Reaction Engineering—Plenary Lectures. 1983 | doi: 10. J.acs. et al.Downloaded by UNIV OF ARIZONA on December 2.

In Chemical Reaction Engineering—Plenary Lectures. RAY Polymerization Reaction Engineering 119 Downloaded by UNIV OF ARIZONA on December 2. et al.org Publication Date: July 28. J. American Chemical Society: Washington. a n d * .ch005 100-1 0 1 0 2 0 3 0 Residence Time 4 0 5 0 6 0 (min) Figure 7. 1983 | doi: 10.. Wei..1021/bk-1983-0226. Isothermal m u l t i p l i c i t y f o r the emulsion p o l y m e r i z a t i o n of methyl methacrylate i n a CSTR '(20h). .03 moles/L-water. 1983. o. [ s ] = [ i ]_ = 0. 2012 | http://pubs.5.t h e o r e t i c a l steady s t a t e s .experimental steady s t a t e s . DC. ACS Symposium Series.acs.x .

and ( i i i ) what p h y s i c a l phenomena are o c c u r r i n g i n the pores and on the c a t a l y s t s u r f a c e . these extensive modelling s t u d i e s show that In Chemical Reaction Engineering—Plenary Lectures. . There i s some concensus that the p h y s i c a l p i c t u r e i n s i d e the growing polymer p a r t i c l e i s as f o l l o w s . S o l i d . A t h i r d area where extremely c h a l l e n g i n g p o l y m e r i z a t i o n r e a c t i o n engineering problems a r i s e i s i n t r a n s i t i o n . American Chemical Society: Washington. has the increased heat and mass t r a n s f e r r e s i s t a n c e of the heterogeneous polymeriz a t i o n produced the great nonuniformity i n polymer chain length? To produce some answers to these and other questions requires a combination of mathematical modelling and d i a g n o s t i c experimentation. Figure 11 i n d i c a t e s the corresponding molecular weight d i s t r i b u t i o n to be expected. which must d i f f u s e to the c a t a l y s t surface to be c a t a l y t i c a l l y i n s e r t e d i n t o the polymer chain. ACS Symposium Series. Monomer. propylene and t h e i r copolymers. et al. F i g u r e 9 i l l u s t r a t e s some of these models while Figure 10 (taken from (256)) shows the p r e d i c t e d propylene monomer c o n c e n t r a t i o n p r o f i l e to be expected i n a polypropylene polymer p a r t i c l e over a 4 hour period i n a s l u r r y batch r e a c t o r . DC. 1983 | doi: 10.256. Experimental r e s u l t s from our l a b o r a t o r y (201. Therefore a number of r a t h e r complex models f o r the c a t a l y s t p a r t i c l e have been developed and t e s t e d computationally with r e a l i s t i c parameters f o r heat and mass t r a n s f e r as w e l l as k i n e t i c s . (20. The c a t a l y s t p a r t i c l e f r a c t u r e s i n t o t i n y fragments as the pores are ruptured by growing polymer.acs.120 CHEMICAL REACTION ENGINEERING Downloaded by UNIV OF ARIZONA on December 2.253. o l e f i n p o l y m e r i z a t i o n with a Z i e g l e r . ( i i ) what causes the d e c l i n e i n c a t a l y s t a c t i v i t y observed i n these r e a c t o r s . As described i n d e t a i l elsewhere (121.254) f o r a d i s c u s s i o n of t h i s ) . J. sees an i n c r e a s i n g path f o r d i f f u s i o n as p o l y m e r i z a t i o n progresses and the c a t a l y s t fragments become more and more encapsulated by polymer.257). Wei. There i s great i n t e r e s t i n developing a q u a n t i t a t i v e understanding of the fundamental nature of these o s c i l l a t i o n s so that reactor design c r i t e r i a f o r a v o i d i n g them can be developed.122. 2012 | http://pubs. For heterogeneous c a t a l y t i c systems polymerization occurs on the c a t a l y s t s u r f a c e producing polymer chains which f i l l the pores and grow out from the a c t i v e s u r f a c e .ch005 i n d u s t r i a l p r a c t i c e ( c f ..1021/bk-1983-0226. 1983.m e t a l c a t a l y z e d polymerization of o l e f i n s such as ethylene.org Publication Date: July 28. Unambiguous measurements are few. There i s great controversy at present over issues such as ( i ) which f a c t o r s c o n t r o l the molecular weight d i s t r i b u t i o n and t a c t i c i t y . Recent developments by Rawlings (255) would seem to provide a f i r s t step i n t h i s d i r e c t i o n .C a t a l y z e d O l e f i n P o l y m e r i z a t i o n .N a t t a type c a t a l y s t y i e l d s narrow molecular weight d i s t r i b u t i o n s when the system i s homogeneous and very broad molecular weight d i s t r i b u t i o n s when the p o l y m e r i z a t i o n becomes heterogeneous. C l e a r l y t h i s i s a very complex p h y s i c a l s i t u a t i o n and simple models are not adequate to represent a l l the important phenomena. 124..202) shown i n Figure 8 provide only one example of t h i s troublesome problem. Has the nature of the c a t a l y s t changed so that some s i t e s are producing short chains while other s i t e s produce long chains? Or. so t h e o r i e s abound. For example.

1021/bk-1983-0226.ch005 121 in a CSTR. I =0.5. 1983 | doi: 10.acs. Example o f o s c i l l a t o r y b e h a v i o r [ S ] . DC..0.01 mo l e s / l .. temperature = hO °C (201). R e c i p e 8. 0 2 mo l e s / l . Wei. . 1983.02 moles/ -water.01 moles/ -water.0 . 2012 | http://pubs. American Chemical Society: Washington. ACS Symposium Series. J. r <3 0 r i i i Ι Γ Γ "Τ" 1 300 400 5 00 300 40Θ 500 1 1 1 1 1 1 1 £00 rf f i l l Γ00 1 1 1 1 SO© '300 300 90Θ ι ι ι ι I ι ι ι ι I I I I 600 7O0 MINUTES Figure 8. In Chemical Reaction Engineering—Plenary Lectures..w a t e [I] .org Publication Date: July 28. Residence time = min. CSTR emulsion p o l y m e r i z a t i o n o f methyl methacrylate. Run 15.w a t < ΪΓ ι Downloaded by UNIV OF ARIZONA on December 2. RAY Polymerization Reaction Engineering Continuous p o l y m e r i z a t i o n . et al. S = 0.

org Publication Date: July 28. In Chemical Reaction Engineering—Plenary Lectures.. DC. and MGM ( m u l t i g r a i n model). 2012 | http://pubs. J. American Chemical Society: Washington.1021/bk-1983-0226. . et al. 1983. 1983 | doi: 10..ch005 S C M P C M P F M M Q M GROWTH Figure 9.acs. ACS Symposium Series. PCM (polymeric core model). SCM ( s o l i d core model).122 CHEMICAL REACTION ENGINEERING Downloaded by UNIV OF ARIZONA on December 2. Schematic i l l u s t r a t i o n o f p a r t i c l e d i s i n t e g r a t i o n and the p o s t u l a t e d morphological models. Wei. PFM (polymeric flow model).

RAY Polymerization Reaction Engineering 5ΘΘΘ- 123 5ΘΘΘ Y I Ε L Ο R ft Τ Ε ΤIHE. J. et al. . 1983 | doi: 10. M u l t i g r a i n model p r e d i c t i o n s f o r propylene polymeriza­ t i o n i n a semibatch r e a c t o r : Q = M^/M .acs.. 1983..Downloaded by UNIV OF ARIZONA on December 2. DC. HOURS ΤIHE/ HOURS Figure 1 1 . 2012 | http://pubs. American Chemical Society: Washington. Wei. r a t e = gm polymer/gm c a t .h r .ch005 5. . ACS Symposium Series. n In Chemical Reaction Engineering—Plenary Lectures.1021/bk-1983-0226. y i e l d = gm polymer/gm-catalyst.org Publication Date: July 28.

. ( i i i ) D e t a i l e d q u a n t i t a t i v e matching of molecular weight d i s t r i b u t i o n data requires even more complex mathematical models. 1983 | doi: 10. before there w i l l be a comprehensive understanding of t r a n s i t i o n . F. J . D. Albright.-Rev.ch005 ( i ) mass t r a n s f e r r e s i s t a n c e can e x p l a i n at l e a s t some of the observed broadening i n MWD f o r ethylene and propylene polymerization. 10.Type Plastics and Their Monomers". J .011. Concluding Remarks As may be evident from the few examples above. Gardon. Keane. Proceedings 4th ISCRE 1976. Chem. Chapman and H a l l . London. Ray. Chappelear..1021/bk-1983-0226. both experimentally and t h e o r e t i c a l l y . K. G. I . and lead to s t i c k i n g and agglomeration problems e s p e c i a l l y f o r gas phase processes. Macro.D. . 9. Min. C & Ε News. f o r small p a r t i c l e s . et al. W. Bouton. L . Piirma. Ray. r i c h with d i v e r s e and c h a l l e n g i n g design problems. Macro. 7. Literature Cited 1. 1972. polymerization r e a c t i o n engineering i s a f a s c i n a t i n g d i s c i p l i n e . L . T.647.m e t a l c a t a l y z e d o l e f i n polymerization. much remains to be done. Gerrens. Macro. ρ 585. 2. H. "Kinetics of Ziegler-Natta Polymerization". as yet there i s not a commensu­ r a t e l e v e l of i n s t r u c t i o n and research i n the u n i v e r s i t y . Macro. 177. American Chemical Society: Washington. "Continuous Polymerization Reactors".acs. 1976. 1976. U. "Emulsion Polymerization".382 and 4.org Publication Date: July 28. H. Karol. New York. W. DC. May 3. 1982. AIChE Symposium Series 160.D. ACS Symposium Series.124 CHEMICAL REACTION ENGINEERING Downloaded by UNIV OF ARIZONA on December 2. C8. 4. 1972. 1983. S i m i l a r l y . T. J . H. C u r r e n t l y there i s considerable research and development a c t i v i t y i n t h i s area i n i n d u s t r i a l l a b o r a t o r i e s and there e x i s t s a high demand (even i n these times) f o r Ph. "Processes for Major Addition .. K e i i . W. Thus we i n the u n i v e r s i t y should i n c l u d e more from t h i s area i n our teaching. 1979. graduates i n t h i s important area of chemical r e a c t i o n engineering. New York. In Chemical Reaction Engineering—Plenary Lectures. Chem. 3. C . Acknowledgments The author i s indebted to the N a t i o n a l Science Foundation and t o the Mobil O i l Foundation f o r research support.-Rev. 6. T.S. However. ρ A7 Elsevier. Wei. Sci. C11. Sci. ( i i ) P a r t i c l e overheating can occur e a r l y i n the polymeriza­ t i o n . F. R. Proceedings 2nd ISCRE 1972. Series 24. 1974.. ACS Symp. McGraw-Hill. ρ 24. graduates with polymerization r e a c t i o n engineering e x p e r t i s e . 2012 | http://pubs. government and industry could do more to provide the resources necessary t o support u n i v e r s i t y research and stimulate the number of Ph. Patents 4. . However. 5. 1974. C.646. J. 8. 1.

C. J. Odian. 50. T. K. Osmanov. "Polymerization Reaction Engineering". Rubber Chem. M.. "Ziegler-Natta Catalysis and Polymerization". James.. Chem.ch005 16. ACS Symposium Series 104. June. ρ 109. H. Tirrell. 1979. V. "Polymerization Reactors and Processes".. M. 716. R. 25. G. 951. Springer Verlag. C. Prentice Hall. Wiley. Jaćović.. Laurence. Chem. 1423. Sci. J. Schildknecht. in "Chemical Reactor Theory". Mashelkar. W. T. 489. Poly. New York. 18.. 18. 601. 27.E. "Emulsion Polymerization". Polymer 1980. W. 15. 19. 31. Abkin. Tech. Dougherty. Poly. 20.I. 792.5. 28. J. Chem. Soh. Amundson. American Chemical Society: Washington. F. Boor. O. P. T. Kulkarni. K.. L. Murakami. 34. Ν. F.). Couchman. 21. 1299. G. N.. Ebert. Appl.. Yasukawa. Polymer 1981. Ed. Appl. 24. "Emulsion Polymerization of Vinyl Acetate". D. Sci. 1980. 3199. Berlin. Macromol.Ch. Eng. 1977. 32. A. 27. 2nd Edition. New York. 1982. Marten. Sci.acs. 12. J. K. J. H. Ing. 377.. London. ρ 380. Bassett. ρ 434. "Polymerization Processes". 20. 1982. 21. 1981. 29. Tulig. Sci. Poly. J. Poly. New York. 2012 | http://pubs. G. 1980. Henderson. R. A. J. 38. C.. 16. Sci. Poly. T In Chemical Reaction Engineering—Plenary Lectures. 459. H. 1501. J.. 1983. 1982. El-Aasser. Wiley. 17.. L. C. 1979. P. N. Academic Press. E. D. New York. S. K. Publ. D. S. Poly. S. W. I. M. in press. M. Proceedings MMI Symposium on Transition Metal Catalyzed Polymerization (Gordon & Breach). Chem. 22. Gerrens. L. Sundberg. Sebastian. Eur.org Publication Date: July 28. Polymerization Reaction Engineering Ray. 477. 1978. 1977. F. 1981. Sundberg. Dvornić. Gerrens. J.. E. Dionisio. A. Poly. D. Quirk. R. R. A.. 13. Eng. H. E. Madruga. et al. Vanderhoff. 499. 1980. 1983. 1981. J. 15. Bouton. 12. 1981. Hamielec.. . Poly. Sci. J. Poly.. P. 1981. J.. L.1021/bk-1983-0226. Macromol. E. 41. 1982. 26. San Roman. D. J. A. 21. 1. Khomikovskii. 1980. 14. R. Ray. 1982. J. 30. Chem. 1983. I. 35. Gromov. 52. Downloaded by UNIV OF ARIZONA on December 2. 14. Wei.. New York.. Gerrens. Tech. 27. Wiley. R. Poly. "Polymerisationstechnik" in Ullmanns Encyklopädie der Technische Chemie 1980. T... "Emulsion Polymers and Emulsion Polymerization". 1983 | doi: 10. M. Lapidus. "Principles of Polymerization". 1977. translation in German Chemical Engineering 1981. A. et al. Ito. Tirrell. 1982. Biesenberger. R.. M. J. RAY 11. J. ACS Symp. 0 Driscoll. Academic Press. Hamielec. H. A. 37. Galperina. J. R.. (Ed.. 523. 19. Series 165... Piirma. P. ACS Symposium Series.. Skeist. I. July 1982. J. del Puerto. M. Poehlein. K. Poly. 21. Tulig. W. 16. 22. 36. 23. Chapter 9. "Dynamic Behavior of Polymerization Reactors" in "Modelling of Chemical Reaction Systems".. T. H. 33. D. M. 529.. H. DC. "Polymerization Engineering". Sci. 1981. D. Tech. 1982.

Α. 263. Chem. 70. Sci. F.. 1981. M. K. Poly. Eng. Int. Sci. C. 1981. 20.Ch. Sebenda. Eng. 36. Kumar. Poly. J. 791. Appl.. G. M.. 1983 | doi: 10. K. Johnson. 1983. 41. Polymer 1980. Poly. 1218. 14. CHEMICAL REACTION ENGINEERING Soh. Khaligh. 617... 56. Poly. S. 1982. Chem. C. Appl. J. Tirrell. 98. Chen.-Y. Tandon.. Gupta. K. Soh. Poly. 20. . 26. Sci... C. Kazanskii. 1315. K. 13. Saraf. A. 47. Y. J. C. Lopez-Serrano. DC. Omi. Poly.. 305. Tirrell.Y. 190. 14. Katuscak. B. 25. T. D.ch005 42. 389. A. Poly. Tulig. W. 1981. 14. Phukan.. 54. 53.. Y. 1980. M. 25. 66. 60. 1980. D. J. Sci. H. 1980. 1345. Gromley. J. 1... S. T. R. Tirrell. 1981.. Soviet Polymer Science 1981. Kuo. K.. 123. Castro. Herzfeld. Poly. 45. T. S.. in press. K.. Dubrovskii. Motoc.org Publication Date: July 28. D.. Schiessl. Meeting New Orleans. Kumar. Α.. 63. Eur. Polymer 1981. M. J. P. Makromol. 1981.-F. R. F. 1789. Downloaded by UNIV OF ARIZONA on December 2. 1980. ρ 775. Sci. Reddy. F. M. J. Sci. 62. R. Tai. D. 1981. Rajadurai... 182nd ACS Meeting. Poly. Sundberg. Khaligh. J. Probst. Pitchumani. Sci. 18. 1323. 1979. Α. J. Wei. 1117. N. 381. 1501. Johnson. M. Kuruville. Sebastian. K. Ramsay. 1982. K. Poly. Gupta. 341. 57.. 61. 299. 115.I. Modelling Simul. Poly.. 1982. Sundberg.. Pure & Appl.. S. Polymer 1980. Polymer 1981. Chapiro. 313. 1981. Arai. Macromol. A. Ramsay.126 39. K.. 68. ACS Symposium Series. Macromol. 1049.. 55. 1559. O. Poly. Prog. In Chemical Reaction Engineering—Plenary Lectures. 1981. S. Gupta. 1981. Kodaira. Gupta. J.. 17. Sci. 1331. Poly. K. K. Α. S. S. J. 19. Tirrell. 1981. Tirrell. et al. S.acs. Babu. C. Chem. Gupta. 101. American Chemical Society: Washington. Naik.. Stephanopoulos. 52... K.. Sci. Poly. 1981. Eng. Gandhi. A. Pure & Appl. 65. 1209. J. J. Sci. J. Macromol.. 64. Poly. Poly. Kumar. K.. R. Biesenberger. M. Macosko. 1981. Chem. J.Y. Raman. Α. 21. K. 69. 481. J. Chem. J. 195. Appl. 6. S. Tsoukas. 1982. S.. Teranishi.. S. 53. Sci. J.. T. M. C. Poly. 67. 1982. 367. Tulig. J. 26. Harwood. J. R. Ito. S. S.. Ivin. R. H. Α... W. 50.E. J. Chem. 51.. 2012 | http://pubs. 643. Eng. Chem. K. Chem.. A. Kumar. M. Α. Saraf. ACS Meeting N. 22. Vancea. C. Bejger. V. U. 14. A. Sundberg. Tomas. Sci.. Soh. Sci. F. 49. T. 21. Briehl. 43. 22. Appl. 1978. J. Ito. Angew. J. in press. G... 59. 46. 1981. 40. O'Driscoll. Chem.. H.. Poly. Tagawa. D. J. 1982. S.. Macromol. S. 21.. K. S. V. P. K.1021/bk-1983-0226. 44. J. Kolb. B. 20. Kumar. 58. Ito. 48. 53. Tirrell. 1981. I.

J. 633. Kuraschev. Makromol. S.. 27. Polymer 1982. in press. 1981.. Rafler. 94. 31.. 23. M. Poly. Polymer 1981. H.. R. Ε. E. Davtyan. 91. 1980. I. K. M. 69. 1981. L. 1982. Ch. Poly. Appl. R. 22. 84. Gupta. K. C. Naik. Kumar. 95. Can. 267. N. Williams. V. Κ... Kumar. 23. Gupta. J. 96. Gajewski. 1982. 27. Radchenki. Kaneko.. Martinez. Polymer 1982.. Gajewski. Α. R. J.1021/bk-1983-0226. K. 22. Angw.. Acta Poly. Kumar. Frontini. Belavtseva. Durand.. Rajora. Frunze. Polymer. V. Zacharias. Tsvankin. Simon. S. K. Rafler. Appl. Chiu. S.. E. J.. T. Α. S. 87.org Publication Date: July 28... Polymer 1982... J. Sci. 1980. S. Phukan. 85.. D. Mashelkar. 63.-I. G.. Tandon.. Poly. Sci. 60. 215. K.. 23. Α.-Y. P. H.. Gröbler. 89. 80. Chem. 1980. in press.. Munoz-Escalona. 83. Η. T. B. K. S. G. Ravindranath. Cuadrado. Kumar. Gandhi. 570. R. Simitzis. Gupta. Reichert. 3179. Zacharias. A. Reinisch. Gajewski... Kumar. 18.5. 263. Gupta. J. I. V. Poly. 1.. Z. Bonatz. S. Polymer 1982. Poly. Gajewski. P. 1983 | doi: 10. K. Sukthankar. Kumar.-C. . 22. Polymer 1982. 1099. Acta Poly. V. Kulshreshtha. 89. Κ. N. Zacharias. Rev. K. C.. 74. P. Rafler. Gupta. Kotel'nikov. 76. 26. J. Takacs. G. P.. Bohm.. W. H. L.acs. 97. Pomakis. Acta Polymerica 1981... K. RAY 71. Y. Sci. K. 1982.. Poly. 88. 1983. Gupta... Ya. B. Rafler. C. Keszler.. Polymer 1981... Ε. 1982. Tsutsumi. 1759.. Shleifman. 602. Borrajo. Wei.E. Polymerization Reaction Engineering 127 Heikens. Sci.. 145. Downloaded by UNIV OF ARIZONA on December 2. 357. L.. Vaz.. D.. 23. K. 73. P. Mashelkar. J. Shah.. A. P. Appl. I. Angw. 27. Eng. C. S.. Chem. Gajewski. A.A. Sci. 1980. in press.. 93. 79. J. V. G. R. U. 75. Aranguren. G. Ya. Zacharias. Sci. J. 86. Aneja.. 1609. Lin. Poly.. 19.. Ishida. 684. M. Sci. R. Κ. Sci. Polymer 1981. Appl. 2153. A. 27..ch005 78... 1523. Κ. American Chemical Society: Washington.. S. 57. 222. 26. Agarwal. J... 23. H.. Phys.. Α. Poly. Acta Poly. Zacharias.. Gupta. 98. Ravindranath. Bonatz. 471. Α.. Madan. Poly. V. 1118. Genin. Poly. 1981. 92. A. Ε. K. G. J. 99. H. M.M. R. H. In Chemical Reaction Engineering—Plenary Lectures. Bonatz. 1758. Hidalgo. 732. J. J.-M. 1980. K. 1980. D. 31. T. G. 31. R. A. DC. Gajewski. 32. J. 818. 77. Polymer.. S. Williams. Α. 1981. D. J. 1980. K.. Bruneau. 59. 1981.M. Agarwalla. 31. Reinisch. ACS Symposium Series.. Michael. Makromol. 2012 | http://pubs. 81. 82. L. Zacharias. Appl. Volkova. Poly. J. 90. et al. Appl. Acta Poly. Α. K.. G. Κ.. Chem.. Α. Α. C. Blaesche. K. 72.

Ueki. 857. E. 1982. Sci. Taylor. M. Downloaded by UNIV OF ARIZONA on December 2. S.. 480.. Reichert. 1980. Y. Nagahara. 109. 469.. 22. S. Katal. 123. & Dev. Chem.. Polymer 1982. H. A. 108. Poly. Int. 59. Munoz-Escalona. R. K.Ch. P. 103. Soc. 52. E. Norwood. et al.. Y. 1981. Angew. Yuan. Ray. Kinet. Choi.. Bull. A. W. C. Bukatova.128 99. Takada. T. Katal.ch005 105. Vermel'. Yechevskaya. In Chemical Reaction Engineering—Plenary Lectures. Reichert.-G. 415. 124. Brockmeier. Proc. Can.. 117. Poly... 1982. Proc.. Poly. Sailors. Meeting Houston 1979. W. 107. 104. 1. P. V. Ε. V. 26. 250. K. H. J.1021/bk-1983-0226..Ε. H. Y.. W. Doi. Poly. 22.. 22. Polymer 1981. J. Ayres. N. Tamura. Ε. H. Kinet.. Reichert. 110. Ray. 1981. V.. Yamamoto. 814. Α... 1980. H. 120. 1982. Shida. 112. Aug. Poly. T. R. P. Hogan.. 113. Κ.. 27. Doi. American Chemical Society: Washington. Α.. P. Ye. Symp. Hoff. Transition Metal Catal. Η. Zaikovskii. Fenelonov. T. 23. T. Α. Katal. H. 111. T.. Wei. Plenum. Sci. Franz. Taylor. Sci-Chem.. 602.. Meyer. Kinet. C H E M I C A L R E A C T I O N ENGINEERING Munoz-Escalona. 1981. T. F. J. Hogan. . Moroz.. Poly. 1982.. 258. 19. Α. J Appl.. Ζ. Chem. H. Poly. M. Frias.. Likholobov. V. Sudakova. Ray. J. H. MMI Symp. Lin. R. T. in "StructureProperty Relationships of Polymeric Solid". Symp. DC. J. G. Zakharov. R. 21. J. 1981. Vermel'.. 1980. Ed. 116. Yuan.. J. Pullukat. I. Ray. Appl. S. A17.. A15. Y. Keii. 118. 102.org Publication Date: July 28. 1981 Doi. 21. Taylor. 1980.. 372. Y. Pino. G... Japan 1979. Parada. Sci. 12. D. H.. Κ. 1377. Y. 122. V. S.I. Nishimura. Choi. V. Angw. Nagel. 101. 36. D. Crystal Growth 1980. V. H. N... NY. Ermakov. USSR 1980. 119. Poly. Doi. W. Brockmeier. 226. Α. MMI Symp. K. T. 106. 2927. M. 19. Α.-H. J. 1983. Int. M. W. Choi. Ε. 2012 | http://pubs. Kirillov.. Κ. Y. P. 904. R. Α. Κ. H. 21.acs. J. A.. Sci. Shkurina. Mülhaupt.. 1981. V. Yu. Michale. Transition Metal Catal. B. McDaniel. 94. Κ. C. F. Proc. ACS Symposium Series. V. Macromol. K. H.. Villamizar. 19. Engl. 1351.. T. S. 1081. 1982.. Tanaka. Y. Zagrafskaya.. Keii. G. Eng. 125. 1967. Polymer 1981. 48. Sci.. L.. 1902.. Ye. Chem. Polymer 1980.. Macromol. J. D. 22. Transition Metal Catal.. 1691. Sci. 100. Moroz. W. 1982 IUPAC Macro. J. Keii.-Chem. J. 1981. 1981. 23. E. Zakharov.. P. Macromol. 121. (Gordon & Breach). Appl. Reichert. 114. W.. Keii. Ueki. Sci. Chem. M. I&EC Product Res. Poly. 1979. R. 1983 | doi: 10. 115. Bukatov. 49. Appl. Poly. Makromol. 892. G. I. Tsutsui. C. Chem. Zakharov.

Z.. D. 589. 1981.. 1981. Techn. Sci. H. P. Eng. Polymerization Reaction Engineering 129 Seidl. Eng. 1981. R. M. S. N. 1982. Stoiljkovich.. V. D. Teoret. 1981. Setthachayanon. A. 1401. 1983. B. Appl. Poly. M. 1983 (submitted for publication). Slee. 129.. S. Ottino. Jovanovich. M. 95.Ch. P. Weiss. Cicuta. 1981. C. W. 702. 14.. 157. 36. J. 53. 133. 1981. H. 145. Macromol. Chem. 1981. 1263.Ch. Böhme. C. Savadori. R. K. P. 1001. A15. B.E. 1980. T. 1981. A. Chem. Maione..-Rev. Osnovy Khim. 1087.... 36. 150. Ehrlich. M... 1980.. 2nd World Congress Chem. Meira. Makromol. Bostandzhiyan. Makromol. J. 130. Schaart. Gianotti. Yamamoto.-Tech. Chem. 182. J. L. 132. Eng. Sci. 36. 672. S. D. 148.. Jovanovich. Mihail. 14. Mattice. I. 1981. Eng.-Chem. N. 19. 14. 85. R. 1981. E. 135. American Chemical Society: Washington. 1092. Kirchner.E. V.-H.. Savel'ev. Kuan. Clinch. Kuan. L. Akramov. Setthachayanon. 141. D. Chartier. J. Chem. 36. Too... J. T.. 20.. Sci. S. P. Sci. Eng. J. Richter. W. 7th ISCRE 1982. 787. Τ. D. RAY 126. K. 131. 156. Chem. Wei. T.-Ing. Tumarkin. Chen. 28. 147. W. H. J. Eng. 127. Harriott. 21. Sek. A. J. Eng. Chen. Reichert. 26. C. P. D. 1979. Tekh. P.. C. 1981. 2811. Poly. 26. R. Sci. Poly. Chem. White. A. Stolzenberg. Appl. paper in press. T. 1479. T. Poly. Preprints Atlanta ACS Meeting. Siadat. C20.. H. 1980.acs. H.. 138. Eng. A.. B.I. Α. R. Brooks. Ya. Kemblowski. J. 21... Proc. In Chemical Reaction Engineering—Plenary Lectures.. Tekh. Umoh. H. Lindt. Ray. 19. 472.. 151.I.. Eng. Ray. N. N. Takahashi. 185. J.. Chem.5. W..1021/bk-1983-0226. April 1981. J. G. T. Baade. Sofiev... W.ch005 134. Luft. D. Chem. 2nd World Congress Chem. H. A. Sci. W. 154. Boyarchenko. J.. 152. Ray. P.. Α. Fan. B. Stehling. 3745. K. 543. Murav'eva. K. 136.. Angw.. Hughes. 181. 10. Eng. A. Macromol. 1981. Polymer 1980. M. 149. Hamer. W. Osnovy Khim.. Eng. 1. 1981. H. A. B. Zhirkov. Schmidt. Sci. V. A.. 207. Sci. J. D. 1321.. 128. 143. 140. 535.. et al. 1980.. J. Makromol. 155. Α. 1981. Chem. Macromol. Stoiljkovich. Bersted.. Sci. Chen. A. Schi.. S. Quevedo. 1981. Middleman. G. ACS Symposium Series. Downloaded by UNIV OF ARIZONA on December 2. Chem. 215. Chem. 2012 | http://pubs. Sci. 2nd World Congress Chem. Chem. Eng. J. R. Chella. 142. Poly. 1981. 144. Α. 1897. 153. DC. 26. S. 1194. F. 1983 | doi: 10. J. Chem. 21. Polymer 1980. Β. Teoret. I. Romanini. 139. P. 741. Straja. 1197. G. Poly. H. 894. L. J. Schmidt. 1981. . Sci. Vol'ter. Lin. Briedis. 1981. 1982..org Publication Date: July 28. L. S. 539. 1981. Bohdanecky. Sci. Macromol. A. W. 137. B. Janssen. Chartier. Faitel'son... Nassar. 1980. 21. F. 33. J. Poly. 146.

Ottino. J . J. J . M. Ottino. 159. F. K..130 158. J . 25.. 2nd World Congress Chem. Hedrick. H. V. 847. 177. Makromol.Ch. 161.. W.. Ponomareva. Poly... V a l l e s . 1981. Sci.E. 164. 872. 167. 160. W. J . Hoogstraten.. J. 1980. In Chemical Reaction Engineering—Plenary Lectures. 168. F. 28. M. Ε. W. Druz. M i l l e r .ch005 165. Α. Chem.. 899. W.. . J . Agur. R. C. L. 1981. 461. C. 26.. Eng. Meeting New Orleans. Poly. J . 2317. Eng. Gabbert. S c i . Vysokomol. 181. S i d . Ray. Kamal. 166. L. Proc. W. J . S c i . 162. 1981. 1981. Manzione. 3475. Poly.Ch. 1981. Biesenberger. 1980. 1981. Appl.. Poly. Ε.. 921. Vlachopoulos. Poly. J . Appl. Pes. 2152. 1981.. 149. Eng. S c i . A22. Gogos. G. V.. C.. 1981. 175. 1283. M. Macosko. DC. 19. C. Gianchandani. C. 170. Ranz. J . M. 2nd World Congress Chem. 504. T.I. E. S. D. W. Stevenson. R. 2nd World Congress Chem. 176.. 1982. 20. M. 20. Panke. D. P. J . J . W. J . 2nd World Congress Chem. A. 26. J . 171..I. Eng. 2nd World Congress Chem. 250. Castro. 178. 2nd World Congress Chem. 20. C. J . Joosten. C h e l l a . W. Eng. Macosko. R. C. J . Wei. 163. ACS Symposium Series. M. 1981. 447. Lee. K. K. Lee.org Publication Date: July 28.. Eng. M. Nigam. 20. Sci. . W.acs. E. P.. M. Eng. J. 1981. 173. 1981. 20. D. 180. Hamer. Eng. Castro. K i p a r i s s i d e s . Cuwerkerk. Bergles. S c i . V. 2012 | http://pubs. 765. W. 45. soyed. M. Eng. C r i t c h f i e l d . Eng. J . 1980. L. Appl. Appl. Castro. 177. Ye. Sci. S e r i e s No. D. R.. J . 272. 2nd World Congress Chem. Ε. H. C. D. S t e i n l e . 3207. D. 465. Richter. M. Gianchandani. 182. 104 1979. Belyayev. 182. Poly. C. C. Chem. Castro... 526.. ACS Symp. 1981 Annual A. D. W. 1981. Ε. Macosko. Throne. Gonzalez. Lynch. 471. 475. R. Progelhof. D. Lopez-Serrano. Poly. G.. A..E.. G. Eng. 1981. Camargo. Nigam. Appl. J . D. Gogos. 1981. J. E.. . . C. R. Poly. M. Macosko. Sci. Throne. W. S c i . J . Macosko. Tirrell.. 1983 | doi: 10. H. Poly. Saxena. Eng. C H E M I C A L REACTION ENGINEERING J o s h i .I. 1981.. Poly. L. J . C. J .E. J . Eng... 172. American Chemical Society: Washington. M. 26. Macosko. E. 1979.1021/bk-1983-0226. A. Tirrell. C. Wiley. 27. J . 26. Macosko. Eng. S. Tan. 2nd World Congress Chem. Α. 179. Singh.Ch. Eng. 1980. Downloaded by UNIV OF ARIZONA on December 2. 1983. Eng. B. 20. F. 1981. L. Poly. S c i . E. Sci.. V. Macosko. 169. S c i . L. Poly. 785. 1980. et al. 519. Domine. 1980. M. J . Ind. Appl... 1981. 2067. Dev. 26. W. Ε.. P. 184.. 174. Budtov. Lambla. 868. 183. C. S.. 1980. 2nd World Congress Chem. 838.. J .

In Chemical Reaction Engineering—Plenary Lectures. W. 181. J. Schork. 28. McCulley. J.E. W. Foster.5.Y. 1981.. A. 1065. Chen. F.1021/bk-1983-0226. R. J. N. H. 112. 194. Nyeu. A. H. Α. J. 19.-Ing. Poly. 1055. Schröder. 1979. G. Moritz. Eng. M.. Zhizhin. 1981. Sci. ACS Sym. Cameron. A. G. B. Lodge. Meeting New Orleans. 207. 14. Chem. Sci. 2555. Chem. American Chemical Society: Washington. C. J. Series 1981. 505. A. F. Polymer 1981. 3909. D. 1979. H. 1982. 22. W. P. M. Sci. L. Moritz. Eng. Poly. 1979. E. 1983 | doi: 10. 22. 1295. Α. 48. 191. Kondo. 449. Drexler. 182nd ACS Meeting N. J. Hamielec. Denton. 1981. Kiparissides.ch005 190. L.. C. J. Cutter. R. 213. 21 415.. 56. in press.. Ζ. Chem. H. Piotrowski. 1981 Annual A. Hulme. L. Poly.. Schork. Langner. Can.. Chem.. E. 329. 1981.E.. F. 200. 1981. F. Nakashio. C. Appl.. Appl. B.. H. H. Gregge. B.. Eng. 194. T. T. F. 26. 53. 2nd World Congress Chem. Y. Daroux.. J. C. F. Ikeura. Bordet. 1982 IUPAC Conf. R. Yang. Κ. L. Stolin. Hatate.. 197.. 1980. Wang. Reichert. M. C. 65. 38. E.. R. 211. Merzhanov. 535. RAY 185. L.. 39. J. Hamann. 1981. Eng. Poly. 1981. Reichert. 748. Sci. H. 1980.. Chem. 182nd ACS Meeting N. Downloaded by UNIV OF ARIZONA on December 2. K. Sci.. 206. Chem. Meira. D. 21. 195. S. 747. 1981.. Y. T. 20. 816. Α.-C. 196.-Tech. L. Y. Meeting Chicago. F... R.-U. B.. 188. 1593. 220.I. Α. DC. Ko. A. Moritz. Appl. Wei. H. 1980. Johnson. 208. Gilbert. J. Meyer. J. 1982. Ray. Sci. 193. Dworak. H. J. Eng. Eng. 1..-U. J. J. Ger. Polymerization Reaction Engineering 131 Kovenklioglu. C. Κ.. Langner. 1981. Malkin. Laurence.. CEP July 1982. H.. Schork. Ray. 201. .Ch. 2. Ger. Simmons.acs. 187. Eng. Sci. H. G. F.. 214. Poly. 209. 202. P. Rawlings. 199. 1979. Β.-A. E. Makromol. 1981.I. 1980 Annual A. 25. S...-Ing. J.. MacGregor. D. Schork. M. Tong. 181st ACS Meeting Atlanta 1981. A. 53.. PMM USSR 1981. Mhaskar. Reichert. Allsopp.. Pure & Appl. Shinonome. Lundeen. 495. Langner. 1981.. Sci. 1983. Jr. J.. Trathnigg. ACS Symposium Series. Lin. 1983. Proc. 204. G. 2012 | http://pubs. 1981. Aug. 182nd ACS Meeting N. 210. Thibodeau. M. F. Eng. B. M. Chem.. S. R. G. Zamani. Ray. H. Wu. A. 58. Κ. M. Eng.Y. H.. R.. 62.-F.-Tech. Blanks.-Ing.. Chem. 200. J.. 386. A. T. T.-W. et al. 192. 186. Κ. Poly. Chem... K. 203. 212.Y. 2. F.. Rao.. V. Japan 1981. J. 205. W. 215. W. Reichert. 44. Schwab..-N..Ch.-U. Chem. Tech. W. Poly. Timm. Harwood. C. H. J.. A. 1980. Grulke.. Sci. Ray. D. Hwu. Poly. R. 52. 162. Huang. 189. S. H.org Publication Date: July 28. 198. Α. Eng. J. 53. F. Eng.. Gusika. Chu.. 26. ISA 1980. M.

F.Ch. 223. D. ACS Meeting N. 1981. 222. J. ACS Symp. Vanderhoff. K. Goebel. 1979. 1981. Nomura. Faraday I 1980.Y. Κ. Chem. 226.I... I. 233. C.. Wei. M. Almog. Sci. H. Min.132 C H E M I C A L REACTION ENGINEERING Downloaded by UNIV OF ARIZONA on December 2. Moritz. Poly. J. 239. ACS Symp. W. M. 237. Poly. Fukui Univ. L. H. I. J. 327. K. Kujita.. K. M. 23. Kiparissides.-Ing. Prod.. B. B. 272. 240. F. A. 1. Q. 225. Chem. J. R. Guillot. 20. 76. 1982. Pham.C. J. Sundberg.. 1982. Appl. Α. 165 1981. Ser. ACS Symp. E. R. 35. 1983 | doi: 10.1021/bk-1983-0226. K.-Tech. A17. 18. L. D. 220. Makanjuola. J. Schneider. Dev. Oldshue. 165 1981. Poly. J. C.. C. Kiparissides. Ser. Mork. Grinnell. M. J. K.S. Hsieh. No. Mechler. J. Poly. Kubo.. W. A.. C. 224. 121. M.. W. J. S. Reichert. D.. Langner. 10. 20. 230. Sci. 232. D.. 235. Poly. R. 241. H. Gostin. El-Aasser. J.. J. H. 29. Harada. 1983. Linow..-R. 1980. Yamamoto. ACS Symp. 363. Dautzenberg. Eng. H. 165 1981. M. H.. 489. Soh. 519. M. 243.. Nomura. M. I. D. 27. James. T. M. S. Chem. J.. B. Sci.. D. Makromol. H. Bataille. 74. 236. 1980. Sci. 371.. Polymer 1982. American Chemical Society: Washington. F. Eng.. Ser. 369. No. J. Ind. Κ. Van. G. 31. 229. P. Coll. 90. Chem. Poly.. Harada. Chem. 165 1981. 167. Hansen.. Ser..-H... 2012 | http://pubs. Poly. in press. Brooks. 1981. 1982. Hamielec. Y. 242. Chem. Purz.. Cauley. R. Acta Poly. Sci. Rapid Commun.-Chem. 53. Y. Ohtsuka.. 1981. M. W. Nomura. 903. Chang.. 26. I. 1980. 234.acs. J. H. J. W. 53... R. 228. Chen. Y.. Fac. J. 17. 377. Thompson. S. J. . 27. Baade. K. Poly. Richter. K. Tseng. 1981. J. Zichy. Brooks. Poly. J.-J... 18. Phys. W. Pure & Appl. K. Chem. Wolf. P. 221. 218. 145... 219.. No.. et al. 18. ACS Symposium Series. W. Y... 217. O. Chem. Poly. Reichert. CEP May 1982.. Ham. Kawaguchi. Piirma. Chem. F. 795. Sci. MacGregor. Piirma.. Koch.-U. G.. E. 77.. Sci. DC. 417. 53. Y. B. Baldus. Ranee. Macromol. E. Ε. C. 323. Poly. Poly. 1980. Commun. 20. Sugi. Appl. Chem. W. 227. 238.ch005 216. Sundberg. Η. 1771. Appl. Sci.. 1981.. J. Jaeger. 472. 231. 283. Nomura. Ponnuswamy. Ugelstad. 13. Fujita. In Chemical Reaction Engineering—Plenary Lectures. 697.. Res. M. D. G. I. Eng. H. Sci.. Interface Sci. 1982. 1981. 1599. Bassett. 335. Sci. S. 1982. Hoy. O. Chem.E. Friedman. Mem.org Publication Date: July 28. 1981. Reinisch. No. J. Levy.. Eng. D. C. Poly. 1980. 68. Pure & Appl. M. Horie. 1980. B.

I. 415. 1983. W.-Chem. 26. Ray. Ray. C. 1983 In Chemical Reaction Engineering—Plenary Lectures.Ch. J.I.acs. Chem. Appl. K. 1982 Annual A. 252. 693-98. Ser.org Publication Date: July 28. Sci. T. Makromol.. H.I. Lin. W. 257. J. E. Tech. C. Johnston. Chonde. Sci. No. 248. V. J. W. ACS Symposium Series.. 246. 1971. Taylor. Meeting Los Angeles. R A Y Polymerization Reaction Engineering 133 244. 26. Wei. 251. Ku. W. Jr.-C. 26. Estaque. Α. Kawaguchi. Patterson. I. J.. Eng. K. T. Sci. MacRury.Downloaded by UNIV OF ARIZONA on December 2. J. 33. Bataille. W. Sci. 1. 1978. Rollin. No. Kirillov. 165 1981.. 697. Poly. Appl. . Κ.. (submitted for publication). H. Kuchner. 1982. ACS Symp. H. 1981. 254.. Ray. E.E. T. 1637.-Y.. 250. Pichot. 43. H. M.E. 1981.. Guerrero. Guillot. Kaspar. G. 253.1021/bk-1983-0226. W. Gerrens. Ohtsuka. Ing. Snuparek. W. 255. Poly. 369. 1327... L. Ray. B..E. R.. Sci. Rapid Commun. J. Ley. D.. J. 1983 | doi: 10. Chem. P. B. Poly. J. Poly.. 165 1981. J. 1982 Annual A. Chiu. RECEIVED April 26. 247. Α. G. Ham.. A. Meeting Los Angeles. H. Y.ch005 5. Y.Ch. Choi.I. 4081. ACS Symp. Ser. H. Y. Chem. L.. 26. Meeting Chicago 1980. Bassett. 2012 | http://pubs. American Chemical Society: Washington. 1819. 1981. Y. Macromol. Sci. A17.. J. 1499. Appl... DC.. 249.. 389. R. Appl.. Krieger.. Sugi. 256.. Poly. 1980. H.Ch. J. J.-C. 1981. Guillot. Guyot. et al. L. Rawlings. A. Appl. 245. Sci. Taylor.

This page intentionally left blank .

the f i e l d of mixing i n chemical engineering i s immense. 2012 | http://pubs.1021/bk-1983-0226. It is concluded that a comprehensive and predictive theory for micromixing should not be sought through turbulence theory alone. phenomenological models for mixing earliness i n the age space. DC..80/ 0 © 1983 American Chemical Society In Chemical Reaction Engineering—Plenary Lectures.6 Mixing in Chemical Reactors JACQUES V I L L E R M A U X Downloaded by CORNELL UNIV on December 2. mechanism of micromixing i n physical space and segregation phenomena at the microscopic l e v e l . Nancy. t h i s review w i l l be r e s t r i c t e d . ACS Symposium Series. Of course. Wei. et al.ch006 Institut National Polytechnique de Lorraine. American Chemical Society: Washington. mixing in stirred tanks and static mixers.org Publication Date: July 28. d i r e c t i o n s i n which such a theory should be sought are now i n view.. 1983 | doi: 10. although t h i s important operation also poses unsolved problems to i n d u s t r y . J. Laboratoire des Sciences du Génie Chimique. macromixing and residence time distributions. whose parameters could be interpreted on a fundamental basis by this theory. but rather in phenomenological interaction models. However. Contacting reactants and subsequent mixing of r e a c t i n g species i s one of the major features c o n t r o l l i n g the behaviour of chemical r e a c t o r s . Therefore.acs. The aim o f t h i s chapter i s t o review recent and s i g n i f i cant c o n t r i b u t i o n s which may l e a d t o such a general treatment. France Recent progress in the understanding and modelling of mixing phenomena in chemical reactors is reviewed. The following items are discussed: characterization of the degree of mixing. CNRS-ENSIC. Eulerian approach to turbulence theory with application to modelling combustion. 1983. The purely p h y s i c a l aspects of mixing won't be considered. That mixing i n chemical r e a c t o r s i s a subject of very a c t i v e research i s a t t e s t e d by the recent p u b l i c a t i o n of s e v e r a l review 0097-615 6/ 8 3/0226-013 5 $ 13. . In s p i t e of recent advances. An example is presented of the application to continuous free radical polymerization. a u n i f i e d theory p r o v i d i n g the engineer with general r u l e s a p p l i c a b l e to any case of competit i o n between mixing and chemical r e a c t i o n i s s t i l l l a c k i n g . to those phenomena where mixing and chemical reactions are c l o s e l y l i n k e d . with perhaps a few exceptions.

C).ch006 136 C H E M I C A L REACTION ENGINEERING papers. Since the p i o n e e r i n g work of Danckwerts ( 12) . where AC i s the value o f Sc before mix­ i n g (or at the reactor°inlet). In a non-uniform mixture. The l a s t point that should be o u t l i n e d i n t h i s i n t r o d u c t i o n i s that mixing i n chemical reactors r e a l l y c o n s t i t u t e s an o r i g i n a l chapter of Chemical Reaction Engineering.1021/bk-1983-0226. i t i s encouraging to see i n d u s t r i a l p a r t i c i p a n t s attending meetings and g i v i n g t h e i r o p i n i o n about the relevance of research topics and about what should be done to improve our knowledge i n the f i e l d (9. Instead o f d u p l i c a t i n g these reviews and r a t h e r than present­ i n g an exhaustive l i t e r a t u r e survey. whose a n a l y s i s would be o f the g r e a t e s t i n t e r ­ est t o t h e o r i c i a n s o f mixing. DC. Zwietering (13) and others. The RTD and the segregation concepts f o r i n s t a n c e . In doing so. . et al. p(C) may be c h a r a c t e r i z e d by i t s mean C. then AC = 2 C ( l .. papers d e s c r i b ­ i n g the e f f e c t of a g i t a t i o n on y i e l d i n p i l o t p l a n t reactors (7. From these q u a n t i t i e s . and to give personal views on these s u b j e c t s . I ac­ cept the r i s k that t h i s review may appear p a r t i a l or incomplete to those authors whose (sometimes e x c e l l e n t ) papers w i l l be l e f t out. That mixing i n chemical reactors i s also a problem of v i t a l importance to i n d u s t r y appears i n some. The m a x max σ In Chemical Reaction Engineering—Plenary Lectures. I have chosen t o emphasize the points which seem the most c r i t i c a l and c o n t r o v e r s i a l . This should prevent "too many academics pursuing too many non-problems" (Jl). ACS Symposium Series. 2). too r a r e . American Chemical Society: Washington. Of course t h i s doesn't mean that we must neglect the con­ t r i b u t i o n of the l a t t e r d i s c i p l i n e . Several c r i t e r i a are used f o r a q u a n t i t a t i v e c h a r a c t e r i z a t i o n of the " q u a l i t y of mixing". Wei. Another critérium i s Δ = AC/AC . Nevertheless. l e t p(C) be the l o c a l c o n c e n t r a t i o n d i s t r i ­ b u t i o n of a species.org Publication Date: July 28. Smarting from two_streams o f ( r e ­ duced) c o n c e n t r a t i o n 0 and 1. 1983 | doi: 10. as w i l l be seen below.. 16. 2012 | http://pubs. or those where s i g n i f i c a n t progress has been made i n recent years. J. s e v e r a l c r i t e r i a may be de­ f i n e d (17). 15.) or the d i f f i c u l t i e s of conserving a good s e l e c t i v i t y when s c a l i n g up a mixing device to the commercial s c a l e (8). I t i s a p i t y that p r o p r i e t a r y requirements r e s t r a i n the p u b l i c a t i o n of such indus­ t r i a l case s t u d i e s . its_ variance and the average value AC of the d e v i a t i o n AC = |C . These have been r e c a l l e d by Hiby (17). and t h i s point w i l l not be discussed here. namely 6 = AC/C. D e f i n i t i o n and c h a r a c t e r i z a t i o n of the degree of mixing A d e f i n i t i o n of mixing i s proposed i n many papers and t e x t ­ books (14. i t i s c l e a r that chemical r e a c t i o n engineering c o n s t i t u t e s a s c i e n t i f i c d i s c i ­ p l i n e with i t s own methods. have completely renewed the d e s c r i p t i o n of the beha­ v i o u r of r e a c t i n g mixtures i n r e a c t o r s .10). which appeared a few years ago or while the present was i n p r e p a r a t i o n (J_-6) .C| from the mean. I am convinced that f u t u r e progress can be expected i n pursuing novel concepts rather than i n more s o p h i s t i c a t e d combinations of chemical k i n e t i c s and f l u i d me­ chanics. 6 = A C / C and ό = σ/C.acs. 1983.Downloaded by CORNELL UNIV on December 2. But t h i s i s a general problem i n Chemical Reaction Engineering.

05 or 0 . then the a u t o c o r r e l a t i o n f u n c t i o n of c o n c e n t r a t i o n i s (2):g (r) = c(x) c ( x + r ) / o . We s h a l l see that i n Lagrangian coordinates.σ /(do /dt) i s a l s o a mixing time. . A f i r s t remark about these mixing i n d i c e s i s that a c e r t a i n confusion p r e v a i l s i n the l i t e r a t u r e owing to the m u l t i p l i c i t y of d e f i n i t i o n s . . .where a i s the age of a molecule. I t would be d e s i r a b l e to adopt one s i n g l e measure f o r the degree of mixing (and/or homogeneity). Wei. c o n c e n t r a t i o n f l u c t u a t i o n s have been measured using a c a t a l y t i c wire (24). The segregation index J of Danckwerts (12) i s one of the most famous ones. I t a p p l i e s to continuous r e a c t o r s and r e l i e s upon the v a r i ­ ance of age : J = Var a /Var a. 1 .δ. l i g h t a b s o r p t i o n . or Δ. A second remark i s that an experimentally measured degree of mixing depends on the s p a t i a l r e s o l u t i o n of the probe used f o r mea­ s u r i n g " p o i n t " values of the concentration. t h i s i s a l s o known as the c o n c e n t r a t i o n mac r o s c a l e . down to some pres­ c r i b e d small value ( f o r instance 0. 22). or I to f a l l from t h e i r i n i t i a l value (before m i x i n g ) . The s p a t i a l r e s o ­ l u t i o n of p h y s i c a l methods ( o p t i c a l .1021/bk-1983-0226. The s c a l e of segregation gives i n f o r m a t i o n on the s i z e of se­ gregated regions. Their common property i s that the s m a l l e r they are. e t c . et al.acs. 0 1 ) . The s c a l e of segregation i s then defined as : 2 s 0 0 g = c c σ g Downloaded by CORNELL UNIV on December 2. The d e f i n i t i o n s of the degree of mixing presented above aim at a l o c a l c h a r a c t e r i z a t i o n of the mixture homogeneity i n the phy­ s i c a l space. which plays an important r o l e i n the i n t e r p r e t a t i o n of micromixing phenomena. American Chemical Society: Washington.. 19). the b e t t e r the q u a l i t y of the mixture. An o r i g i n a l method based on the con­ tinuous i n j e c t i o n of r a d i o a c t i v e t r a c e r s i n an i n d u s t r i a l mixer has a l s o been proposed (23).C) . e l e c t r i c a l microprobes) i s about 100 ym (19) so that these are w e l l s u i t e d to macromixing s t u d i e s but cannot compete w i t h chemical methods f o r the study of mixing at the molecular s c a l e . ACS Symposium Series.C). based f o r instance on the reduced variance of the c o n c e n t r a t i o n d i s t r i b u t i o n . Let c(x) and c(x+r) be the f l u c t u a t i n g concen­ t r a t i o n s at p o i n t s χ and x+r (c = C .ch006 2 2 L s = 8 s ( r ) dr ο In turbulence theory./ Ï J . DC. p In Chemical Reaction Engineering—Plenary Lectures. but /ΐζ = σ/σ bas a l s o been used. In l i q u i d s .org Publication Date: July 28. VILLERMAUX 137 Mixing in Chemical Reactors I n t e n s i t y of Segregation d e f i n e d by Danckwerts is I = σ^/σ = o / C ( l . 2012 | http://pubs..6. The e s t i m a t i o n of mixing times i n s t i r r e d tanks w i l l be discussed i n a further Section. J. the most commonly used methods are e l e c t r i c a l c o n d u c t i v i t y (18. 1 .6 . fluorescence (30) and che­ m i c a l methods based on the c o l o r change of an i n d i c a t o r under the i n f l u e n c e of an instantaneous r e a c t i o n (21. I f two species A and Β are mixed. In gases. 1983 | doi: 10. Mixing times are the times r e q u i r e d f o r 6. The corresponding degrees of homogeneity may a l s o be defined as 1 . There a l s o e x i s t more i n d i r e c t mixing i n d i c e s . the d e f i n i t i o n of I becomes 02) *s "~ A B^Ao*^Bo* R e l a t i o n s h i p s between a l l these i n d i c e s are obvious. . 1983.

based on the assumption of homogeneous i s o t r o p i c turbulence. based on i n f o r m a t i o n theory and on the e s t i m a t i o n of the "entropy" of a mixture. who are very f a m i l i a r w i t h the methods of f l u i d mechanics. As mixing proceeds. ACS Symposium Series. the use of the formalism of turbulence alone seems to lead to a deadlock.org Publication Date: July 28. 2012 | http://pubs. 26).) r e l i a b l e methods f o r monitoring c o n c e n t r a t i o n f l u c t u a t i o n s are l e s s known. . 1983. This allowed a comparison of e f f i c i e n c y of d i f f e r e n t a g i ­ t a t o r s (26). J i s s t i l l a very popular q u a n t i t y i n the l i t e r a t u r e where i t i s used by many authors to compare t h e i r micromixing models.1021/bk-1983-0226. Another i n d i r e c t mixing index was proposed by Ogawa et a l . (25. However I t h i n k that w h i l s t i t c o n s t i t u t e s some u s e f u l reference for mixing e a r l i n e s s .. J. These reviews r e v e a l no major breakthrough. DC.from which i t i s seen that M= 0 i n a plug flow r e a c t o r and M = 1 i n a continuous s t i r r e d r e a c t o r . the degree of homoge­ n e i t y of the mixture i s defined as Μ = H/H^. when complex chemical r e a c t i o n s are i n ­ volved. et al. This method was used to study the mixing r a t e i n s t i r r e d v e s s e l s . However. where H^ i s the f i n a l entropy of the homogeneous mixture. An ex­ c e l l e n t p r e s e n t a t i o n of the s t a t e of the a r t can be found i n the recent l i t e r a t u r e e s p e c i a l l y by Brodkey (16. 1983 | doi: 10.C H E M I C A L REACTION ENGINEERING Downloaded by CORNELL UNIV on December 2. _2. As an i n t e r e s t i n g g e n e r a l i z a t i o n . as has been pointed out by s e v e r a l authors.. Most of them can be deduced from s p e c t r a l measurements. i t seems h e l p f u l to r e c a l l (Table I) the p r i n c i p a l q u a n t i t i e s c h a r a c t e r i z i n g v e l o c i t y and c o n c e n t r a t i o n f l u c t u a t i o n s . American Chemical Society: Washington. This "entropy" i s defined from the t r a c e r d i s t r i b u t i o n among η zones i n the r e a c t o r as Η = . E u l e r i a n approach: M i x i n g and Turbulence Turbulence theory provides a c l a s s i c a l approach to mixing phenomena. f a s t response In Chemical Reaction Engineering—Plenary Lectures. I n t e r e s t i n g data were r e c e n t l y obtained by using l o c a l conductometry microprobes i n t e r f a c e d w i t h a high g a i n . J = 1 i n a t o t a l l y segregated mixture ( a l l the ages are the same w i t h i n a " p o i n t " α = αρ) and J takes a minimum value depending on the residence time d i s t r i b u t i o n when mixing e a r l i n e s s i s at a mi­ nimum.J " E ( t ) In E ( t ) dt. where V* i s the reduced volume of zone i and p i t h e i = l " p r o b a b i l i t y " of occurence of the t r a c e r i n zone i (see reference (25) f o r more d e t a i l s ) . I f the techniques f o r determining v e l o c i t y f l u c t u a t i o n s p e c t r a are w e l l e s t a b l i s h e d (hot wire anemometer.acs. This i s a n a t u r a l way f o r mechanical engineers and spe­ c i a l i s t s of combustion..ch006 138 dp the mean age at " p o i n t " Ρ and Var denotes the variance of the d i s t r i b u t i o n s over a l l " p o i n t s " or a l l molecules i n the r e a c t o r . l a s e r . M was p l o t t e d as a f u n c t i o n of time from a record of the concentrations at v a r i o u s places i n the v e s s e l . As the r e s u l t s of turbulence theory are sometimes used i n c o r ­ r e c t l y i n the l i t e r a t u r e .. and only slow progress on a d i f f i c u l t road. i t i s of l i t t l e i n t e r e s t f o r the design of chemical r e a c t o r s as i t cannot be measured d i r e c t l y nor be used for a s t r a i g h t f o r w a r d c a l c u l a t i o n of chemical conversion. 27) and P a t t e r s o n (3).d o p p l e r anemometer. the macromixing ho­ mogeneity i n a continuous r e a c t o r having a RTD E ( t ) may be defined as (25) : M = .£ V? In p^. Wei.

the second term of (3-2) i s o f t e n n e g l i g i b l e and T ifc 2 ( L 7 ) / . (See S e c t i o n on s t i r r e d tanks). J. In l i q u i d s . λκ i s t y p i c a l l y between 10 and 100 urn. L to L and found ( Ι ^ / ε ) / * = (Lf/ε)' (Ι^/ε) = q/ε A t y p i c a l value f o r i n an i n d u s t r i a l s t i r r e d tank i s a few m i l l i m e t e r s (19). The problem i s to estimate the turbulent energy d i s s i p a t i o n per u n i t mass ε from macroscopic data. Here a l s o .org Publication Date: July 28. i t i s not obvious that a l l the power Ρ d i s s i p a t e d at the shaft contributes to ε and s e v e r a l authors (2_.1021/bk-1983-0226. I t i s c l e a r from Table I that there are two p a r a l l e l f a m i l i e s of c h a r a c t e r i s t i c s p e r t a i n i n g to v e l o c i t y f l u c t u a t i o n s on one hand and to c o n c e n t r a t i o n f l u c t u a t i o n s on the other hand.. The Kolmogorov microscale λκ i s f r e q u e n t l y used i n the i n 1 s s 3 e c 1 s 1 / 3 f In Chemical Reaction Engineering—Plenary Lectures. ACS Symposium Series. Patterson (3) proposed a s s i m i l a t i n g :e Tc. . 3J_. In order to estimate T . 1983. some authors using f o r instance v e l o c i t y macro or m i c r o s c a l e s . Wei. This d i s t i n c t i o n i s not always made i n the l i t e r a t u r e . or of the segregation. viLLERMAUX Mixing in Chemical Reactors conductimeter (28.. DC. 30). The c l a s s i c a l treatment of C o r r s i n . 32) have been led to introduce an unknown " e f f i c i e n c y " η such that ε = ηΡ/pV. i n s t i r r e d tanks.ch006 139 g g s s 1/3 2/3 (3-1) f o r gases τ Se s 1/3 2/3 il 3 1/2 In Sc for liquids (3-2) In l i q u i d s . 1983 | doi: 10. In t h i s respect. Taylor and C o r r s i n microscales Xf and A are those of the maximum of d i s s i p a t i o n e i t h e r of the turbulent k i n e t i c energy. the C o r r s i n microscale X and the a s s o c i a t e d time constant T play an important r o l e . λβ. depending whether ve­ l o c i t y or concentration f l u c t u a t i o n s are considered. Energy loss below t h i s s i z e only occurs v i a viscous d i s s i p a t i o n . s e v e r a l s c a l e s have been i n t r o ­ duced i n the framework of turbulence theory. I t must a l s o be r e c a l l e d that d i f f e r e n t length and time s c a l e s have very p r e c i s e meanings and should not be used at random on the s i n g l e b a s i s o f dimension­ a l a n a l y s i s . widely used i n the l i t e r a t u r e on mixing.acs. An a d d i t i o n a l d i f f i c u l t y i s that ε i s not uniform w i t h i n the tank volume and may vary by a f a c t o r 10 from one place to the other. but there are s t i l l problems of space and time r e s o l u t i o n (19) and new methods should be developed f o r the determination of concentration f l u c t u a t i o n s s p e c t r a i n chemi­ c a l r e a c t o r s . (which are b e t t e r known) i n place of c o n c e n t r a t i o n s c a l e s . or that of the i n l e t tubes i n tubular r e a c t o r s . et al. American Chemical Society: Washington. The macroscales L and L c h a r a c t e r i z e l a r g e i n i t i a l eddies.6. The smallest s i z e f o r turbulent eddies i s given by the Kolmogorov microscale λ^. For i n s t a n c e . whose s i z e i s g e n e r a l l y comparable to that of the i m p e l l e r i n s t i r r e d tanks. namely λκ. y i e l d s the f o l l o w i n g expressions : f Downloaded by CORNELL UNIV on December 2. and Xç (see Table I ) . 2012 | http://pubs. 29.

ch006 3 ο 2 w m 3 ο H Ο W 25 Ο > > g ο PI Ο a 4^ Ο . f lOv .. DC.In Chemical Reaction Engineering—Plenary Lectures. τ 12$c' ε c' s E (k) L g(r) 2 c(x) c(x+r) „. E ( k Γ ο 2 1 k dk.2 ~..2 f ( r ) dr ÏÏE(Q) . et al.1021/bk-1983-0226.) E(k. 1 1 E(k..2 0 A l l directions Taylor microscale Spectra energy d i s s i p a t i o n 2 = 10 λ rt dt = (ν 3 2 .2 = 2 = (ο&^/ε)^ . Downloaded by CORNELL UNIV on December 2. ACS Symposium Series. 1983.2 f /ε) J ο Γ 10 J 3/2 dt dk. One ε = /2 u(x) (uV =f energy o f t u r b u l e n t motion Turbulent Kinetic L f(r) autocorrelation Macroscale u' = U .org Publication Date: July 28. 2012 | http://pubs..U + u Mean square f l u c t u a t i o n Velocity Table I . 1 E(k.1/2 B a t c h e l o r m i c r o s c a l e λ_ )dk E(k. J. American Chemical Society: Washington.) k.2 (c ) Concentration C = C + c Homogeneous I s o t r o p i c Turbulence du' dt u(x+r) .2 de dt (Corrsin) 2 / g(r) /ρ V > f E(k) -Γ de* dt 0 r 6 5) Γ 1 „. 3 « @bv 1/2 1 M (5)/ε) 2 λ /λ s i 2 microscale : 2 λ -Λ/ν time c o n s t a n t λ„ dissipation intensity microscale /ε) Se Corrsin Small Corrsin Corrsin Segregation Segregation - τ s 2 x f k 1 k 2 2 k -1 " E (k) s dr dk dk Λ 2 λ' s 12<© dk E (k) dk .2 30 v u' ε = 30 ν u' E ( k ) . Wei. .) direction <*£L .)dk. 1983 | doi: 10. constant dissipation time Kolmogorov m i c r o s c a l e Viscous Taylor .acs.

z )~0. w i t h C o r r s i n s time constant T . ACS Symposium Series. Their data have been (and are s t i l l ) e x t e n s i v e l y e x p l o i t e d f o r t e s t i n g t h e o r e t i c a l mo­ d e l s . Among experimental studies of chemical r e a c t i o n s i n turbulent media.. American Chemical Society: Washington. a new s e r i e s of experiments was r e c e n t l y performed by Bennani e t a l . For i n s t a n c e . Previous studies (2) had confirmed that the decrease of I w i t h a non-reacting species (passive s c a l a r ) obeys C o r r s i n s equation : 9 Downloaded by CORNELL UNIV on December 2. as w i l l be discussed i n a later section. A more f r u i t f u l s o l u t i o n to the c l o s u r e problem i s provided by the use of p r o b a b i l i t y d e n s i t y functions f o r the f l u c t u a t i n g com­ ponents. et al. . d . a 13-equation model i s required ! ( 3 ) .ch006 8 G 1 s g 1 dl (3-3) dt where T i s given by (3-2). Bennani e t a l . f a s t r e a c t i o n s i n tubular reactors w i t h m u l t i j e t i n j e c t i o n of reactants are very popular. although one may ask i f homogeneous i s o t r o p i c turbulence was p e r f e c t l y c o n t r o l l e d i n these experiments. w i t h a s t o i c h i o m e t r i c p r o p o r t i o n of r e a c t a n t s . Wei. 30. I n order to r u l e out t h i s o b j e c t i o n . The s i t u a t i o n i s even more complicated when the temperature and the density of the r e a c t i n g mixture are a l s o f l u c t u a t i n g .. 1983. C j . Various shapes (spiked.60 j spectrum decreasing as kj-5/3^ Let us now consider the case of a moderately f a s t second o r ­ der r e a c t i o n A + Β -> products. square wave. (_28.6. and a l s o C ^ C J . I n a d d i t i o n t o tho­ se f o r v e l o c i t i e s (U = U + u_)_and concentrations (Cj = Cj + C j ) . as u u./Τζ ( 2 ) . (28) found /ïg~ α. ÎÎ C J . 1983 | doi: 10.. and the d i s s i ­ pations ε and ε can be w r i t t e n (3). 29_. a simple r e s u l t which can a l s o be found by a p p l i c a t i o n of the IEM model (see (33)). The chemical product t i o n term i n v o l v e s the c o r r e l a t i o n c^c^ : s Q a n ( a In Chemical Reaction Engineering—Plenary Lectures. i f not to solve (2). 2012 | http://pubs. 36) i n a 0.acs. DC. since the f i r s t experiments of Mao and Toor (34) and V a s s i l i a t o s and Toor (35). The general equations f o r chemical r e a c t i o n i n a turbulent medium are easy to w r i t e . balance equations f o r q = A u ^ the segregation ( ? .29 m i . the s o l u t i o n of these equations poses d i f f i c u l t problems of c l o ­ sure. P a r t i a l s o l u t i o n s to t h i s problem have been proposed. J. c?Cj . gaussian d i s t r i b u ­ t i o n s ) have been s u c c e s s f u l l y t r i e d 0 3 ) . Turbulence was created by a g r i d and c a r e f u l l y c o n t r o l l e d by v e l o c i t y f l u c t u a t i o n measurements. I n the case of instantaneous r e a c t i o n s ( t ^ << T ) the "eq u i l i b r i u m assumption" a p p l i e s : the mixed reactants are immediat e l y converted and the apparent r a t e of r e a c t i o n i s simply that of the decrease of segregation. the extent of r e a c t i o n X i s given by 1 . I n t h i s case. (ζ . Whatever the shape of the r e a c t o r under c o n s i d e r a t i o n ( u s u a l l y a tube or a s t i r r e d tank).org Publication Date: July 28.. tube e l i m i n a ­ t i n g the i n f l u e n c e of boundary l a y e r s . Another c l o s u r e approximation r e l i e s on the use of higher o r ­ der moments. VILLERMAUX 141 Mixing in Chemical Reactors t e r p r e t a t i o n of micromixing phenomena. i n the r e a c t i o n terms have to be evaluated.1021/bk-1983-0226. r = k2 C^Cg. but t h i s i s almost a deadlock as f o r only two reac­ t i n g components.

1983 | doi: 10.org Publication Date: July 28. whereas chemical r e a c t i o n s would simply be superimposed to t h i s mass t r a n s f e r .ch006 C C A B (3-5) C Ao* Bo This i s very encouraging because i t i n d i c a t e s that C o r r s i n ' s time constant T i s a b a s i c q u a n t i t y a l l o w i n g the p r e d i c t i o n of the segregation both i n the absence and i n the presence of chemi­ c a l r e a c t i o n s . w i t h the frequency ω.~ Γ k . As an example. i n the pre­ sence of a chemical r e a c t i o n : the a l k a l i n e h y d r o l y s i s of methyl formate (29). The sodium hydroxyde c o n c e n t r a t i o n C was monitored by f a s t conductimetry. have brought a d d i t i o n a l i n f o r m a t i o n i n studying c o n c e n t r a t i o n f l u c t u a t i o n s i n t h e i r tube. where these two processes are uncoupled.142 C H E M I C A L REACTION ENGINEERING . the r e a c t i o n going on between each coalescence. This l e d s e v e r a l au­ thors to simulate segregation decrease v i a a coalescence-dispersion (C-D) process.. Using a c l o s u r e w i t h a gaussian p r o b a b i l i t y d e n s i t y func­ t i o n . This sup­ p o r t s lumped models of the IEM type (see S e c t i o n on phenomenologi­ c a l models below). Bennani et a l . We have seen that the formalism of turbulence theory (when used alone) l e d to p r a c t i c a l l y unmanageable equations. . Canon (39) and P a t t e r s o n (3) f i t t e d the experimental data w i t h the expression ω = 1333(ε/ΐ|) ' (the s A 3 s T 1 1 s s 1 3 In Chemical Reaction Engineering—Plenary Lectures.1021/bk-1983-0226. they showed (30) that p h y s i c a l mixing ( 1 / T ) and chemistry act i n an a d d i t i v e manner i n the decay of segregation. (39) s u c c e s s f u l l y i n t e r p r e t e d V a s s i l i a t o s and T o o r s experiments by a C-D model where the f l u i d was d i v i d e d i n t o small c e l l s undergoing p e r i o d i c and random coal e s c e n c e . Bennani et a l . Thus Canon et a l . Some au­ thors have t r i e d to avoid the c l o s u r e problem by i n t r o d u c i n g phenomenological parameters. J. Wei. 2012 | http://pubs. c^ was found to f i r s t increase then to de­ crease as ζ"~^·6 w h i l e i t s spectrum e x h i b i t e d an unexpected decay i n k f . et al. Mc Kelvey et a l . A more general c o n c l u s i o n of the above r e ­ s u l t s i s that C o r r s i n s theory and T o o r s hypothesis provide the framework f o r a simple model where turbulence causes mass t r a n s f e r w i t h a time s c a l e T ^ (Lg/ε) . (38) attemp­ ted to model uc^ and ucg i n a tubular r e a c t o r w i t h a t r a n s v e r s a l d i s p e r s i o n c o e f f i c i e n t . American Chemical Society: Washington. DC. ACS Symposium Series.. 1983. (37) have shown that c^cg can be c a l c u l a t e d when the segregation I of a non-reacting species was known.r e d i s p e r s i o n s .acs. i n s e t t i n g g C Downloaded by CORNELL UNIV on December 2. This confirms T o o r s hypothesis according to which the i n f l u e n c e of turbulence on a chemical r e a c t i o n w i t h unmixed reactants can be determined from the s o l e knowledge of the segregation decay of a non r e a c t i n g species i n the same c o n d i t i o n s . whose frequency ω only depends on the l o c a l value of L and ε. Berker et a l . (36) were able to p r e d i c t the value of the c o r r e l a t i o n c^cfi < 0 from t h e i r experiments w i t h a passive t r a c e r ." 2 (C A C ' B + C C A B ) I t i s found e x p e r i m e n t a l l y that c^cg < 0. In ad­ d i t i o n .

acs. viLLERMAUX 143 Mixing in Chemical Reactors numerical c o e f f i c i e n t should be used w i t h some p r e c a u t i o n . Decreasing the space time i n a CSTR. This work i s e s s e n t i a l l y experimental and has been c a r r i e d out w i t h the famous "Belousov-Zhabotinsky" r e a c t i o n . Thus. i n which mixing occurs v i a a C-D process whose frequency i s given by the expression above (HDM model (40)). This leads to i n t e r e s t i n g scale-up c r i t e r i a i n s t i r ­ red r e a c t o r s (2) : the mixing c h a r a c t e r i s t i c s are the same i f ε/Lg i s kept constant. This may be as high as i f one assumes that L ^ L. as the r e s u l t i s not e x a c t l y expressed i n t h i s way i n the o r i g i n a l paper).6. should be an i n t e r e s t i n g t o o l f o r the study of micromix i n g i n l a b o r a t o r y r e a c t o r s . once i t s k i n e t i c mechanism i s e n t i r e l y e l u c i d a t e d and w e l l accepted. .. recent work on what has been c a l l e d "chemical turbulence" must a l ­ so be mentioned. DC. the t u r b u l e n t f i e l d f o r chemical r e a c t i o n i s determined once L and ε are known a t any p o s i t i o n i n the r e a c t o r . 1983 | doi: 10. J. mixing i n a s t i r r e d tank can be.g. ACS Symposium Series. which w i l l be d i s ­ cussed f u r t h e r . s 3 3 Downloaded by CORNELL UNIV on December 2. American Chemical Society: Washington. The e m p i r i c a l exponent a c t u a l l y l i e s i n b e t ­ ween 3 and 5. In c o n c l u s i o n to t h i s S e c t i o n devoted to the turbulence approach to mixing the main p o i n t s are : . In t h i s S e c t i o n devoted to turbulence and chemical r e a c t i o n . They c l a i m that t h i s i s a purely chemical phenomenon which has nothing to do w i t h any c o u p l i n g between d i f f u s i o n and r e a c t i o n . most authors have been l e d to introduce s i m p l i f y i n g assumptions and c l o s u r e hypotheses which g r a d u a l l y brought them nearer to the Lagrangian approach and i t s phenomenological c o e f f i c i e n t s . Wei. the c o n s i d e r a t i o n o f the s i g n of c o n c e n t r a t i o n c o r r e l a t i o n s y i e l d s u s e f u l r u l e s to determine the e f f e c t of segregation on s e l e c t i v i t y (41). a f t e r s t a r t i n g from the ambitious and general formula­ t i o n provided by the E u l e r i a n equations of turbulence theory. develop­ ment of new techniques (e.ch006 S s s In Chemical Reaction Engineering—Plenary Lectures. I n a d d i t i o n . 1983. 2012 | http://pubs. This does not mean that turbu­ lence theory i s useless i n t h i s matter : i t provides the p h y s i c a l i n t e r p r e t a t i o n of the phenomenological c o e f f i c i e n t s and may y i e l d t h e i r value as a f u n c t i o n of experimental parameters. the Belousov Zhabotinsky reac­ t i o n .1021/bk-1983-0226. o p t i c a l . some authors (42) have obser­ ved a t r a n s i t i o n from p e r i o d i c to c h a o t i c c o n c e n t r a t i o n f l u c t u a ­ t i o n s . -Improvement of the techniques f o r monitoring l o c a l i n s t a n t a ­ neous concentrations down to the viscous d i s s i p a t i o n microscale (e. In p a r t i c u l a r .g. as w i l l be discussed i n the next Sections. This i s the b a s i s f o r a f a m i l y of C-D models. et al. I n any case.Need f o r more data on s p e c t r a E of c o n c e n t r a t i o n f l u c t u a ­ tions . This c o n c l u s i o n should be checked by designing experiments where mixing c o n d i t i o n s and p h y s i c a l u n i f o r m i t y of the mixture are to be c a r e f u l l y c o n t r o l l e d . represented by a set o f s m a l l c e l l s connected by s p e c i f i e d f l o w r a t e s . r a d i o a c t i v e t r a c e r methods).org Publication Date: July 28. the power input Ρ should be p r o p o r t i o n a l to L L . As ε ^^P/pV and V ^ L . According to these models. owing to i t s s e n s i t i v i t y to concentra­ t i o n gradients (43).. s p a t i a l and time r e s o l u t i o n o f c o n d u c t i v i t y probes).

This should be an i n c e n t i v e f o r chemical r e a c t i o n e n g i ­ neers to develop t h e i r o r i g i n a l methods and to apply them i n neigh­ bouring f i e l d s . i t represents an impor­ tant f i e l d of a p p l i c a t i o n f o r the theory of chemical r e a c t i o n s i n turbulent media w i t h the a d d i t i o n a l d i f f i c u l t y that the k i n e t i c schemes i n v o l v e d are o f t e n complex (e. J. 1 £ 8 8 Downloaded by CORNELL UNIV on December 2. However. This supports the Lagrangian approach to mixing phenomena (e. 1983. . I t i s i n t e r e s t i n g to n o t i c e that authors faced w i t h the c l o s u r e problem have indepen­ dently imagined models of the Lagrangian type where i n t e r a c t i o n between t u r b u l e n t eddies i s accounted f o r by an apparent mass t r a n s f e r between each eddy and i t s average environment (See Spalding and h i s EBU model (50). ACS Symposium Series. Here a l s o . X Macromixing and Residence Time D i s t r i b u t i o n s (RTD) The RTD concept i s now w e l l e s t a b l i s h e d and w i d e l y used f o r d e s i g n i n g . f r e e r a d i c a l r e a c t i o n s ) and that temperature and d e n s i t y f l u c t u a t i o n s have to be taken i n ­ to account. and although being the subject of a c t i v e research won't be reviewed i n d e t a i l here. coalescence. .144 C H E M I C A L REACTION ENGINEERING . 54). d i s p e r s i o n w i t h ω ^ \/T ).acs. s i n g l e i n l e t and o u t l e t . 50). American Chemical Society: Washington. This i s e x a c t l y the same approach as i n the IEM model developed i n Chemical engineering. and p u r e l y convective motion In Chemical Reaction Engineering—Plenary Lectures. scaling-up and o p t i m i z i n g chemical r e a c t o r s . . Wei.Check f o r homogeneous i s o t r o p i c turbulence i n t e s t e x p e r i ­ ments ( i n f l u e n c e of boundary l a y e r s . p e r t u r b a t i o n s c l o s e to impel­ lers) . Most c l a s s i c a l textbooks (55) mainly deal w i t h the simple case of steady s t a t e incompres­ s i b l e f l o w . et al. This sub­ j e c t was r e c e n t l y reviewed by Nauman (J_). NO. .Need f o r more t h e o r e t i c a l or experimental i n f o r m a t i o n on the " e f f i c i e n c y η" of u t i l i z a t i o n of macroscopic d i s s i p a t e d power Ρ at the molecular s c a l e (ε). I t i s very encouraging to see that the chemical engineering approach r e l y i n g on the RTD concept and d e s c r i b i n g mi­ c r o s c o p i c mixing v i a C-D processes accounts w e l l f o r the produc­ t i o n of p o l l u t a n t s . 2012 | http://pubs.. 1983 | doi: 10.C l e a r d i s t i n c t i o n between macromixing e f f e c t s (large s c a l e motions due to average v e l o c i t i e s ) and micromixing e f f e c t s ( t u r b u ­ lent fluctuations). C l a s s i c a l treatments using turbulence theory are a v a i l a b l e (48.org Publication Date: July 28. i n cooperation w i t h the s p e c i a l i s t s of these d i s ­ c i p l i n e s who may e n r i c h them w i t h t h e i r own experience. 49..ch006 S Turbulence and combustion This domain i s t r a d i t i o n a l l y at the f r o n t i e r of Chemical Reac­ t i o n Engineering.C o r r s i n s theory and i t s c h a r a c t e r i s t i c s time constant τ ^ ^ / c o n s t i t u t e s a sound b a s i s f o r r e p r e s e n t i n g segregation i n t u r b u l e n t r e a c t i n g media. A major problem i s the p r e d i c t i o n of the formation of p o l l u t a n t s l i k e CO. i g n i t i o n phenomena and s t a b i l i t y of combustors (53. DC.g. N0 (44-47).g.1021/bk-1983-0226. most authors recognize that the rigorous c l o s u r e problem comes to a deadlock (46) and plead f o r simple models (51) a l l o w i n g e a s i e r p r e d i c t i o n s (52).

J. ACS Symposium Series. Recent work has attempted to g e n e r a l i z e RTD theory to l e s s r e s t r i c t i v e assumptions. This model i s introduced because i t has i n t e r e s t i n g p r o p e r t i e s (56) and provides a concrete p i c t u r e of the RTD so that a frequent use of t h i s r e p r e s e n t a t i o n w i l l be made i n the next S e c t i o n s . 2/0 * ( 0 ( 5 6 ) (60) (61)(62)(1) (56) RTD problems' i n v a r i a b l e regimes can be d e a l t w i t h as s p e c i a l cases o f the p o p u l a t i o n balance method (56).6. The f l u i d flows a t constant v e l o c i t y (the par­ t i c l e s o f the same age are on the same v e r t i c a l l i n e ) and the e l e ­ mentary f l o w r a t e dQ i n each tube i s such that dQ = E ( t ) d t . t o ­ gether w i t h the corresponding references : s s g Downloaded by CORNELL UNIV on December 2. so that i t might apply to more r e a l i s t i c s i t u a t i o n s encountered i n p r a c t i c e . . et al. Wei. 2012 | http://pubs.. periodical­ ly variable (0(56) (58) (59) Density constant variable (0(56) convective dispersive (0(57) Flow regime Inlet/Outlet Number of Inlets/Outlets 1/1 Semi-batch r e a c t o r 2/1 n/n 1/0 .. equal to the residence time t .ch006 s Table I I : G e n e r a l i z a t i o n of the RTD theory Classical assumption Generalization Reference steady transient. 145 Mixing in Chemical Reactors viLLERMAUX of the f l u i d across the i n l e t / o u t l e t s e c t i o n s . The locus of the tubes extremity then p i c t u r e s the f a m i l i a r F ( t ) cur­ ve.C*5> + ? = 0 at The (5-1) 9α l o c a l age d i s t r i b u t i o n f u n c t i o n i s defined as f = ψν/Ν. American Chemical Society: Washington. The type of flow and the ope­ r a t i n g c o n d i t i o n s of the r e a c t o r are given i n Table I I below. A u s e f u l represen­ t a t i o n of t h i s s i t u a t i o n i s the "Bundle of P a r a l l e l Tubes" (BPT) model ( f i g u r e 1) where the r e a c t o r volume i s reorganised i n the form of a bundle of small tubes of i n c r e a s i n g l e n g t h . DC. 1983. a + da. periodical (0(56) Volume constant variable. 1983 | doi: 10.1021/bk-1983-0226. Let ipdadV be the number of p a r t i c l e s i n volume dV w i t h i n the age i n t e r v a l a. f i s In Chemical Reaction Engineering—Plenary Lectures. The t o t a l number of p a r t i c l e s i n the reac­ tor i s Ν = j γ ifjdadV and ψ obeys the w e l l known p o p u l a t i o n b a l a n ­ ce equation a | f + V.acs.org Publication Date: July 28.

2012 | http://pubs.1021/bk-1983-0226.org Publication Date: July 28. The f l o w r a t e i n a tube w i t h residence time between t and t ^ dQ = E ( t )dt . ACS Symposium Series. 1983 | doi: 10. Olson and Stout a l s o make use o f such a model / ο i n t h e i r review (177). ... The h e i g h t o f the p i l e i s Q.ch006 146 C H E M I C A L REACTION ENGINEERING Figure 1. J. The f l u i d flows i n the tubes at constant v e l o c i t y . 1983. American Chemical Society: Washington. DC. The BPT (bundle o f p a r a l l e l tubes) model. The l o c u s o f tube e x t r e m i t i e s i s a p i c t u r e o f F-curve ts E(t) d t ) . et al.acs.Downloaded by CORNELL UNIV on December 2. s In Chemical Reaction Engineering—Plenary Lectures. A l l p a r t i c l e s on a v e r t i c a l have the same age. Wei.

. C v a r i e s i n each par­ t i c l e as C-Q(a.org Publication Date: July 28.Lectures.1021/bk-1983-0226. ACS Symposium Series. t ) = Q(t-a)/V. 20036Wei. from which the IAD i s w r i t t e n I ( a .6..t) I ( a . The instantaneous f l u i d volume i s V = J £ Q i t ^ d t ' .C.C . 1983 | doi: 10. DC. Consider a species of c o n c e n t r a t i o n C produced w i t h the r a t e n t . i t i s easy t o show by averaging that n o u t n o u t g Downloaded by CORNELL UNIV on December 2. ( t . I ( a .acs. a = 0. C . t) (batch conversion) such that : _ = & .out η V ^ μ Ν d"t V }+ l = ( 5 ° " 3 ) where i s the n^ti order moment of E ( t . This l i n k s the n ^ order moment of the RTD to the n-l*-* order mo­ ment of the IAD. t ) and μ that o f I(a. t ) i s the i n s t a n ­ taneous i n t e r n a l age d i s t r i b u t i o n (IAD). et al. W.1 ) . J. Then f = I ( a . viLLERMAUX 147 Mixing in Chemical Reactors normalized and could be the impulse response to an i n j e c t i o n o f t r a c e r a t the i n l e t . o u t n. The IAD approach can a l s o be g e n e r a l i z e d to the case o f s e v e r a l f « f l f ô f l ^ ^ICïA Society Library 1155 16th St. l e t us consider a semi-batch r e a c t o r . 1983.t). one obtains the f a m i l i a r mass balance equation s n η U 1 QC in +&V = ± (VC) (5-4) whereas i f the f l u i d i s t o t a l l y segregated. t ) i s the instantaneous RTD.. f o r i n s t a n c e by using the IEM model (see next S e c t i o n and (56)). In Chemical ReactionWashington. t ) can be used to c a l c u l a t e the chemical conversion i n d i f f e ­ rent segregation s t a t e s . I f the mixture i s assumed to be w e l l mi­ xed a t the molecular s c a l e . Engineering—Plenary D. For i n s t a n c e . f ^ = δ(a) and f = E ( t .a ) B n (5-5) The average c o n c e n t r a t i o n i n the r e a c t o r i s then given by C(t) = C_(a. N. t ) i n a chemical r e a c t o r i s s p e c i a l l y i n t e r e s t i n g and i t does not seem that s u f f i c i e n t a t t e n t i o n has been p a i d t o the p o s s i b i l i t i e s o f f e r e d by t h i s f u n c t i o n . American Chemical Society: Washington. 2012 | http://pubs. ° These equations a l l o w v a r i o u s s p e c i a l cases t o be t r e a t e d . and l e t Q(t) be the feed f l o w r a t e of an incompressible f l u i d . The IAD I ( a . t ) da y O (5-6) JD The conversion i n p a r t i a l l y segregated f l u i d can be c a l c u l a ­ ted i n a s i m i l a r manner.ch006 The corresponding moment equation i s 1 d Q y — \ a. From ( 5 . L e t f_ be the average value o f f over the r e ­ a c t o r volume and f £ and f be the f l u x averages over the i n l e t and o u t l e t s e c t i o n s r e s p e c t i v e l y .

I n p a r t i c u l a r .^ all c l a s s i c a l p r o p e r t i e s of steady s t a t e RTD except that they vary w i t h time. .acs. ) t Qut o u t ( t ) = C(X = 0. In steady s t a t e continuous r e a c t o r s .t) dt B [s' m s J out s' s v c (5-7) and f o r maximal mixedness : .C tt -»] H W (A. according to an ex­ pansion f a c t o r = Q^/Qi^. 1983 | doi: 10. and W (t . For minimal mixedness : n s s out g o u t g 9 F n E = F t wn c n a v e t n 9 t a n d n e Downloaded by CORNELL UNIV on December 2. 1983. there e x i s t simpler treatments a p p l i c a b l e to s p e c i a l cases. Wei. namely ν = V / V and Og = t b a t c h ^ t o t a l * The authors show that t h i s p e r i o d i c operation i s equivalent to that i n a continuous r e a c t o r whose degree of macromixing can be v a r i e d between that of a plug flow r e a c t o r and that of a CSTR. the volume of a semi-batch r e a c t o r i s v a r i e d p e r i o d i c a l l y (at constant f l o w r a t e Q) between V and V . The general p o p u l a t i o n balance equations presented above t h e o r e t i ­ c a l l y give the s o l u t i o n to the problem i f the RTD approach i s r e ­ tained f o r c a l c u l a t i n g chemical conversion.t) = 1 . C. The f i l l i n g and empty­ ing stages are separated by a p u r e l y batch p e r i o d . J.t) = 1 -F . ACS Symposium Series.org Publication Date: July 28. f r a c t i o n of m a t e r i a l l e a v i n g a t time t which remained i n the r e a c t o r f o r a d u r a t i o n g r e a t e r than t . DC. (58). Nauman (J_) propo­ sed a s o l u t i o n v a l i d f o r segregated mixtures whose density only depends on an a x i a l coordinate i n the r e a c t o r . I n t h e i r model. chemical conversion can be c a l c u l a t e d i n the two l i m i t s o f mixing e a r l i n e s s (see next S e c t i o n ) . Two washout f u n c t i o n s are defined : W£ (t . I f the expansion i s ignored. He used a v a r i a n t of the Bundle of P a r a l l e l Tubes model i n which a l l the tubes have the same length but d i f f e r e n t f l o w i n g v e l o c i t i e s .148 CHEMICAL REACTION ENGINEERING Nauman (J_) has proposed an i n t e r e s t i n g treatment of RTD i n unsteady-state r e a c t o r s . the ex­ p l o i t a t i o n of a RTD experiment leads to an apparent number of tanks 0 m Q m In Chemical Reaction Engineering—Plenary Lectures.t) SC 3λ c t o o n t (. et al..t) which i s a g e n e r a l i z e d form of Zwietering's equation. ( t . namely E ^ = i / s out ^ o u t ^ ^.1021/bk-1983-0226.. 2012 | http://pubs. f r a c t i o n o f m a t e r i a l e n t e r i n g a t time t which w i l l remain i n the r e a c t o r f o r a d u r a t i o n greater than t .. The case of an unsteady CSTR has been e s p e c i a l l y studied (J_) . Ε . Thanks to t h i s formalism..F .ch006 s C _(t) = out C f t . p e r i o d i c regimes can be d e a l t w i t h ( e s t i m a t i o n of average conversion). However. The model de­ pends on two parameters. V i l l e r m a u x (56) extended the well-known tanks i n s e r i e s model to the case where the flowrate Q i s v a r i a b l e from tank to tank.t )1 Ε ( t . Mixing e f f e c t s i n variable-volume chemical reactors were considered by Roth e t a l . From tfiese f u n c t i o n s . an important case en­ countered i n p r a c t i c e i s that of mixtures w i t h v a r i a b l e d e n s i t y . . American Chemical Society: Washington. two RTD can be defined.

Downloaded by CORNELL UNIV on December 2. At present. The case of r e a c t o r s w i t h two i n l e t s was considered more than ten years ago by Treleaven and Tobgy ( 6 0 ) . et al. h Ξ 1 and î f ^ ( t ^ ) i s the RTD.org Publication Date: July 28. The conversion along the tube can be c a l c u l a t e d according t o e g S s r g c o f : = k F < j> c ( 5 ~ 9 ) and the o v e r a l l extent of r e a c t i o n (under the assumption of m i n i ­ mal mixedness) i s X = J" X( )%( ) t i (5-10) t i This g e n e r a l i z e s the well-known equation e s t a b l i s h e d i n the case of RTDs. . and l e t k be the average value of k over the whole r e a c t o r . For homogeneous i s o t h e r m a l r e a c t o r s .1021/bk-1983-0226. Consider a chemical r e a c t i o n w i t h r a t e equation r = k F(C-) and assume that k i s a l o c a l l y v a r i a b l e parameter owing t o s p a t i a l d i s t r i b u t i o n s of e x t e r n a l p o r o s i t y e ( c a t a l y t i c r e a c t i o n ) . D e f i ­ ning the l o c a l parameter h = k/k.. 1983 | doi: 10. DC. J. I n the case of non-isothermal r e a c t o r s . i f there e x i s t experimental methods f o r measu­ r i n g the RTD and the CTD by means of t r a c e r t e s t s .ε^/ε and 7^(tj_) i s the contact-time d i s t r i b u t i o n (CTD) introduced by Nauman and C o l l i n g e ( 1 ) . A somewhat academic problem a l s o seems to have found i t s so­ l u t i o n i n the work of Nauman (57) who showed that RTD i n systems governed by the d i s p e r s i o n equation could be defined as i n c l o s e d systems provided the time spent by the t r a c e r outside the r e a c t o r owing to d i f f u s i o n be excluded from the count. nothing has been p u b l i s h e d about the experimental determination of the l a t t e r d i s t r i b u t i o n . 1983. I t would be i n t e r e s t i n g to see whether t h i s apparent number can be used to o b t a i n an a p p r o x i ­ mate value of the conversion. The BPT model allows an i n t e r e s t i n g r e p r e s e n t a t i o n of the flow i n these r e a c t o r s ( 5 6 ) ( f i gure 2 ) . andj£(t£) i s a "thermal time d i s t r i b u t i o n " . The l a s t item deserving emphasis i n t h i s s e c t i o n i s the pro­ mising concept of " g e n e r a l i z e d r e a c t i o n time" (J_) (56). This w i l l be u s e f u l when micromixing phenomena w i l l be d e a l t w i t h (next S e c t i o n ) . This b r i e f review on RTDs would be incomplete without a few g β In Chemical Reaction Engineering—Plenary Lectures. American Chemical Society: Washington. temperature. The value of t ^ f o r a p a r t i c u l a r tube (residence time t ) i s t« = <h> t where <h> i s the average value of h along the tube a x i s .. h = k ( T ) / k ( T ) .acs. e t c . . U n f o r t u n a t e l y . t h i s l i m i t s the p o t e n t i a l a p p l i c a t i o n s of such an approach. Wei. ACS Symposium Series. there e x i s t s a " r e a c t i o n time d i s t r i b u t i o n " JCitO s i m i l a r to the RTD E ( t ) . 2012 | http://pubs. where h i s the l o c a l value of k/k along the tube of the BPT model ( f i g u r e 1 ) . h = (1 . . Now consi­ d e r i n g a l l the tubes. viLLERMAUX 149 Mixing in Chemical Reactors i n s e r i e s l a r g e r than the a c t u a l one. N o t i c e t h a t t£ = t .ch006 6. For i s o t h e r m a l heterogeneous r e a c t o r s . i t i s p o s s i b l e to introduce a g e n e r a l i z e d r e a c t i o n time t ^ such that d t ^ = h dt .

Wei. J.acs. 1983 | doi: 10. ACS Symposium Series.org Publication Date: July 28. E x t e n s i o n o f the BPT model t o the case o f a r e a c t o r having two i n l e t s (two unmixed feedstreams o f r e s p e c t i v e f l o w r a t e s Q. 1983.1021/bk-1983-0226. DC. The p i c t u r e shows how t o b u i l d the o v e r a l l RTD from those o f each separate feedstream by a s s o c i a t i n g tubes having the same residence time.. .. 2012 | http://pubs. et al.and Q^).Downloaded by CORNELL UNIV on December 2. In Chemical Reaction Engineering—Plenary Lectures.ch006 150 C H E M I C A L REACTION ENGINEERING Figure 2. American Chemical Society: Washington.

I t must be c l e a r l y s p e c i f i e d that these two problems are d i s t i n c t and independent. a p o i n t which does not seem to be obvious i n the mind of a l l authors.. 2012 | http://pubs. DC. research i n the RTD area i s always a c t i v e and the i n i t i a l concepts of Danckwerts are g r a d u a l l y being completed and extended. et al.org Publication Date: July 28. Bourne e t a l . (66) who s t u d i e d mixing i n r e a c t o r v e s s e l s by means of a gamma camera and a Technetium 99 t r a c e r . Mixing e a r l i n e s s i n the age domain . . Tracer methods are now r o u t i n e l y u t i l i z e d i n i n d u s t r y and i n l a b o r a t o r i e s . would s t i l l be welcome i n the f i e l d of unsteady s t a t e systems ( v a r i a b l e volumes and flow r a t e s ) . 1983 | doi: 10. v a r i a b l e d e n s i t y mixtures. American Chemical Society: Washington. simple procedures. the subject of t h i s S e c t i o n .acs. 1983. There i s s t i l l a need f o r a good t r a c e r f o r p a r t i c u l a t e s o l i d s . i n s p i t e of the e f f o r t s of s e v e r a l authors. I n a continuous r e a c t o r . I n t e r e s t i n g v i s u a l i s a t i o n techniques were a l s o devised by Q u r a i s h i and Fahidy (65) who induced the change of col o r of an i n d i c a t o r a t a surface by e l e c t r o l y s i s and by C a s t e l l a n a et a l .Downloaded by CORNELL UNIV on December 2. ACS Symposium Series. e t c . but i t i s w e l l known that t h i s i s not s u f f i c i e n t to describe the whole mixing process i n the r e a c t o r . Conochie and Gray (64) developed a s p e c t r o photometer f o r the study of mixing i n a channel s i m u l a t i n g a metall u r g i c a l r e a c t o r . what i s the degree of mixing between molecules contained i n these p a r t i c l e s ? This i s the problem of "segregation". t a k i n g i n t o account the RTD c o n s t r a i n t ? This i s the problem of "mixing e a r l i n e s s " . discussed i n the next Sect i o n .ch006 6.. systems i n which the mass-flowrate i s not conserved. . (63) desc r i b e d a r e v e r s i b l e photochromic t r a c e r f o r RTD measurements i n h i g h l y viscous l i q u i d s . Once p a r t i c l e s having the same l i f e expectancy (or r e s i d u a l l i f e t i m e ) are c l o s e t o each o t h e r . The p o p u l a t i o n balance approach provides a t h e o r e t i c a l framework f o r t h i s g e n e r a l i z a t i o n . P h y s i c a l mixing among p a r t i c l e s i s c h a r a c t e r i z e d by a d i f f e r e n t n o t i o n : the s t a t e of segregation which may l i e between two In Chemical Reaction Engineering—Plenary Lectures. VILLERMAUX 151 Mixing in Chemical Reactors words on experimental techniques. the f l u i d i s i n a s t a t e of Minimum Mixedness (Min Mix) i f mixing between p a r t i c l e s occurs a t the l a t e s t moment : Neighbouring part i c l e s have the same age. J. easy to use by p r a c t i t i o n e r s . On the other hand. Magnetic t r a c e r s should be developed f o r t h i s purpose (9). Conversely the f l u i d i s i n a s t a t e of Maximum Mixedness(Max Mix) i f p a r t i c l e s of d i f f e r e n t ages are m i xed as soon as they enter the r e a c t o r . phenomenological models The RTD (one or two i n l e t s ) c h a r a c t e r i z e s macromixing. m u l t i p l e i n l e t / o u t l e t r e a c t o r s . . the promising " g e n e r a l i z e d r e a c t i o n time d i s t r i b u t i o n " approach could be developed i f s u i t a b l e experimental methods were a v a i l a b l e f o r i t s determination. mixing occurs a t the earl i e s t moment and neighbouring p a r t i c l e s have the same l i f e expectancy. However. I n other words a f l u i d i n a s t a t e of maximum mixedness may w e l l remain segregated i f microscopic i n t e r a c t i o n between p a r t i c l e s i s u n e f f e c t i v e . A d d i t i o n a l i n f o r m a t i o n i s r e q u i r e d and two questions must be answered : how are p a r t i c l e s of d i f f e rent ages mixed and brought i n t o c o n t a c t .1021/bk-1983-0226. Wei. In c o n c l u s i o n to t h i s s e c t i o n .

(68) i s h e l p f u l . i t may happen that we accept t h i s assumption i n order to e x p l a i n t h e i r treatments but we must keep i n mind that t h i s i s not necessary. j . DC. Leshaw et a l . = m a c r o f l u i d and Max.org Publication Date: July 28. ( C . I t i s e s s e n t i a l l y a two-environment model i n which the assumption c i t e d above: Min. i t behaves l i k e a m i c r o f l u i d i . 1983. jo Conversely.V τ^π to be i n t e g r a t e d from λ = °° to λ = 0. then minimal mixedness corresponds to a p e r f e c t i n s u l a t i o n between tubes and the conversion f o r a s i n g l e r e a c t i o n i s w r i t t e n Cj = Γ C 0 * d C ( c j B ° E ( a ) d a 5 . 2012 | http://pubs. the f l u i d g r a d u a l l y passes from a Min. then maximum mixedness i s achieved. For t h i s purpose.£ . Wei. where no p h y s i c a l mixing a t a l l takes place between p a r t i c l e s . 1983 | doi: 10. I n a d d i t i o n . et al. An ex­ c e l l e n t review of a l l the models proposed f o r r e p r e s e n t i n g impremixed feedstreams r e a c t o r s was published by R i t c h i e and Tobgy ( 6 ) .acs. s t a t e (Figure k). Mix. da j ) .« i • .1021/bk-1983-0226. J.. e .) i n the i n t e r v a l g g g g s In Chemical Reaction Engineering—Plenary Lectures.r ^ . I f the bundle i s arranged i n such a way that the p a r t i ­ c l e s of same r e s i d u a l l i f e t i m e are s i t u a t e d on the same v e r t i c a l l i n e . the r e p r e s e n t a t i o n proposed by Spencer. then.& . . = m i c r o f l u i d i s i m p l i c i t l y made. ( .1 ) and (6-2) are w r i t t e n at steady s t a t e . We may now r e c a l l the fundamental equations f o r c a l c u l a t i n g chemical conversion i n the l i m i t i n g s t a t e s of Min Mix and Max Mix. ACS Symposium Series. There i s an ambiguity between these two notions i n the l i t e r a t u r e because many authors make the i m p l i c i t assumption that once the f l u i d i s mixed i n the age domain. s t a t e t o a Max. i f the f l u i d i s w e l l micromixed. American Chemical Society: Washington. The residence time i n t h i s p a r t i c u l a r tube l i e s i n the range t . t + d t and the flowr a t e i s dQ = Q E ( t ) d t . and the " m i c r o f l u i d " . Mix.E.α = 0 k C. Z w i e t e r i n g s equation a p p l i e s : T . I t i s u s e f u l to t r y to s e t some order i n t h i s host of models. The flow t r a n s f e r r e d from t h e E n t e r i n g Environment (E.B = 6 " 1 } C.Downloaded by CORNELL UNIV on December 2. I n what f o l l o w s . Mix. Equations ( 6 . The problem of modeling i n ­ termediate mixing s t a t e s has been and i s s t i l l the subject of many t h e o r e t i c a l i n v e s t i g a t i o n s .. Along the a x i s o f a s m a l l tube o f the BPT model. which i s i n t i m a t e l y mixed on the molecular s c a l e .ch006 152 CHEMICAL REACTION ENGINEERING extreme s i t u a t i o n s : the " m a c r o f l u i d " . i f the p a r t i c l e s on a same v e r t i c a l l i n e are r e a l l y mixed. Chen (67) has shown how to g e n e r a l i z e them to unsteady regimes by using the p o p u l a t i o n balance formalism. Mix. The BPT model provides a convenient p i c t u r e of the two s i t u a t i o n s ( f i g u r e 3 ) .) t o t h e Leaving Environment (L.E. minimum mixedness i s confused w i t h s e g r e g a t i o n and maximum mixedness w i t h molecular mixing.

M i x i n g i s c h a r a c t e r ­ i z e d by the f u n c t i o n η(λ. 1983. (unshaded) t o a Max.E. Min. This zone may a l s o be considered as an "accumulator" (dimensionless volume v) t r a n s i t i n g along the time a x i s and r e c e i v i n g the Max. (shaded). Max. E.1021/bk-1983-0226. 2012 | http://pubs. 2 s In Chemical Reaction Engineering—Plenary Lectures. et al. Wei. t ) such t h a t over dX. J.org Publication Date: July 28. Mix. r i g h t . American Chemical Society: Washington. ts+dts ts λ+dX λ DISCHARGE yzQ t<0 t Figure k. f l u i d before being discharged a t time t = 0 ( d ) .ch006 6. viLLERMAUX Mixing in Chemical Reactors 153 Figure 3.Downloaded by CORNELL UNIV on December 2.acs. 1983 | doi: 10. d Q = h(X. f l u i d having the same l i f e expectancy λ can be c o l l e c t e d (b) i n a s i n g l e zone w i t h f l o w r a t e QMax ( c ) . the f l u i d g r a d u a l l y passes from a Min.. ACS Symposium Series. Mix. Mix. The two l i m i t i n g cases f o r mixing e a r l i n e s s .: p a r t i c l e s having the same l i f e expectancy are c l o s e together (on the same v e r t i c a l ) . A l l the Max.. Mix. DC. Mix.: p a r t i c l e s having the same age are c l o s e together (on the same v e r t i c a l ) .E. Along the a x i s o f a tube o f the BPT model.t )dXdQ (a). L e f t . L. s . tyodel o f Spencer and Leshaw (68). Mix.

t ) + j h(X. the f r a c ­ t i o n of f l u i d i n the Min.." He w i l l a l s o agree that one can e a s i l y imagine an almost endless set of models of t h i s kind by varying the shape of the sf u n c t i o n without r e a l l y b r i n g i n g i n anything new.t ) dz z — —°° (6-4) ν i s the accumulator volume at time t < 0. t ) φ 1 (tube inîet) and s ( 0 . t ) i s a mixing f u n c t i o n which can a l s o be expressed from the RTD by i n t r o d u c i n g h ( X . t ) : A ( X . . Most "micromixing models" published i n recent years can be compared on the base of t h e i r "segregation" f u n c t i o n . Spencer et a l .t )dX (6-3) where one may have s ( t . It leaves the r e a c t o r and discharges at time t = 0. As t h e i r a b s t r a c t mathematical character may render the o r i g i n a l p u b l i c a ­ tions d i f f i c u l t to understand to n o n . Wei. t ) . Mix. f l u i d i s d Q = Q g(X)dX with g(X) = }χ A ( X . t-z k C.B C ( z ) .1021/bk-1983-0226. In the whole r e a c t o r . t ) d X d t where A ( X . t ) φ 0 (tube O u t l e t ) . 2012 | http://pubs. the flowrate of the Max. the Max. t ) E ( t ) . t ) = h ( X .t ) .s i s i n the Max. From (6-4) and f i g u r e 4. s t a t e i s s and the complementary f r a c t i o n 1 . 1983. The accumulator entered the r e a c t o r at time ζ < 0 (-ζ < . American Chemical Society: Washington.org Publication Date: July 28.154 C H E M I C A L REACTION ENGINEERING άλ i s : d^Q = Q A ( X . s ( X . as the above remark i n d i c a t e s . For a given l i f e expectancy λ. also w r i t t e n s(X. Once we know how the f l u i d i s t r a n s f e r r e d from the E n t e r i n g In Chemical Reaction Engineering—Plenary Lectures. This Lagran­ gian formulation i s very i n t e r e s t i n g as i t allows the representa­ t i o n of t r a n s i e n t regimes by a succession of accumulators which are g r a d u a l l y f i l l e d during t h e i r t r a n s i t i n the r e a c t o r and are discharged when they leave i t .ch006 m a x = = f A (-z.Mix flowrate i s thence Q = § J " g(X') dX . 1983 | doi: 10.acs. DC. et al.-t) C i. The conversion i s then given by the f o l l o w i n g equation : dC. s t a t e . ACS Symposium Series. t ) d t = J~ h ( X . J. . The reader w i l l recognize well-known models o f "intermediate micromixing.a) i s known as the "segregation f u n c t i o n " although.Mix. (68) consider t h i s volume as an "accumulator" whose dimensionless volume ν was d e f i ­ ned by s g g g g g g X g s s s s s g M a x s g g s f Downloaded by CORNELL UNIV on December 2. t ) E ( t ) d t . dz +31 (6-5) J C j ^ Is the f a m i l i a r batch expression and the equation has to be i n t e g r a t e d from t = -°° (vCj ·> 0) up to t = 0. I have t r i e d to i l l u s t r a t e t h e i r p r i n c i p l e i n a more concrete manner by represen­ t i n g both the two environments i n the BPT model and the r e l a t e d segregation functions i n the (λ.α) space (Figures 4 and 5).. I dt A(-z.t ) = s(0. This t r a n s f e r between two environments can a l s o be described as a Lagrangian process where a small band of volume d^Max ^Max ^ moves with a constant v e l o c i t y along the X axis i n the d i r e c t i o n of decreasing X. s(X. In our p a r t i c u l a r tube.s p e c i a l i s t s .Mix. "segregation of ages" would be b e t t e r .

I t has been thoroughly i n v e s t i g a t e d i n a s e r i e s of papers by r e s e a r ­ chers of Exeter U n i v e r s i t y (UK). : t = α + λ). r e p r e s e n t i n g the average number of coalescences per p a r t i c l e during i t s stay i n the r e a c t o r .acs. viLLERMAUX 155 Mixing in Chemical Reactors to the Leaving Environment. In a t h i r d f a m i l y of models.E. 1983 | doi: 10. . 1983. s 3a t 1 where C. the molecules i n the p a r t i c l e s are mixed up and the composition i s thus averaged before d i s p e r s i o n . i f any. I n a continuous r e a c t o r w i t h space time τ.(A) .F(X) w (6-6) q m C. DC. ( x . was i n i t i a l l y developed f o r represen­ t i n g micromixing i n s t i r r e d r e a c t o r s (33. However. Each p a r t i c l e i s assumed to exchange mat­ ter w i t h an average environment made up of a l l p a r t i c l e s having the same l i f e expectancy.E. i t can ea­ s i l y be extended to any RTD (84). The random-coalescence process i s g e n e r a l l y simulated by a Monte-Carlo method. This method was f i r s t used by Spielman and L e v e n s p i e l (82) and then e x t e n s i v e l y e x p l o i t e d by Kattan and A d l e r (83) and R i t c h i e and Tobgy (77). a d i s ­ t i n c t i o n i s made between age mixedness and species mixedness : Ma­ ximum age and species mixedness i s achieved i f p a r t i c l e s w i t h the same l i f e expectancy are mixed. For i n s t a n c e . 109) or between two s p e c i f i e d c a ­ tegories of p a r t i c l e s (79)..ch006 6.1021/bk-1983-0226. there remains the need to s p e c i f y the mechanism of i n t e r a c t i o n between p a r t i c l e s having the same l i f e expectancy i n the L. J. A more r e s t r i c t i v e case i s that where p a r t i c l e s are able to mix only i f they have both the same m s In Chemical Reaction Engineering—Plenary Lectures. The case of r e a c t o r s w i t h two unmixed feedstreams i s e s p e c i a l ­ l y i n t e r e s t i n g ( 6 ) . 2012 | http://pubs. In a second k i n d of model.c . t ) ac. i s w r i t t e n c.. Chemical r e a c t i o n s . The BPT model o f f e r s a convenient p i c t u r e of the r e a c t o r where both feed streams have t h e i r own RTD and the two bundles are placed side by s i d e i n such a manner that p a r t i c l e s w i t h the same l i f e expectancy are s i t u a t e d as usual on the same v e r t i c a l l i n e ( f i g u r e 6).B. The b a s i c equation f o r conver­ s i o n of a species i n the L. the i n t e r a c t i o n i s represented v i a a d e t e r m i n i s t i c process. A t each coalescence. T h i s i s the problem of so c a l l e d segrega­ t i o n decay. 32). et al. e i t h e r between a p a r t i c l e and i t s average environment (81. occur w i t h i n the p a r t i c l e s between two coalescences.Downloaded by CORNELL UNIV on December 2.(λ) = j 1 . A f i r s t way to represent t h i s i n t e r a c t i o n i s to assume that p a r t i c l e s w i t h the same λ undergo random coalescence-disper­ sions (C-D) w i t h frequency ω. the IEM Model ( I n t e r a c t i o n by Exchange w i t h the Mean). Wei.org Publication Date: July 28. I n a f i r s t paper (60).t) E ( t ) dt j b S b (6-7) The c h a r a c t e r i s t i c parameter i s the micromixing time t ( N. ACS Symposium Series. American Chemical Society: Washington. This p o i n t w i l l be examined w i t h more d e t a i l i n the next S e c t i o n . because more r e a l i s t i c f o r a p p l i c a t i o n s . i n t e r a c t i o n between p a r t i c l e s i s assumed to occur by molecular d i f f u s i o n .(X. the corresponding parameter i s I = ωτ.

E. provided t > r ^ . Each p a r t i c l e stays i n the E.E.) t o the L.. which i s a l s o the s e r i e s model o f Weinstein and A d l e r (69). (shaded area. Min. 2012 | http://pubs.a) Figure 5. I n the s(λ. a p a r t i c l e having a given residence time t de­ s c r i b e s a t r a j e c t o r y between the plane α = 0 and the plane λ = 0. DC.E. f o r a d u r a t i o n p r o p o r t i o n a l t o i t s residence time.E.a) space. 1983. r d model o f Spencer e t a l . (68).1021/bk-1983-0226.. ) . d. c . 1983 | doi: 10. M i x . b. α * model o f Spencer e t a l . Each p a r t i c l e stays f o r a constant time i n the E. F l u i d flows from l e f t t o r i g h t a t constant v e l o c i t y and i s t r a n s f e r r e d from the E. Models. J.ch006 SU.E.E.acs. general case. A l l p a r t i c l e s w i t h t < r s t a y i n the E. g g g In Chemical Reaction Engineering—Plenary Lectures. Wei.. Max. Mix. ACS Symposium Series. a. .org Publication Date: July 28. (un­ shaded tubes. et al. (68_) . The other ones are immediately t r a n s f e r r e d i n the L.156 CHEMICAL REACTION ENGINEERING Downloaded by CORNELL UNIV on December 2. p a r a l l e l model o f Weinstein and A d l e r (69). American Chemical Society: Washington.

e. s = exp(. J. s 1 g In Chemical Reaction Engineering—Plenary Lectures.Ra)· For r e p r e s e n t i n g the r e d u c t i o n o f s i z e o f e n t e r i n g p a r t i c l e s i n an unmixed feedstream r e a c t o r . ACS Symposium Series. f . This i s a two-parameter model (p.w) d e r i v e d from the one on F i g u r e 5c.Downloaded by CORNELL UNIV on December 2. and the r e s t i s immediately t r a n s f e r r e d i n the L. VILLERMAUX Mixing in Chemical Reactors 157 Figure 5· Models. P l a s a r i et a l .a / t ^ ) . 1983 | doi: 10. . model o f Valderrama and Gordon (73.K t ) but other f u n c t i o n s may be proposed. DC. h . American Chemical Society: Washington. The segreg a t i o n f u n c t i o n s o n l y depends on t .. Wei. and a l l those o f the L. g. a given f r a c t i o n o f the p a r t i c l e s s t a y i n the E. On the f i g u r e .org Publication Date: July 28.E. 1983..J§) .E.acs. 2012 | http://pubs. (71) have used a model o f t h i s k i n d where s = ( l . have been p i l e d up t o g e t h e r .E. model o f Ng and R i p p i n (72)· I t i s somewhat s i m i l a r t o the preceding one. s = e x p ( . i n V i l l e r m a u x and Z o u l a l i a n s model (T0_) (when s only depends on t ) .ch006 6. an a l t e r n a t i v e representat i o n i s p o s s i b l e where a l l the tubes o f the E.1021/bk-1983-0226. et al. . except t h a t s only depends on the age.E. model o f V i l l e r m a u x and Z o u l a l i a n (TO) » F o r each residence time.

J. DC. minimum age. . maximum species mixedness (mixing i n t h i s case can a l s o be assumed t o occur by molecular d i f f u s i o n between two tubes having the same and (79)). 2012 | http://pubs. mixing between p a r t i c l e s o f t h e same l i f e expectancy by a random-coalescence process (77.acs. 1983 | doi: 10.Downloaded by CORNELL UNIV on December 2. American Chemical Society: Washington. Wei. and r i g h t ..1021/bk-1983-0226.)· In Chemical Reaction Engineering—Plenary Lectures.. Maximum age. middle. maximum species mixedness. Q 2 Figure 6. L e f t . et al. M i x i n g i n a flow r e a c t o r w i t h two unmixed feedstreams (60). ACS Symposium Series. 1983.org Publication Date: July 28.ch006 158 C H E M I C A L R E A C T I O N ENGINEERING Q.

DC. The reader w i l l understand that with a l i t t l e imagination an almost endless s u i t e of models of t h i s k i n d can be conceived.E. a three environment model has been proposed by R i t c h i e and Tobgy (87) (Two E. E s l ( t ) s dt s (6-8) C (X. 2012 | http://pubs. and two L. parameter R T . Equation (6-6) s t i l l holds but the mean value Cj(A) at a given l i f e expectancy must comprise both feedstreams 1 and 2 : L 11 p C j ( A ) l . .The C-D model.E. r e s p e c t i v e l y . Wei. and the L.1021/bk-1983-0226. The IEM Model can also be used f o r t h i s purpose. ^ ( λ ) = a E ( t ) d t and s i m i l a r d e f i ­ n i t i o n s f o r feestream 2. A gene­ r a l i z a t i o n to four environments (Two E. parameter I = ωτ .) was s t u ­ died by Mehta and T a r b e l l (88). American Chemical Society: Washington. I t i s concluded that C-D provides a bet­ ter c o r r e l a t i o n of experimental r e s u l t s . A Three-Environment model where the segregation f u n c t i o n only depends on t was published by R i t c h i e (78). In the models c i t e d above.E. I now come to a very important observation.The IEM model. the r e p r e s e n t a t i o n of f i g u r e s 5-6 i s v a l i d . ACS Symposium Series.org Publication Date: July 28. 1983 | doi: 10.E. J.ch006 0 g g d u l i Ig and I f o r the E.The Models of Ng and R i p p i n . 1983.t ) a j 2 s 2 E ( t ) dt 2 s £ with a = Q /(Q + Q ) . and i t i s shown that a s i n g l e i n t e r a c t i o n parameter I = ωτ accounts f o r chemical conversion when the s t o i e c h i o m e t r i c r a t i o and the Damkohler number (kC x) are v a r i e d . e. Mixing i s simulated by Monte-Carlo method (random coa­ lescence) (77)» This t h e o r e t i c a l work i s supported by an e x p e r i ­ mental study where a r e a c t o r was f e d with two unmixed feedstreams having d i f f e r e n t RTD (85).E.g.. Maximum species mixedness).R t ) ] . The model depends on three parameters : two i n t e r a c t i o n mo­ Downloaded by CORNELL UNIV on December 2.The Shrinking-Aggregate Model (71). The l a s t paper of the s e r i e s (79) compares the merits of a r e a c t i o n / d i f f u s i o n mo­ del and of the C-D model.. The models presented on f i g u r e 5 can e a s i l y be extended to the case of two separate feedstreams by j o i n i n g the corresponding E n t e r i n g and Leaving E n v i r o n ­ ments side by side ( f i g u r e 7). parameter T / t . and the "segregation parameter R x [s = e x p ( . i n t e r a c t i o n between the e n v i r o n ­ ments from the two feedstreams was modelled by a C-D mechanism. In t h i s case.E. . We have seen that i n t e r a c t i o n between the environments (or between the p a r t i c l e s themselves i f t h i s i s assumed equivalent to segregation decay) could be represented by d i f f e r e n t one parameter models. Chemical r e a c t i o n measurements are r e ­ p o r t e d (86).acs.) with the segregation f u n c t i o n s(a) = exp(-R a).FM = - p FAX) C j l g ( A . For i n s t a n c e .6. VILLERMAUX 159 Mixing in Chemical Reactors l i f e expectancy λ and the same age α (Minimum age. t ) a. parameter τ/te ··· Numerical simulations and t h e o r e t i c a l arguments (based on con­ c e n t r a t i o n variance or chemical conversion) l e a d to the very i n t e r ] 1 1 2 1 g g m S In Chemical Reaction Engineering—Plenary Lectures. et al. and one L.

1 E. In Chemical Reaction Engineering—Plenary Lectures. assumption o f Figure 6. 1983. when the segregation f u n c t i o n o n l y depends on residence time. I n the general case. Three environment model w i t h three parameters R s = exp(-R t ^ ) . American Chemical Society: Washington.org Publication Date: July 28. . J.Downloaded by CORNELL UNIV on December 2.2 Λ* Qi —•α Q 2 Figure 7. DC. 1983 | doi: 10. et al.1021/bk-1983-0226. there are four environments (two e n t e r i n g . 2012 | http://pubs.ch006 160 C H E M I C A L REACTION ENGINEERING E. 1^ ( i n t e r a c t i o n modulus i n the l e a v i n g environment). m i d d l e ) . Bottom. 1^ ( i n t e r ­ a c t i o n modulus i n the e n t e r i n g environment. Top. Wei.E. extension o f Spencer and Leshaw's model t o the case of a r e a c t o r having two i n l e t s (unmixed feedstreams).. ACS Symposium Series. two l e a v i n g ) . t h i s r e p r e s e n t a t i o n i s a l s o v a l i d (78).E.acs..

and that the choice i n favor of one or the other i s o f t e n more a matter of computational convenience than of p h y s i c a l relevance. the conversion of a r e a c t i v e t r a c e r may allow i d e n t i f i c a t i o n of intermediate micromixing s t a t e s . a s a t i s f a c t o r y agreement i s observed between the p r e d i c t i o n s of both models. On Figure 9 the y i e l d of intermedi­ ate product R i n a system o f consecutive competing r e a c t i o n s A+B-+R R+B—*S i s p l o t t e d against the conversion o f Β i n a CSTR with un­ mixed feedstreams (33.acs. In a l l the cases. Dudukovic (90) has shown that these r e c y c l e models are not recommended f o r represent­ i n g intermediate micromixing as i t i s d i f f i c u l t to r e t a i n the same RTD w h i l s t varying the r e c y c l e r a t i o .. 1983 | doi: 10.6.ch006 5 The l a s t point that w i l l be discussed i n t h i s s e c t i o n i s con­ cerned with i d e n t i f i c a t i o n o f micromixing by using r e a c t i v e tracers. et al. Wei. 1983. 92) that the number of m u l t i p l e steady states could depend on the degree of segregation i n chemical reac­ tors where some forms of Langmuir-Hinshelwood r e a c t i o n s were c a r ­ r i e d out. VILLERMAUX Mixing in Chemical Reactors 161 e s t i n g r e s u l t that they y i e l d approximately equivalent r e s u l t s i f the f o l l o w i n g r e l a t i o n s h i p between the parameters i s e s t a b l i s h e d (33. he found (91. P a r i n i and H a r r i s (95) proposed to determine the r e l a t i v e p o s i t i o n of mixing zones i n models having the same RTD by studying the conversion i n a pulse In Chemical Reaction Engineering—Plenary Lectures.org Publication Date: July 28. We can conclude from t h i s that a l l these phenomenological models are approximately equivalent. For each model. as f o r instance i n reference (89) where the f l u i d flows i n a plug flow reactor with d i s t r i b u t e d l a ­ t e r a l o u t l e t and r e c y c l i n g at a given age. J. I t i s known that the spread of an i n e r t t r a c e r during i t s t r a n s i t i n the reactor can only y i e l d information on macromixing (unless concentration f l u c t u a t i o n s are measured as explained above). 94) but we have seen above that t h i s i s rather an academic e x e r c i s e . For instance. Other models i n the l i t e r a t u r e are based on systems with r e c y c l e loops. However. when the p a r t i c l e s undergo s t a t i s t i c a l ­ l y very few coalescences during t h e i r t r a n s i t i n the r e a c t o r . owing to i t s s e n s i t i v i t y to mixing h i s t o r y .1021/bk-1983-0226.. However. t h i s would be less good f o r small values of the i n t e r a c t i o n parameters (see f i g u r e 8). 2012 | http://pubs. Figure 8 shows the conversion f o r an instantaneous r e a c t i o n i n a CSTR f e d with unmixed feedstreams i n s t o i c h i o m e t r i c amounts (33). American Chemical Society: Washington. DC. 78) : m e Let us give three examples f o r t h i s equivalence i n comparing the C-D and the IEM models. Figure 10 compares r e s u l t s obtained f o r a second-order r e a c t i o n i n a r e a c t o r with unmixed feedstreams having d i f f e r e n t RTDs (equivalent t o 2 and 6 tanks i n s e r i e s ) by Treleaven and Tobgy (77) to a s i m u l a t i o n by the IEM model using equations (6-6) and (6-8)(84). Of course. . i n using t h i s model and others. Downloaded by CORNELL UNIV on December 2. ACS Symposium Series. 80). some authors s t i l l evaluate Danckwert's degree of segregation J and t r y to l i n k i t to the segregation i n ­ t e n s i t y (93.

DC. The y i e l d o f R i s p l o t t e d against the conver­ s i o n o f Β ( 80_. k2/k =0. Unmixed feedstreams o f A and Β i n a CSTR. Wei.. Equivalence between the C-D model and the IEM model.. Figure 9· Equivalence between the C-D model and the IEM model. 2012 | http://pubs. 1983. 1983 | doi: 10.org Publication Date: July 28. k 2 A Bo 1 In Chemical Reaction Engineering—Plenary Lectures. et al. Instantaneous r e a c t i o n between two unmixed feedstreams o f A and Β i n s t o i c h i o m e t r i c amount i n a CSTR (33).5. American Chemical Society: Washington.acs. J. ACS Symposium Series. Q . k R + B * S .1021/bk-1983-0226. 33). i Consecutive competing second-order r e a c t i o n s A + Β •R. C = C .ch006 162 C H E M I C A L REACTION ENGINEERING Figure 8.Downloaded by CORNELL UNIV on December 2.

VILLERMAUX Mixing in Chemical Reactors 2 3 4 5 10 163 20 30 50 Figure 10. Reactor w i t h two i n l e t s having d i f f e r e n t RTDs e q u i v a l e n t t o t h a t o f 2 and 6 tanks i n s e r i e s . DC. Equivalence between the C-D model and t h e IEM model. C^ =8 » A °·^· e l e a v e n and Tobgy (77) f o r ?he C-D model.org Publication Date: July 28. et al. ACS Symposium Series.acs.1021/bk-1983-0226.. 2012 | http://pubs. Unmixed feedstreams o f A and Β (equal f l o w r a t e s ) .. 1983 | doi: 10. Wei. J. 1983. r e s p e c t i v e l y .ch006 6. second-order r e a c t i o n . American Chemical Society: Washington. . k C T = D a t a o f T r In Chemical Reaction Engineering—Plenary Lectures.Downloaded by CORNELL UNIV on December 2.

1021/bk-1983-0226. This S e c t i o n w i l l thus be devoted to a Lagrangian approach to the problem already discussed i n E u l e r i a n coordinates The aim i s to give a p h y s i c a l d e s c r i p t i o n amenable to q u a n t i t a t i v e p r e d i c t i o n of segregation decay. I n a p o o r l y mixed CSTR.. the term "par­ t i c l e " has not been a c c u r a t e l y d e f i n e d .. 0) the recommended i n j e c t i o n shape i s a square pulse c o n t a i n i n g both A and B.Downloaded by CORNELL UNIV on December 2. or more g e n e r a l l y any segregated region of the f l u i d which the mixing process has to destroy and d i s p e r s e i n order to achieve mixing at the molecular s c a l e (or a t l e a s t a t a s c a l e where chemical reac­ t i o n s can o c c u r ) . i t may denote a f l u i d b l o b . et al. Wei. Most of them are more or l e s s e q u i v a l e n t . When the f l u i d i s c l o s e to Max. (α* % 1. Simultaneously. When the f l u i d i s c l o s e to Min. 1983. ACS Symposium Series. an o p t i c a l l y d e t e c t a b l e product. A s i m i l a r study was made by Wood and Hop (96). American Chemical Society: Washington. U n t i l now.d e f i n e d RTD. 1983 | doi: 10. Instead of imagining more and more s o p h i s t i c a t e d mathematical ways to pass from the E n t e r i n g to the Leaving Environment. the soundest b a s i s f o r t h i s d e s c r i p t i o n was p u b l i s h e d by Beek and M i l l e r t h i r t e e n years ago (98). The conversion i n the o u t l e t pulse i s then s t r o n g l y dependent on micromixing.Mix. lamina) a group of molecules.acs. segregation was found to i n c r e a s e w i t h v i s c o s i t y but the i n t e r p r e ­ t a t i o n o f the experiments i s d i f f i c u l t owing to an i l l . 2012 | http://pubs. The c o n c l u s i o n to t h i s S e c t i o n i s c l e a r : there are now enough phenomenological models i n the l i t e r a t u r e f o r r e p r e s e n t i n g i n t e r ­ mediate micromixing (mixing e a r l i n e s s ) i n flow r e a c t o r s . According to t h e i r own words. i t would be a d v i s a b l e to c o l l e c t more ex­ perimental data on r e a l r e a c t o r s (the r e a c t i v e t r a c e r method i s e s p e c i a l l y promising i n t h i s way) and to t r y to c o r r e l a t e the value of the micromixing parameters to physicochemical p r o p e r t i e s of the mixture and o p e r a t i n g c h a r a c t e r i s t i c s of the r e a c t o r . As w e l l a Danckwer^s "point". An experimental i l l u s t r a t i o n of the method i s given i n the next paper by Spencer and Lunt (97).3).2 and 5. J. Segregation and mixing at the microscopic l e v e l : mechanism of mi­ cromixing i n the p h y s i c a l space. (α* % 0 or large i n the models of f i g u r e s 5.ch006 164 C H E M I C A L REACTION ENGINEERING of r e a c t i v e t r a c e r . This leads us d i r e c t l y to the next S e c t i o n .n i t r o p h e n y l acetate and sodium hydrox­ ide which undergo a second-order r e a c t i o n t o produce p-nitropheny l a t e . Spencer e t a l . the best d i s c r i m i n a t i o n i s ob­ tained when A and Β are i n j e c t e d i n the form of two sharp pulses separated by a short i n t e r v a l .org Publication Date: July 28. t h e fundamental mechanism o f i n t e r a c t i o n be­ tween f l u i d p a r t i c l e s w i l l be d i s c u s s e d . More r e c e n t l y . DC. proposed and i n t e r e s t i n g method to determine mixing e a r l i n e s s by using two r e a c t i v e t r a c e r s A and Β (68).Mix. c y l i n d e r . three stages may be d i s t i n g u i s h e d i n the mixing process : In Chemical Reaction Engineering—Plenary Lectures. In t h i s s e c t i o n . The r e a c t i v e t r a c e r s were p . . s l a b . clump or aggregate of any shape (sphere. such a comprehensive d e s c r i p t i o n should pro­ v i d e a p h y s i c a l i n t e r p r e t a t i o n f o r the phenomenological parameters of the models depicted i n the preceding S e c t i o n . In my o p i n i o n . r e l y i n g on experimental parame­ ters .

n n denotes a dyadic product (the dyadic product of v e c t o r s a and b i s the tensor a^bj) and I) : n n denotes the s c a l a r product of the two tensors (the s c a l a r product of tensors T^ = T^j and W = W x i s the s c a l a r q u a n t i t y Τ : W = Σ Σ Τ — Wj^). (99^.D : n n ν ν — (7-2) This equation can be i n t e g r a t e d i n p a r t i c u l a r v e l o c i t y f i e l d s to In Chemical Reaction Engineering—Plenary Lectures. the a b s t r a c t c h a r a c t e r o f the mathematical formalism used i n these papers might d i s c o u r ­ age p r a c t i t i o n e r s who are not very f a m i l i a r w i t h t e n s o r a n a l y s i s . ACS Symposium Series.6. a ô = 1. American Chemical Society: Washington. Assume that we s t a r t w i t h two m i s c i b l e f l u i d s A i J and Β (having f o r instance d i f f e r e n t c o l o r s ) . 105) are then f o r the r a t e of change o f l i n e a r s t r e t c h (λ/λ) and area s t r e t c h ( Λ?). Wei. Let us review the models pro­ posed f o r the l a s t two processes (32). 2.L ) . J. Mixing by molecular d i f f u s i o n ..D : n n (7-1) A few words of e x p l a n a t i o n are not useless i n order to understand t h i s formalism. D i s t r i b u t i o n o f one f l u i d through the other and u n i f o r m i z a t i o n of average composition without decreasing l o c a l concentra­ tion variations.org Publication Date: July 28. we o b t a i n a l a m e l l a r mar­ b l e d s t r u c t u r e c h a r a c t e r i z e d by a s t r i a t i o n thickness 6 and a spe­ c i f i c " i n t e r f a c i a l " area a . Stage 1 i s c l e a r l y macromixing. 2012 | http://pubs.1 be the v e l o ­ c i t y g r a d i e n t . D i f f u s i o n i s f u r t h e r superimposed on to the p a t t e r n created by convection. P u r e l y convective mixing.by a p p l i c a t i o n o f (7-1) k v v â /a = . Two q u a n t i t i e s are of s p e c i a l i n t e r e s t : the m a t e r i a l time r a t e of change of l i n e a r s t r e t c h . Ranz and coworkers (99-106) i n the l a s t three years. An important c o n t r i b u t i o n t o the s o l u t i o n of t h i s problem was given by O t t i n o . 1983 | doi: 10. I f the f l u i d i s i n c o m p r e s s i b l e . we may d e f i n e the ^ i s t r e t c h i n g tensor D = (1/2)(L + L ) and the v o r t i c i t y tensor Q = (1/2)(L .. The fundamental r e l a t i o n s h i p s e s t a b l i s h e d by O t t i n o . Ranz e t a l . The theory considers only convective mixing under the i n f l u e n c e of the v e l o c i t y f i e l d .1021/bk-1983-0226. η/η = V. i t i s p o s s i b l e t o p r e d i c t the deformation of any m a t e r i a l p o r t i o n of f l u i d as a f u n c t i o n of the Lagrangian time attached to t h i s element. . 101.è/ό = . The main i d e a i s that once the v e l o c i t y f i e l d i n s i d e the r e a c t o r i s known. As a consequence of m i x i n g .lf = . the medium i s assumed to have a l a m e l l a r s t r u c t u r e and n i s a u n i t v e c t o r which remains normal to the m a t e r i a l s l i c e s undergoing deformations i n the v e l o ­ c i t y f i e l d . Then. 1983. Let L = V. 103. and that of area s t r e t c h . Reduction of s i z e of the regions of uniform composition and increase of contact between regions of d i f f e r e n t composition. From t h i s . although the u n d e r l y i n g concepts are f i n a l l y r a t h e r simple.ch006 1. VILLERMAUX Mixing in Chemical Reactors 165 Downloaded by CORNELL UNIV on December 2. 3. However. et al.acs. DC.U . Upon mixing. respec­ tively: x T T Π = D :η η λ/λ .

102. U δ/δ 1 / 2 (7-5) = 0. In a newtonian f l u i d . Conversely.acs. American Chemical Society: Washington. x 1 (7-7) This k i n d of s t r e t c h i n g occurs f o r instance i n " t a f f y p u l l " . 105) : D : η η ^ (D : D ) 1 / 2 = (ε /2ν) 1 / 2 (7-3) γ where ε i s the viscous d i s s i p a t i o n per u n i t mass. I f the sheet i s f o l d e d up a f t e r a given s t r e t c h i n g d u r a t i o n t and the r e s u l t i n g sheet i s streched up again. 104) : x δ/δ y 2 2 2 2 δ = δ x = αχ.org Publication Date: July 28.. Uy = . 2012 | http://pubs.-»D : η n -> D : η η (£ = D) (ε /2ν) 1 / 2 ν the l a t t e r being v a l i d f o r newtonian f l u i d s o n l y . DC. O t t i n o s treatment assumes continuous motion. U χ = . .166 C H E M I C A L REACTION ENGINEERING y i e l d the v a r i a t i o n of the s t r i a t i o n thickness as a f u n c t i o n of time (see below).G/(l + Gt) and δ = δ (1 + G t ) " y = 0.1021/bk-1983-0226. and hence c o n s e r v a t i o n of t o p o l o g i c a l features (105). et al. (7-3) imposes a lower bound tg ^ (2ν/ε)'/^.G t / ( 1 + G t ) and δ = 6 (1 + G t ) " 2) Stagnation flow ( U t i a l l y normal to Oy) (104) U z = G / ( l + Gt). Wei. 1983 | doi: 10..ay. laminae i n i t i a l l y nor­ mal to Ox) (99. J. 105). 1983. U = 0. This i s the b a s i s f o r the " S h r i n k i n g Aggre- In Chemical Reaction Engineering—Plenary Lectures.ch006 ->. Q t t t t 0 1 E r o s i v e (or d i s p e r s i v e ) Mixing. Let us give three examples (the reader may t r y to f i n d these r e s u l t s by a p p l i c a t i o n o f ( 7 . namely connectedness of m a t e r i a l s u r f a c e s . 103. In a l l these processes.at) (7-6) 3) S t r e t c h i n g at constant v e l o c i t y (υ = 0) z 2 = . e f f i c i e n t mixing i s achieved when the laminae are p e r i o d i c a l l y r e o r i e n t e d w i t h r e ­ spect t o the d i r e c t i o n o f s t r e t c h i n g (101). I f we d e f i n e a s t r e t c h i n g time tg as tg = -ό/ό. (7-3) a l s o allows a l o c a l e f f i c i e n c y to be defined as : ν Downloaded by CORNELL UNIV on December 2. This remark i s a l s o im­ portant i n the design of s t a t i c mixers. 1) Shear flow ( U = Gy. The average v a l ­ ue o f e over the whole r e a c t o r volume leads t o the o v e r a l l e f f i ­ ciency " e f f " of the mixing process t e l l i n g us how the viscous d i s ­ s i p a t i o n i s u t i l i z e d to promote the t h i n n i n g of the laminae (107. U = 0. laminae i n i ­ z exp(. one may t h i n k of a mixing process t h a t would g r a d u a l l y p u l l o f f s m a l l ­ er fragments from the segregated clumps by t u r b u l e n t f r i c t i o n at t h e i r e x t e r n a l surface. i t can be shown that (99.2 ) ) . ACS Symposium Series. then the number of f o l d s i s 2 ' o and δ = δ 2"" ' o.

J.shown (110) that 2 μ = {HH ' L = Ϊ~ΓΤ a n d h e n C e C D = (p 0( + P + 3)& ( 7 _ 9 ) where ρ = 0 f o r s l a b s . Wei. 1983 | doi: 10. In turbulent media. The p a r t i c l e s merge at random with the average frequency ω. For s p h e r i c a l shape. The c h a r a c t e r i s t i c time constant i s t^p = Ι/ω. (71). et al. 1 g Mixing by molecular d i f f u s i o n . i t i s g e n e r a l l y accepted that t^p i s p r o p o r t i o n a l to C o r r s i n s time constant T (See above). .ch006 l ^ I/O Ο Κ = Ô726W -1/3 S c e ^ Ο Κ 276^ /"7 Q\ η. The prob­ lem. This process has already been mentioned i n the preceding S e c t i o n s . case of l a m e l l a r s t r u c t u r e with s t r i a t i o n thickness 6 = 2 R ) . and spheres (diameter 2 R . t h i s leads to a l i n e a r s i z e de­ crease as a f u n c t i o n of age : & = Z (\ . a p p l i c a ­ ble to small p a r t i c l e s immersed i n t u r b u l e n t media : hl/<Sb = 0.org Publication Date: July 28.. I t can be. 2012 | http://pubs. when molecular d i f f u s i o n i s r e t a i n e d as the mixing mechanism In Chemical Reaction Engineering—Plenary Lectures. % ( 7 _ 8 ) i n l i q u i d s (Se ^ 1000). A f t e r mixing. i t seems necessary to introduce e f f i c i e n c i e s η j and η 2 f o r the u t i l i z a t i o n of mecha­ n i c a l energy and k i n e t i c energy d i s s i p a t i o n r e s p e c t i v e l y (71. For instance l e t us consider v a r i o u s shapes : slabs (thickness 2 R . The p e e l i n g . 108) ε = η j ε] + η 2 2 * These are questions f o r f u r t h e r research. American Chemical Society: Washington.1021/bk-1983-0226. two new p a r t i c l e s are instantaneously produced by breaking up of the coalesced complex. y i s a shape f a c t o r and L i s the r a t i o of the volume to the e x t e r n a l surface area of the p a r t i c l e ..13 l(e/v ) /^ Sc . i s the f a m i l i a r Kolmogorov m i c r o s c a l e (see above).ct/t ) with the characte­ r i s t i c e r o s i o n time-constant 3 ] 1 / 3 Q ^. case of filamentous s t r u c t u r e ) . 1983. ACS Symposium Series. ρ = 1 f o r c y l i n d e r s and ρ = 2 f o r spheres. case of s p h e r i c a l aggregates).acs. The p a r t i c l e then approximately behaves as a f i r s t order dynamic system o f time constant t ^ with respect to mass t r a n s f e r . e e Q T w o Q Q ε Coalescence-Dispersion Mixing. The time constant f o r t h i s process i s the d i f f u s i o n time tp = \ιΐβ/<&. The dependence of t on experimental parameters i s thus t ^ t <£)-2/3 problems remain to be s o l ved : How to estimate the i n i t i a l s i z e Z of the aggregates ? Is i t p r o p o r t i o n a l to the i n i t i a l v e l o c i t y U of the f l u i d as i t has been assumed i n s t i r r e d r e a c t o r s (71) ? What i s the expression of the energy d i s s i p a t i o n r a t e ? As already pointed out. This i s mainly a phenomenological parameter. This i s the u l t i m a t e and f i ­ n a l l y the only process r e a l l y able to mix the components of a f l u i d to the molecular s c a l e .6. VILLERMAUX 167 Mixing in Chemical Reactors gate" (SA) Model of P l a s a r i et a l . long cy­ l i n d e r s (diameter 2 R .o f f process i s c h a r a c t e r i z e d by a mass t r a n s f e r c o e f f i c i e n t h which i s assumed to be expressed by the Calderbank-Moo Young c o r r e l a t i o n . I i s the diameter of the s h r i n k i n g aggregate. DC.^ e Downloaded by CORNELL UNIV on December 2.

168 C H E M I C A L R E A C T I O N ENGINEERING i s to choose the adequate length s c a l e Ζ (or 2R).acs. DC. 3 1 / 4 1 / 4 Κ 1 β 4 c 1 2 2 8 1 / 3 £ κ Downloaded by CORNELL UNIV on December 2.2 s 0. Wei.. However. and that X^/tf) and x have the same order of magnitude between 0. the approximate values of some microscales and time constants i n t y p i c a l c o n d i t i o n s are reported i n Table I I I . i n p e r f e c t l y w e l l defined c o n d i t i o n s should be devised to s e t t l e t h i s problem. American Chemical Society: Washington. 118. 7_1_. ACS Symposium Series. Corrsin X = (grVc) / ) or w i t h C o r r s i n s m i c r o s c a l e f o r segregation d i s s i p a t i o n λ (λ = 24â) ( L / ) ? This may depend on the mechanism l e a d i n g to the u l t i m a t e stage of molecular mixing.3 m (large r e a c t o r ) s Kolmogorov λ Corrsin A ms 3 0. . .1 m (small r e a c t o r ) 32 ym 70 ym 18 ym 1 6 ym 1 s 0. 2012 | http://pubs. J08. Other processes ate much f a s t e r . Rigorous e x p e r i ­ ments.4 χ 10~" s 5 3. 39. et al. 32). Some authors f i n d a marked i n f l u e n c e of v i s c o s i t y and i n c l i n e towards the choice of Ζ = λ (111-116).1 and 1 second. . Batchelor λ = ( ^ / ε ) . JJJ7. This p o i n t i s s t i l l open to d i s c u s s i o n . Should Ζ (or 2R) be i d e n t i f i e d w i t h the s t r i a t i o n thickness 6 or w i t h one of the viscous d i s s i p a t i o n microscales of Table I (Kolmogorov λ = ( ν / ε ) . i t i s not q u i t e sure that a l l the experiments reported i n the l i t e r a t u r e are f r e e from spurious e f f e c t s (macromixing.45 χ 10" s 3 1.1021/bk-1983-0226. 109. 30.9 s 1/2 . J. Sc = 10 Case 1 : ε = 1 Watt kg L = 0.. As the r a t e of energy d i s s i p a t i o n per u n i t mass ε f i g u r e s i n a l l the expressions f o r the m i c r o s c a l e s . ) . 1983. 1983 | doi: 10. v c g In Chemical Reaction Engineering—Plenary Lectures. e a r l y stages of convective or e r o s i v e mixing. e t c .org Publication Date: July 28.ch006 g Table I I I Experimental parameters : ν = 10 ms .3=10 2 λ /£> = T t κ g 3/2 1/2 ν /(3>ε ) s =2 ô = /2 τ α|/ε) κ 1 / 3 = (2ν/ε) Case 2 : ε = 10 Watts kg"" L = 0. Others f i n d almost no i n f l u e n c e of v i s c o s i t y and con­ clude i n favour of A (2. the problem of i t s spa­ t i a l r e p a r t i t i o n and of the conversion e f f i c i e n c y of the macrosco­ p i c d i s s i p a t i o n i s a l s o posed here.5 χ 10" s I t i s concluded from t h i s Table that X and X l i e between 10 and 100 ym. An experimental clue f o r the choice of the r e l e v a n t microscale i s the i n f l u e n c e of v i s c o s i t y which intervenes i n a d i f f e r e n t manner i n t h e i r expression. I n order to give a few orders of magnitude.3 s 1 \l® = <2>/ε) 1/2 0.

the chemical r e a c t i o n i s f a s t e r than mixing and micro­ s c o p i c c o n c e n t r a t i o n g r a d i e n t s appear: the f l u i d becomes segregat­ ed. i n s p i t e o f i t s great i n t e r e s t : a r b i t r a r y choice o f s p h e r i c a l shape. Several authors have s t u d i e d the competition between chemical r e a c t i o n s and molecular d i f f u s i o n i n f l u i d p a r t i c l e s .6. Bourne and t h e i r group at the E. American Chemical Society: Washington. Ε = A / B and α = V /V . 120).1021/bk-1983-0226.E r o s i v e mixing f o l l o w e d by r e a c t i o n : Two unmixed r e a c t a n t s come i n t o contact i n a CSTR by e r o s i o n of f r e s h aggregates. 120). to the MIRE-model. They developed a model (the MIRE model) e s s e n t i a l l y adapted t o ^ p r e d i c t the ^ y i e l d of consecutive competing r e a c t i o n s A + Β R. 2012 | http://pubs. The parameters are two Thiele c r i t e r i a = k B R / D * t / t . t = 1/k CQ "" f o r an n order r e a c t i o n ) to the micromixing time t (or t ^ . For r e p r e s e n t i n g r e a c t i o n and d i f f u s i o n i n s t r e t c h i n g l a m e l l a r s t r u c t u r e s .. The e r o s i o n product i s e i t h e r a m i c r o f l u i d (71) or small segregated p a r t i c l e s of mixed reactants undergoing f u r t h e r i n t e r a c t i o n by mo­ l e c u l a r d i f f u s i o n (108). We must now d i s c u s s the cou­ p l i n g between the mixing processes and chemical r e a c t i o n s . DC. Nauman (81) introduced a s e g r e g a t i o n number ^Seg Φ** /(^3) τ) . V e r s i o n I I : symmetrical case (par­ t i c l e of n o n . which creates an unwanted dissymmetry between A and Β when V^ = V-Q. Some c r i t i c i s m may be adressed.. where chemi­ c a l r e a c t i o n takes place during v a r i o u s stages of Beek and M i l l e r . The equivalence w i t h the MIRE-model w i l l be discussed below. and l a t e r extended to continuous s t i r r e d r e a c t o r s v i a a somewhat complicated procedure (121-112). a s s i m i l a t i o n of R to h a l f the Kolmogorov m i c r o s c a l e (which i s not obvious as we have seen above) and above a l l . 1983 | doi: 10. The p a r t i c l e s are assumed to be s p h e r i c a l (radius R) and the equations f o r r e a c t i o n / d i f f u s i o n are s o l v e d i n v a r i o u s cases: V e r s i o n I : P a r t i c l e s i n i t i a l l y c o n t a i n ­ i n g A immersed i n pure Β (A i s not allowed t o d i f f u s e w i t h i n the p a r t i c l e . J. VILLERMAUX 169 Mixing in Chemical Reactors M i x i n g and chemical r e a c t i o n . I t s u f f i c e s to set t = t = yL /J«. or a combination of these : .H. when t ^ / t i s l a r g e . When t ^ / t i s s m a l l . et al.acs.org Publication Date: July 28. the f l u i d may be considered as w e l l micromixed from the viewpoint of the chemical r e a c t i o n (98) .> S i n s t i r r e d r e a c t o r s (119. which compares the d i f f u s i o n time w i t h the space time. Wei. The r e a c t i o n / d i f f u s i o n c o m p e t i t i o n can a l s o be simulated by the IEM-Model. Simula­ t i o n s v i a the IEM model or the C-D model have a l r e a d y been p r e s e n t ­ ed i n the preceding s e c t i o n . 1983. other species a r e ) . ACS Symposium Series.S t r e t c h i n g of p a r t i c l e s and simultaneous r e a c t i o n . O t t i n o and Ranz (101) introduced a "warped time" t defined by : 11 1 t n R m Downloaded by CORNELL UNIV on December 2.g.p ) . R + Β __?. assumption that the i n i t i a l r e a c t a n t i n the p a r t i c l e cannot d i f f u s e o u t s i d e . A major c o n t r i b u t i o n to t h i s problem was brought by Rys.T. More s o p h i s t i c a t e d mechanisms may be considered. I t was developed f o r batch and semi-batch r e a c t o r s (119. o f Z u r i c h .ch006 = m 2 2 i Q D R i Q 0 A B s 2 D w In Chemical Reaction Engineering—Plenary Lectures. The key parameter i s the r a t i o o f some c h a r a c t e r i s t i c r e a c t i o n time (e. Conversely. In s t i r r e d r e a c t o r s . The model p r e d i c t s the y i e l d o f S : X = 2S/(2 S + R) a t the end of the r e a c t i o n (when a l l Β i s consumed). .d i f f u s i n g Β immersed i n A). .

ft/S % x / t % 4 τ/t . We may now complete the l i s t of equivalences c i t e d i n ( 6 . ACS Symposium Series. The IEM-Model i s a lumped v e r s i o n of the d i s t r i b u t e d para­ meter r e a c t i o n / d i f f u s i o n model. ( 1 1 9 . and the IEM Model.9 ) by a new one between the d r o p l e t . Bourne et a l . The equations f o r r e a c t i o n / d i f f u s i o n are then e a s i e r to solve i n Lagrangian coordinates.. Model accounts f o r such deformations i n assuming that the micromixing time i s a s p e c i f i e d f u n c t i o n of the p a r t i c l e age (32). In the case of e r o s i v e mixing of two reactants i n a CSTR (1 . Fast consecutive-competing r e a c t i o n s A + B ÎLL>R. R+B _JL> S (kj >> k ) are e s p e c i a l l y i n t e r e s t i n g : i f a small amount of Β i s mixed i n t o an excess o f A. ( 1 2 2 . Therefore.3 ) .1021/bk-1983-0226.d i f f u s i o n model of Nauman ( 8 1 ) or the MIRE-model of Rys.ch006 t w = / c Jo JL^ H t < ) 2 d f or Ιίϋ =S> a dt ENGINEERING 2 (7-10) where the r a t e of change of the s t r i a t i o n thickness i s given by ( 7 .M. . This would mean that a r e d u c t i o n of the s t r i a t i o n thickness below the Kolmogorov m i c r o s c a l e i s conceivable.acs. 1 1 4 ) extended t h e i r MIRE-Model by assuming that the s i z e of the p a r t i c l e s decreases according to ( 7 . This saves much computer time and the d i f f e r e n c e i n the r e s u l t s i s not greater than f o r instance that induced by a change i n the a r b i t r a r y assumptions concerning the p a r t i c l e shape. A p a r t i a l l y segregated f l u i d may be considered as a mix­ ture of m a c r o f l u i d ( f r a c t i o n 3) and m i c r o f l u i d ( f r a c t i o n 1 .. 1983. The s i m u l a t i o n s v i a the IEM model revealed an i n t e r e s t i n g property. my o p i n i o n i s that i n most a p p l i c a t i o n s . R i s formed and immedim a c r o 2 In Chemical Reaction Engineering—Plenary Lectures. J. P a r t i a l segregation can be s t u d i e d through i t s i n f l u e n c e on the conversion and y i e l d of chemical r e a c t i o n s .3 ) / 3 D % ^ ^ Β * interesting r u l e of thumb f o r r a p i d e s t i m a t i o n of the extent of segregation. DC. l e t us denote by X and Xmicro the l i m i t i n g extents of r e a c t i o n one would ob­ serve i n a w e l l macromixed r e a c t o r . m e m T h i s i s a n d I d e n t i f i c a t i o n of segregation by chemical methods. I f the r e a c t o r i s p a r t i a l l y segregated : X = ΒΧ^. where tp i s given by ( 7 . For i n s t a n c e . 1983 | doi: 10. In the case of r e a c t i o n and d i f f u s i o n or premixed r e a c t a n t s i n a CSTR ( f i g u r e 1 3 ) : ( 1 . American Chemical Society: Washington. I t comes out that the r a t i o (1 . The I.1 2 0 ) .-ο + (1 . f o r the pre­ d i c t i o n of X ( 3 2 ) . Wei.2 ) . The c o n d i t i o n f o r equivalence i s t = t ^ .E.org Publication Date: July 28.β)/(3 i s always c l o s e to that of two c h a r a c t e r i s t i c times ( 3 2 ) . ( 3 1 ) and Spalding ( 1 2 3 ) .170 C H E M I C A L REACTION Downloaded by CORNELL UNIV on December 2. Angst et a l . Reaction and d i f f u s i o n i n d i s t o r t i n g s t r u c t u r e s were a l s o s t u d i e d by Palepu et a l . et al. Figures 11 and 12 are exam­ p l e s of such equivalences. even f o r " s t i f f systems" of f a s t r e a c t i o n s .3) XmicroThis a l s o holds f o r the y i e l d of an intermediate product and i s the b a s i s f o r the determination of 3 or conversely. 2012 | http://pubs. In the same way Bourne.5 ) . Numerical s i m u l a t i o n s prove that r e p l a c i n g c o n c e n t r a t i o n p r o f i l e s by average values does not change the o v e r a l l conversion and y i e l d i n the p a r t i c l e very much.9 ) . a simple lumped parameter model may be used i n place of s o p h i s t i c a t e d d i s t r i b u t e d models.

ACS Symposium Series. Wei. The Damkohler numbers are such t h a t f = 0.org Publication Date: July 28. DC.Downloaded by CORNELL UNIV on December 2. more approximate f o r the zero-order one. In Chemical Reaction Engineering—Plenary Lectures.acs. et al.5 micromixing. 1983. .. 2012 | http://pubs. VILLERMAUX Figure 11. J.ch006 6. and the IEM reaction i n for perfect second-order Mixing in Chemical Reactors 111 Equivalence between the d r o p l e t d i f f u s i o n model (81) model f o r a zero-order r e a c t i o n and a second-order a CSTR. American Chemical Society: Washington.1021/bk-1983-0226. The agreement i s e x c e l l e n t f o r the r e a c t i o n .. 1983 | doi: 10.

t . = R A C Q Q = 2 2 Q 2 D 2 /// f . Wei. t ^ = l / k ^ C ^ .105.. DC. The agreement i s s a t i s f a c t o r y . J. t /t R 0. = 0 L / j . Β cannot d i f f u s e w i t h i n the p a r t i c l e (S> = 0 ) . U. 1983 | doi: 10. 5. ACS Symposium Series. CBO = 1> R 0· k C g R / ^ = 2 f o r A and R. et al. r e a c t i o n / d i f f u s i o n time r a t i o . Equivalence between the r e a c t i o n / d i f f u s i o n model and the IEM model f o r second-order consecutive competing r e a c t i o n s k l &2 A + Β R.Downloaded by CORNELL UNIV on December 2. second-order r e a c t i o n k CAo = 2 ( l ) .. even i f the i n d i v i d u a l c o n c e n t r a t i o n p r o f i l e s become different. second-order consecutive competing r e a c t i o n s = 0-β . American Chemical Society: Washington. C = 0 ) ./kp = 2. β = 3/5.1021/bk-1983-0226. I n much " s t i f f e r " c o n d i t i o n s (k^> > k ) . . m 2 ο In Chemical Reaction Engineering—Plenary Lectures. M i c r o f l u i d / m a c r o f l u i d volume r a t i o v s . B a s i s f o r the e q u i ­ valence t . 3 2 . 2012 | http://pubs. R + Β S. Key t o curves: 1 t o If. ) .ch006 172 CHEMICAL REACTION ENGINEERING Figure 12. k-. 1983. (reduced) time i n a s p h e r i c a l p a r t i c l e immersed i n a bath o f constant composition (C^ 0. r e a c t i o n and d i f f u s i o n i n a s l a b (See Rer.org Publication Date: July 28. L = R/3 (sphere). t = t p . F-β represents the t o t a l production o f R (equivalent c o n c e n t r a t i o n i n the p a r t i c l e ) . . s i m u l a t i o n w i t h the IEM model. 10(3). 1 t o 3. The curves represent t h e average con­ c e n t r a t i o n s v s .1 1 D 10 Figure 13. 5 ( 2 ) . k-^/k^ = 10. the agreement i s always good f o r the o v e r a l l produc­ t i o n o f R.acs. I n i t i a l concentrations i n the p a r t i c l e : C = 0.

who enumerated the q u a l i t i e s of a good r e a c t i o n f o r i n d u s t r i a l tests ( 124) (t-R % t . 2 . d i s t r i b u t i o n of products depending on segre­ gation. known mechanism. Wei. They succeeded i n apply­ ing the MIRE-Model provided that the p a r t i c l e s i z e 2R be 2 to 9 times smaller than the Kolmogorov m i c r o s c a l e . the amount o f 2-U dibromoresorcin i n the di-isomer may vary from 30% to 60 % when the a g i t a t i o n speed passes from 0 to 360 r. 1983. taking i n t o account p o s s i b l e macromixing e f f e c t s (comparison of r e a c t i o n time and c i r c u l a t i o n time t ) . I t has many of the advantages c i t e d above. 114). (128) : the p r e c i p i t a t i o n of baryum s u l f a t e complexed by EDTA i n a l k a l i n e medium under the i n f l u e n c e of an a c i d . easy a n a l y s i s and regeneration. instantaneous (gener­ a l l y acid-base) r e a c t i o n s are a l s o used as an i n d i c a t o r of segre­ gation. VILLERMAUX 173 Mixing in Chemical Reactors a t e l y converted to S at the contact of Β i f the f l u i d i s segregated. but a l s o a good s e n s i t i v i t y t o s e g r e g a t i o n .6. In a recent s e r i e s of papers (129. r e l y i n g on the Kolmogorov microscale. 112.137). Some of them e x h i b i t complex pH e f f e c t s (124.micro)· The method was e x t e n s i v e l y e x p l o i t e d by Bourne and coworkers. bromation of 1-3-5 trimethoxybenzene ( 126).p. Beside consecutive-competing r e a c t i o n s . 1983 | doi: 10. J. that the scale up of the state of segrega­ t i o n requires keeping ε and thus N d^ constant.25 s to 1-10 % l a t e r . American Chemical Society: Washington. et al.m. safe and inexpensive chemicals). Fluorescence methods may also be employed (20). In the same paper. The i n t e r p r e t a t i o n of these b e a u t i f u l experiments should be discussed with much care. Bourne and coworkers presented a thorough i n v e s t i g a t i o n of segregation i n s t i r r e d reactors (2. They concluded from t h e i r i n t e r p r e t a t i o n . Therefore. ACS Symposium Series.5 and 63 dm ) with various i n l e t p o s i t i o n s . They showed that the best mixing conditions were achieved with i n l e t tubes placed j u s t beneath the turbine. and β = ( X . O t t i n o (102) de­ duced the r e l a t i o n s h i p t ^ ( t ) between "warped" and r e a l time from the comparison between experimental conversion X(t) along the axis of a tube and the t h e o r e t i c a l expression X ( t ) . ) / ( l " * . 114). 111). Unfortunately.org Publication Date: July 28. 113. 2012 | http://pubs. i r r e v e r s i b l e r e a c t i o n .° X . but the r e a c t i o n i s not s t r i c t l y i n s t a n t a ­ neous and thus dependent on macromixing. e s p e c i a l l y i n m u l t i j e t tubular r e a c t o r s . " e f f " was found to decrease from 20-30 % f o r t < 0.acs. i n t e r v e n t i o n of d i f f e r e n t mixing processes (of stage 2) preceding the d i f f u s i o n a l one. macromixing e f f e c t s ( c i r c u l a t i o n 0 8 g 8 m i c r o m c r o s s Downloaded by CORNELL UNIV on December 2. As a t e s t r e a c t i o n they used the coupling of 1-naphtol (A) with d i a z o t i s e d s u l p h a n i l i c a c i d (B). 127. A new r e a c t i o n i s proposed i n t h i s Symposium by Barthole et a l . The agreement was improved by assuming s t r e t c h i n g of p a r t i c l e s : 6 = δ ( 1 + t / t ) / where t = 2 ( v / ε ) ' (122. DC. the average e f f i c i e n c y " e f f " was estimated i n a s t i r r e d reactor. the r e a c t i o n s proposed to-date do not f u l f i l l a l l these requirements : Azo-coupling (119. e f f ( t ) was found to decrease as a f u n c t i o n of t with 6 = 1/a of the order of 10 ym.. For i n s t a n c e . X i s some kind of segregation index : X i < X < 1. n i t r a t i o n of aromatic hydrocarbons (125).ch006 Q 3 2 0 1 2 ô 3 c w v 1 / 2 v v v In Chemical Reaction Engineering—Plenary Lectures. (124). but here a l s o ..1 2 . bromation of r e s o r c i n (124) .and the s p a t i a l d i s t r i b u t i o n of ε i n the tank. a was then c a l c u ­ lated by (7-10) and the e f f i c i e n c y e f f ( t ) by : (l/a )da /dt = eff(t)(D : D ) .1021/bk-1983-0226.

J. American Chemical Society: Washington. 2012 | http://pubs. obtained on the b a s i s of the IEM model.174 C H E M I C A L REACTION ENGINEERING time ?) cannot be excluded. these authors conclude that C o r r s i n s micromixing time T cannot e x p l a i n t h e i r observations and that the i n f l u e n c e of v i s c o s i t y suggests a d i f f u s i o n time ba­ sed on Kolmogorov m i c r o s c a l e . (116) a l s o performed ex­ periments w i t h NaOH/HCl mixing behind a Sulzer s t a t i c mixer i n a tube. This problem of mixing w i t h chemical r e a c t i o n has drawn the a t t e n t i o n of many authors i n the l a s t few years. ( 130) studied the a l k a l i n e h y d r o l y s i s of c h l o r o a c e t a t e i n a batch s t i r ­ red r e a c t o r ( t ^ % t ) . (131) developed a model e q u i v a l e n t to the IEM model for i n t e r p r e t i n g mixing i n batch s t i r r e d r e a c t o r s (1 and 50 t) both w i t h a non r e a c t i v e t r a c e r and i n the presence of three r e a c t i o n s of d i f f e r e n t r a p i d i t y . Miyawaki et a l . t h e i r r e s u l t s .acs. . and chemi1 s 1 Downloaded by CORNELL UNIV on December 2.1021/bk-1983-0226.ch006 m 3 8 s m m c m T m s m m 2 m 1 2 M R In Chemical Reaction Engineering—Plenary Lectures. In tubes. 1983. i t seems that 6 tends to X but there i s s t i l l some strange behaviour (climb of 6 before s t a b i l i z a t i o n ) and the pro­ blem of the e f f i c i e n c y i n the c a l c u l a t i o n of ε i s a l s o posed. DC. ACS Symposium Series. Bourne et a l . This i s i n c o n t r a d i c t i o n w i t h the r e s u l t s of Pohorecki and Baldyga (117) who a l s o studied the r e a c t i o n of NaOH and HCl c o n t r o l l e d by mixing i n a tube. Bhatt and Z i e g l e r ( 134) determined the m a c r o f l u i d f r a c t i o n i n a CSTR by t a ­ k i n g i n t o account the n o n . Wei. can probably be explained by macromixing ( t ^ t ^ 1/N). Assuming a d i f f u s i o n a l mechanism f o r mixing. whereas i n s t i r r e d tanks conversion i s probably c o n t r o l l e d by r e c i r c u l a t i o n ( t ^ 1/N) as i n reference (130).org Publication Date: July 28.t / t ) ) w i t h t ^ C o r r s i n s T . et al. Takao et a l . Murakami et a l . 1983 | doi: 10. ε was estimated by U(Ap/£)/p and the i n f l u e n c e of the v i s c o ­ s i t y was e s p e c i a l l y s t u d i e d . V i l l e r m a u x and coworkers suggest (32) that depending on experimental c o n d i t i o n s . A f t e r an i n i ­ t i a l decrease. (31) used the "warped -time method d e s c r i ­ bed i n (102) to estimate the s t r i a t i o n thickness 6 as a f u n c t i o n of time i n a m u l t i j e t tube and i n a s t i r r e d r e a c t o r . Bryant (135) considered the case of zero order r e a c t i o n i n fermenters by assu­ ming d i f f u s i o n a l l i m i t a t i o n s i n p a r t i c l e s having the Kolmogorov s i z e λ£· Palepu et a l . The same c o n c l u s i o n was drawn from experiments i n s t i r r e d tanks.. Ghodsizadeh and A d l e r (133) pro­ posed an i n t e r e s t i n g method based on d i l a t o m e t r y to f o l l o w the course of an acid-base r e a c t i o n i n a batch r e a c t o r . the data are compatible w i t h the IEM model (X = 1 . 71.. and found to be n o t i c e a b l e . 108).i d e a l i t y of the segregated phase RTD and by assuming i n t e r a c t i o n by r e a c t i o n and d i f f u s i o n .e x p ( . From t h e i r own experiments (109. ε was deduced from the assumption of i s o t r o p i c homogeneous turbulence. Hanley and C a l l (132) suggested e x p l o i t i n g c o n c e n t r a t i o n f l u c t u a t i o n s at the o u t l e t of a CSTR to c a l c u l a t e micromixing parameters. They found that the IEM-model was a p p l i c a b l e w i t h t = 2 τ ^ ( L ^ / e ) ' where L was equal to the diameter of the i n j e c t i o n tube. They found that N t could be c o r r e l a t e d as a f u n c t i o n of the a g i t a t i o n Reynolds number Nd /v and a Damkohler number. but without any experimental support. (118) s t u d i e d the r e a c t i o n of C O 2 + N H 3 and C O 2 + OH" i n m u l t i j e t tubes and i n s t i r r e d r e a c t o r s . Costa and L o d i (136) a s s i m i l a t e d the IEM mixing time t to (v/ε) ' w i t h a c o r r e c t i o n depending on the Schmidt number. where the IEM-model seemed unable to account f o r a l l experimental data.

. m u l t i j e t t u b u l a r r e a c t o r s w i t h a diameter l a r g e enough f o r pure homogeneous i s o t r o p i c turbulence to be achieved. 1 Downloaded by CORNELL UNIV on December 2.acs. 1983. 140. which remain the b a s i c devices f o r indus­ t r i a l mixing. There are s t i l l u n c e r t a i n t i e s i n the f i n a l i n t e r ­ p r e t a t i o n of mixing and chemical r e a c t i o n a t the molecular l e v e l . 114) ? F u r t h e r research should be de­ veloped i n the f o l l o w i n g d i r e c t i o n s : . The pro­ blem i s to decide what i s hidden behind the micromixing time t ? C o r r s i n s time constant T (32) ? A d i f f u s i o n constant based on Kolmogorov microscale (113. These r e a c t i o n s should be usable i n i n ­ d u s t r i a l r e a c t o r s and perhaps be l e s s " s t i f f than those proposed by Bourne and coworkers.Search f o r r e l i a b l e t e s t r e a c t i o n s obeying the c r i t e r i a s t a t e d i n reference ( 124).C l e a r d i s t i n c t i o n between the mechanisms p e r t a i n i n g to suc­ c e s s i v e o r simultaneous stages of m i x i n g . Sasakura e t a l . . Wei. DC. even by molecular d i f f u s i o n .1021/bk-1983-0226.5 m ). . (138) and Rachez e t a l .Design of experiments where hydrodynamic c o n d i t i o n s are per­ f e c t l y c o n t r o l l e d : small s t i r r e d r e a c t o r s w i t h high power input (no macromixing e f f e c t s . 2012 | http://pubs. 1983 | doi: 10. ACS Symposium Series.6. Conclusion.org Publication Date: July 28. The IEM model seems to provide a simple b a s i s f o r r e p r e s e n t i n g i n ­ t e r a c t i o n between p a r t i c l e s . VILLERMAUX 175 Mixing in Chemical Reactors c a l r e a c t i o n s . a systematic stu­ dy of the i n f l u e n c e of v i s c o s i t y ν and power d i s s i p a t i o n ε should be made. They showed that c i r c u l a t i o n times t were log-normally d i s t r i b u t e d : 3 Q f(t ) c = 1 exp /2-ïïot the mean value t In t .. et al. ..ch006 s 1 1 c R The S t i r r e d Tank A review on mixing i n chemical r e a c t o r s would be incomplete without an account of recent progress i n the understanding of the working of s t i r r e d tanks. This might e x p l a i n the d i s c r e p a n c i e s ob­ served between authors w i l l i n g to i n t e r p r e t t h e i r experiments by one s i n g l e mechanism. I n t e r n a l c i r c u l a t i o n p a t t e r n s and turbulence. there are s e v e r a l mixing mechanisms f o r stages 2 and 3 of Beek and M i l l e r o c c u r i n g simultaneously and i n t e r a c t i n g w i t h chemical processes.f o l l o w e r s (aiming a t a p p l i c a t i o n s f o r fermenters > 0. no s p a t i a l va­ r i a t i o n of ε). J. c i r c u l a t i o n time t << t .μ c σ/2 c and n a t u r a l variance s being given by z In Chemical Reaction Engineering—Plenary Lectures.Once the above requirements are f u l f i l l e d . American Chemical Society: Washington. Bryant and coworkers (135. 141) and Reuss s t u d i e d more s p e c i f i c a l l y c i r c u l a t i o n times i n l a r g e s t i r r e d tanks by using r a d i o f l o w . (139) i n v e s t i g a t e d i n t e r n a l age d i s t r i ­ butions by means of t r a c e r s and proposed r e p r e s e n t a t i v e models o f the c i r c u l a t i o n p a t t e r n .

6 i s defined as the time constant f o r the exponential decrease of pseudo-periodic o s c i l l a ­ tions a f t e r a pulse i n j e c t i o n of t r a c e r i n a batch s t i r r e d reactor. the f o l l o w i n g s p a t i a l v a r i a t i o n s were found : u = 5 to 30 % of TrNd.2 to 2.176 C H E M I C A L REACTION 2 2 2 ENGINEERING 2 = exp(y + σ / 2 ) and s = ( t ^ ) ( e x p σ . many au­ thors have determined turbulence parameters and t h e i r s p a t i a l d i s ­ t r i b u t i o n w i t h i n the tank volume by measuring v e l o c i t y and concen­ t r a t i o n fluctuations(144-147.5. they obtain f o r turbines : 3 7 3 3 m 2 m 1 3 c 3 m 2 c m Downloaded by CORNELL UNIV on December 2. et al. Experimental data on mixing times may be used to estimate the o v e r a l l e f f i c i e n c y f o r batch mixing of viscous f l u i d s .. they found t ^ H/(Nd ) and s ^ H ' / ( N d ) . This item w i l l be reviewed only ve­ ry b r i e f l y as the subject was r e c e n t l y covered i n e x c e l l e n t and In Chemical Reaction Engineering—Plenary Lectures.org Publication Date: July 28. 19. In a t y p i c a l i n v e s t i g a t i o n (19) concerning a s e m i . so that 0 ^ H ^_ /(Nd ) when A i s small. according to the method proposed by Ottino et a l . 2012 | http://pubs. 3 f 4 C e l l models. s / t > 0. They found 6 /"tf^ = A + B( s / t ) . This shows that a s t i r r e d tank i s f a r from being the homogeneous and uniform system assumed i n many academic papers. .. American Chemical Society: Washington. _39.149) also studied a model where c e l l s (or segments) are connected accor­ ding to the average flow p a t t e r n .15 m ) and aqueous me­ dium.9 % 1. 1983 | doi: 10. required f o r redu­ cing c o n c e n t r a t i o n gradients down to a s p e c i f i e d l e v e l by m u l t i p l e r e c i r c u l a t i o n s . (107).1 p/(pN d ) and f o r p r o p e l l e r s N0 (d/d ) m T 2 3 5 C o r r e l a t i o n s f o r jet-mixing can be found i n (157).i n d u s t r i a l tank (0. P a t t e r s o n and coworkers (3. on the b a s i s of a r e c y c l e model. 1983.1021/bk-1983-0226. J.5 % 0. 3 2 s T Multiphase s t i r r e d tanks. ACS Symposium Series. In order to p r e d i c t chemical conversion i n s t i r ­ red tanks. The power input i s thus Ρ % (Nd) (V/t ). c'/C = 2 to 10 χ 10"" ( f o r eddies > 100 ym). Xf = 1 to 5 mm. Wei. L f = 4 to 150 mm. They thus ob­ tained c i r c u l a t i o n time d i s t r i b u t i o n s very s i m i l a r to experimental ones (135. In a d d i t i o n to these macromixing c h a r a c t e r i s t i c s . 140. 141). I f Η i s the height of l i q u i d i n the tank. Commutation according to a spe­ c i f i e d p r o b a b i l i t y at each c e l l ' s o u t l e t allows a s t o c h a s t i c path to be simulatedj f o r instance f o r a flow f o l l o w e r . 40) d i v i d e d the tank volume i n t o 30 mixing segments connected by s p e c i f i e d flowrates Q^j % Nd . Mann and coworkers (148. One of the most comprehensive treatments of t h i s problem was published by Khang and L e v e n s p i e l (143). Many c o r r e l a t i o n s f o r mixing time (see above) have been proposed i n the l i t e r a t u r e (142).8. They also studied the terminal mixing time 0 . DC.acs.ch006 4 2 5 (8-2) = 0. 158) . When Re > 10 . The turbulence l e v e l i n each segment i s c h a r a c t e r i z e d by L (^ d ) and ε(^ d ) (HDM model).1). ε/ε = 0.5 P/(pN d ) (8-3) Ν e (d/d ) * m 3 T 3 = 0.

These were reviewed i n an e x c e l l e n t paper by Kipke (154). . many problems remain unsolved (. 1983.6.l i q u i d r e a c t o r s are a v a i l a b l e as Oldshue showed i n the case of a l k y l a t i o n ( 152). l a r g e d e n s i t y d i f f e r e n c e s .l i q u i d . Although p r a c t i c a l r u l e s f o r the design and scale-up of l i q u i d . DC. et al. Downloaded by CORNELL UNIV on December 2. T a v l a r i d e s presents a s o p h i s t i c a t e d model f o r r e p r e s e n t i n g coalescence and breakage of d r o p l e t s i n l i q u i d .l i q u i d . Future r e ­ search should be d i r e c t e d towards . J o s h i e t a l . This product seems to increase w i t h the gas-flowrate.l i q u i d r e a c t o r s 05. high hold-up f r a c t i o n s (> 20 % ) . L i t t l e i s yet known about the s t a t e of mixing of the dispersed gas and on the i n f l u e n c e of s o l i d i n suspension. l i q u i d . For i n s t a n c e . The s o l u t i o n of such equa­ t i o n s i s d i f f i c u l t and r e q u i r e s the use of Monte-Carlo methods (151) .Large volumes ( s p a t i a l unhomogeneities) .org Publication Date: July 28. VILLERMAUX Mixing in Chemical Reactors 177 quasi-exhaustive surveys by J o s h i e t a l .1021/bk-1983-0226. ACS Symposium Series.Less dimensional a n a l y s i s Less c l a s s i c a l devices : s t a t i c mixers S t a t i c mixers have been e s s e n t i a l l y developed s i n c e 1970. at the ex­ pense of a corresponding increase i n pressure-drop. i n f l u e n c e of s u r f a c t a n t s . 40 . s e v e r a l current problems are s t i l l w a i t i n g s o l u t i o n . l i q u i d . σ/C = a exp(-mz/d ) or by the increase of s t r i a t i o n number produced by passing through η m i ­ xing elements (160) : δ /δ = b . The model r e l i e s on the p o p u l a t i o n balance equation and s t i l l r e ­ q u i r e s the adjustment of 6 parameters. American Chemical Society: Washington.s o l i d . The case of Sulzer-Mixers has been e s p e c i a l l y s t u d i e d (163).Multiphase systems ( g a s . Mixing i n s t i r r e d reactors i s no longer the e m p i r i c a l o p e r a t i o n i t used to be. Wei. f o r g a s .. 156) .Turbulent phenomena .Non newtonien media.Search f o r s i m p l i f i e d models and new concepts . 6 /6 = 4 . A comparison between the e x i s t i n g types of s t a t i c mixers (162) shows that most of them have an e q u i v a l e n t e f f e c t i v e n e s s . About 30 types of these devices are known (159). high v i s c o s i t i e s . ("mostly a r t and very l i t t l e s c i e n c e " (153). Oldshue summarized u s e f u l r u l e s f o r the scale-up of fermenters (153). t n 0 Q n In Chemical Reaction Engineering—Plenary Lectures. 2012 | http://pubs. Their e f f e c t i v e ­ ness can be c h a r a c t e r i z e d i n two ways : by__the r e d u c t i o n of σ/C (See above) along the mixer a x i s (159). How­ ever. The e f f e c t of coalescence and break-up of d r o p l e t s on the y i e l d of chemical r e a c t i o n s was s t u d i e d by V i l l e r m a u x (33). rheology problems (155. M i c r o mixing e f f e c t s may occur even i n batch r e a c t o r s i f there i s a drop s i z e d i s t r i b u t i o n and mass-transfer c o n t r o l . gave a thorough comparison of c o r r e l a t i o n s for N0 . A f a c t o r of 5 i s easy to o b t a i n f o r m w i t h respect to an empty tube. gas-liquid-solid) . 1983 | doi: 10..5) : mass t r a n s f e r e f f e c t s . J.acs.ch006 m Conclusion : areas f o r f u t u r e research.l i q u i d r e a c t o r s (150) and T a v l a r i d e s and Stamatoudis f o r l i q u i d . i n c l u d i n g use w i t h gases (164).l i q u i d d i s p e r s i o n s . For i n s t a n c e . w i t h the Hi-Mixer (161).

How­ ever. 1983 | doi: 10. Another area where micromixing plays a c a r d i n a l r o l e i s con­ tinuous p o l y m e r i z a t i o n .. This p o i n t i s a c t u a l l y very important but deserves a s p e c i a l review.org Publication Date: July 28. complete flow i n v e r s i o n ( r 2 = 1 ~ \> W2 = 1 " Wj). DC. This author proposed a model which c o n s i s t s of a t u b u l a r r e a c t o r comprising Ν zones i n laminar flow ( p a r a b o l i c v e l o c i t y p r o f i l e ) . p o l y m e r i z a t i o n s ) but the published data are s t i l l very scarce and a d d i t i o n a l informa­ t i o n i s r e q u i r e d f o r assessing these p o s s i b i l i t i e s . S t a t i c mi­ xers could be used as chemical r e a c t o r s f o r s p e c i f i c a p p l i c a t i o n s (reactants having large v i s c o s i t y d i f f e r e n c e s . . American Chemical Society: Washington. There­ fore a thorough d i s c u s s i o n of mixing e f f e c t s i n polymer r e a c t o r s would go beyond the scope of t h i s paper. p a r t i a l i n v e r s i o n . as has been pointed out i n the preceding Sections i n the case of f a s t r e a c t i o n s w i t h unmixed r e a c t a n t s . Beside s t a t i c mixers. The RTD i n a Kenics mixer comprising 8 elements could be r e ­ presented by t h i s model w i t h Ν = 3 and complete mixing. The p r a c t i c a l examples of combustion and r e a c t i o n s i n l i q u i d suspension are e s p e c i a l l y i l l u ­ minating i n t h i s respect. et al. a mere i n t e l l e c t u a l e x e r c i s e f o r academics who are short of o r i g i n a l PhD subjects ? I t i s true that micromixing e f f e c t s can g e n e r a l l y be neglec­ ted i n the design of r e a c t o r s f o r simple and slow r e a c t i o n s . and induce dramatic v a r i a ­ t i o n s i n the d i s t r i b u t i o n of products.178 C H E M I C A L REACTION ENGINEERING Mixing i n s t a t i c mixers considered as chemical r e a c t o r s was e s s e n t i a l l y s t u d i e d by Nauman ( 165. Wei. i n t h i s way the f l o w r a t e i s kept unchanged . and was reviewed by Nauman ( 173) and Gerrens ( 174) a few years ago. there are p r a c t i c a l l y no a l t e r n a t i v e s to the " u b i q u i t o u s " s t i r r e d tank. F i r s t estimations show that an "informed" mixing system. ACS Symposium Series. Mixing between each zone i s achieved accross a plane by a permutation of the r a d i a l po­ s i t i o n of f l u i d p a r t i c l e s ( r j ^ » τ^). Ν = 0 c o r r e s ­ ponds to a CSTR and Ν °° to a plug-flow r e a c t o r . 2012 | http://pubs. Downloaded by CORNELL UNIV on December 2. I t i s l i k e l y that s i g n i - In Chemical Reaction Engineering—Plenary Lectures. 171. i f one excepts loop r e a c t o r s (167) and the somewhat s p e c i a l back-flow mixer ( 168). I t i s shown that the best chemical conversion i s obtained w i t h complete flow i n v e r ­ s i o n . and w i l l not be t r e a t e d i n t h i s paper. J. The subject i s t r e a t e d elsewhere i n t h i s Symposium.. An example of the importance of mixing e f f e c t s i n chemical reactors : continuous f r e e r a d i c a l p o l y m e r i z a t i o n .1021/bk-1983-0226. I n the f i r s t case. Imagining en­ t i r e l y new p r i n c i p l e s f o r mixing r e a c t a n t s i s a challenge f o r f u ­ ture researchers. chemical conversion could be e n t i r e l y c o n t r o l l e d by mixing. working as a Maxwell demon would be much more e f f e c t i v e than our present devices (169). Several cases are considered : complete mixing (permutation at random). The reader w i l l f i n d the s t a t e of the a r t and a l i t e r a t u r e survey i n three e x c e l l e n t papers (170. 166). 172).acs. 1983.ch006 T Mixing of S o l i d s . One might now ask the question : are segregation e f f e c t s r e a l l y important i n p r a c t i c e or i s micromixing "a s o l u t i o n i n search of a problem" (173).

even i f encouraging progress has been made i n t h i s d i r e c t i o n . Besides these l a b o r a t o r y experiments.p r i o r i p r e d i c t i o n s from the s o l e knowledge of physicochemical p r o p e r t i e s and operating parameters. and w e l l micromixed flow (M). segregation and micromixing .f A > 2R k R + M *—> R k Initiation P Propagation t P R + Ρ >Ρ + R Transfer to Polymer Downloaded by CORNELL UNIV on December 2. where problems have been attacked from s e v e r a l d i r e c t i o n s (turbulence theory. L i m i t i n g curves f o r segregated flow (S) and w e l l micromixed flow (M) were c a l c u l a t e d from batch experiments.ch006 k R + R -—> Ρ + Ρ Termination ( D i s p o r p o r t i o n a t i o n ) F i g u r e 14 shows a p l o t of the D i s p e r s i o n Index DI = M /M wersus the conversion X of the monomer f o r segregated flow (S. Without r e p e a t i n g the conclusions drawn at the end of each In Chemical Reaction Engineering—Plenary Lectures. Moreover. 2012 | http://pubs.. there i s s t i l l a need f o r a u n i f i e d theory a l l o w i n g a . The se­ cond example i s an experimental one (176). w t General c o n c l u s i o n The end of t h i s survey leaves us w i t h the f e e l i n g that r e ­ search on mixing i n chemical r e a c t o r s i s a very l i v e l y area. namely an i n v e r s i o n of the r e l a t i v e p o s i t i o n of S and M curves when the t r a n s f e r constant k p i s increased. P o l y m e r i z a t i o n and polycondensation r e a c t o r s o f f e r s an es­ p e c i a l l y i n t e r e s t i n g f i e l d f o r f u t u r e a p p l i c a t i o n s of micromixing. This doesn't happen w i t h concentrated and f a s t i n i t i a t o r . Wei. but they are d i f ­ f i c u l t to assess because of a lack of published data. The f i r s t example i s a simula­ t i o n o f f r e e r a d i c a l p o l y m e r i z a t i o n i n a CSTR. American Chemical Society: Washington. et al.1021/bk-1983-0226. The r e t a i n e d k i n e ­ t i c scheme i s kd. RTD and mixing e a r l i n e s s . an i n t e r e s t i n g e f f e c t i s observed w i t h d i l u t e d and slow i n i t i a t o r s . Two examples w i l l show the importance o f micromixing e f f e c t s on the s t r u c t u r a l c h a r a c t e r i s t i c s of polymers ( 175). Continuous polymeriza­ t i o n of styrene was c a r r i e d out i n a CSTR and i n cyclohexane s o l u ­ t i o n i n order to keep the v i s c o s i t y low and constant. even w i t h strong a g i t a t i o n and low v i s c o s i t y .acs.. 1983. VILLERMAUX 179 Mixing in Chemical Reactors f i c a n t progress has been made s i n c e these reviews. ACS Symposium Series. e s p e c i a l l y w i t h t r a n s f e r to po­ lymer. 1983 | doi: 10. . J. . The D i s p e r ­ s i o n Index was measured as a f u n c t i o n of space time and a g i t a t i o n speed. ) .6.org Publication Date: July 28. DC. as f o r instance i n r e a c t o r s f o r f r e e r a d i c a l p o l y m e r i z a t i o n of ethylene where the i n i t i a t o r feedstream i s l i k e l y to be mixed by an e r o s i v e process ( 175) . C l e a r evidence for segregation e f f e c t s can be seen on f i g u r e 15 which shows that p e r f e c t micromixing may be very d i f f i c u l t to achieve. I f the major concepts have been i d e n t i f i e d . The dramatic i n f l u e n c e of segregation can be n o t i c e d a t high conversion. the a n a l y s i s of indus­ t r i a l r e a c t o r s may a l s o r e v e a l segregation e f f e c t s . .

S =7.033 mol I T . Curves S (segre­ gated flow) and M (we11-micromixed flow) c a l c u l a t e d from batch experiments^ I n i t i a t o r : PERKADOX l 6 .8 04 t . ACS Symposium Series. 1983. k : k p = 1.22 mol I T . conversion X.033 1Γ' .. S . Free r a d i c a l p o l y m e r i z a t i o n i n a CSTR. M = 3. f = 0. space time. M = w e l l . 2 : k p = 3-5 x 1 0 mol L " h . Τ = 75 °C. A = 3 x 10" mol L . f = 0. 0.65 mol L " . k = 0. M = 6. D i s p e r s i o n Index DI vs.. S = 2.0i DI S 2-5 '~ s' _ / 2 . 3 1 5 d 1 1 Q 1 Q In Chemical Reaction Engineering—Plenary Lectures.85.33 h " (other parameters un­ changed) .Downloaded by CORNELL UNIV on December 2. 2012 | http://pubs. American Chemical Society: Washington. DC.X Figure ih. 3 : k = 1.2700 N-3600 / ^ ^---ΖΓ--* V .ch006 180 CHEMICAL REACTION ENGINEERING Q2 . E f f e c t of segregation on p o l y m e r i z a t i o n of styrene i n cyclohexane s o l u t i o n .org Publication Date: July 28.56 mol L " .1021/bk-1983-0226.segregated flow. V = 670 cm .m i c r O mixed flow. 1 1 1 1 Ρ 1 1 J 1 Q 3 1 t 1 1 1 1 t p t 1 1 1 d 3.5 x 10 L mol" h " . Standard CSTR with h b a f f l e s and a 6-blade t u r b i n e .* h k = 1.acs. .12 mol L"" ( s o l v e n t ) .5. 1983 | doi: 10. k = 0. Wei. D i s p e r s i o n Index DI v s . A = 3 x 10 mol L " .05 x I0h I T m o l " h " . Influence o f a g i t a t i o n speed. / / / % ^ ' / __/ N-100 RPM (o)N-300 x) ~ " " J ^ N-1800 3 N.05 χ 10 L mol" h"* . I = l i n e a r p o l y m e r i z a t i o n k = 5 x ιοί L mol". et al. Curves 2 t o U: T r a n s f e r t o polymer. A = 0. Q6 . k = 5 x 10" s " . M « —L - τ HOURS Figure 15. J.

ACS Symposium Series. These are f o r instance the space time τ f o r a continuous r e a c t o r . e. e. and one or s e v e r a l micromixing times t . Measurement of c o n c e n t r a t i o n f l u c t u a t i o n s should be developed. The method of " c h a r a c t e r i s t i c times" i s e s p e c i a l l y h e l p f u l f o r determining which processes are c o n t r o l l i n g . t = 1/kC^" . _K).v a r i a b l e p r o p e r t i e s and inhomogeneous r e a c t i n g media. one or s e v e r a l r e a c t i o n times. but s e v e r a l stages f o r mixing.1021/bk-1983-0226. DC. or T ^ (Lg/ε)^' .org Publication Date: July 28. Another c h a r a c t e r i s t i c of current r e ­ search i s a gradual and f o r t u n a t e merging between the E u l e r i a n approach of F l u i d Mechanics and the Lagrangian approach of Chemi­ cal Engineering. 27. each w i t h t h e i r own time constants should be considered. 1983. J. i n d u s t r y would plead f o r l e s s s o p h i s t i c a t e d mathematical models and more phenomenological models g i v i n g us more understanding of what's going on i n the tank" (10). the f i ­ nal s o l u t i o n to micromixing problems should not be sought i n t u r ­ bulence theory alone. a c h a r a c t e r i s t i c time f o r i n t e r n a l macromixing p a t t e r n . sometimes q u a n t i t a t i v e l y .l i q u i d .acs. 1 m 3 s m β c 1 R m 2 e D 1 c D G In Chemical Reaction Engineering—Plenary Lectures. p o s s i b l y i n s e r i e s or i n p a r a l l e l . t (erosion) or t ^ £ / ^ .g. There i s s t i l l a problem as to the u l t i m a t e stage of mixing by molecular d i f f u s i o n where i t i s not c l e a r whether the mixing time i s t = T ^ (Lg/ε) ' or t = ϋ ^ λΖ/Jb.g. there i s a general agreement f o r encouraging research on large volume r e a c t o r s . New ideas on e n t i r e l y novel mixing p r i n c i p l e s and equipments would a l s o be welcome. I n continuous r e a c t o r s .Downloaded by CORNELL UNIV on December 2. Among other recommendations (9. whose parameters could have a fundamental i n t e r p r e t a t i o n by t h i s theory. More a t t e n t i o n should be paid to i n ­ t e r n a l age d i s t r i b u t i o n s and r e l a t e d q u a n t i t i e s such as c i r c u l a ­ t i o n time d i s t r i b u t i o n s i n s t i r r e d tanks. but r a t h e r i n phenomenological i n t e r a c t i o n models. g a s . I t was thus e s t a b l i s h e d that the m i c r o f l u i d / m a c r o f l u i d volume r a t i o was n e a r l y equal to t ^ / t p . c o a l e s c e n c e . This i s the wish of most i n d u s t r i a l s : "In g e n e r a l .s o l i d systems and mixing of non newtonian f l u i d s . theory w i l l progress i n a d i r e c t i o n u s e f u l to p r a c t i t i o n e r s i f more experimen­ t a l data on r e a l i s t i c i n d u s t r i a l s i t u a t i o n s are a v a i l a b l e to r e ­ searchers . the c i r c u l a t i o n time t i n a s t i r r e d tank . models f o r mixing e a r l i n e s s d e s c r i b i n g the t r a n s f e r between Ente­ r i n g and Leaving Environments are superabundant. Further r e d u c t i o n of segregation by i n t e r a c t i o n between f l u i d p a r t i c l e s can be conve­ n i e n t l y represented by simple models (exchange w i t h the mean. 2 . But above a l l . Wei. American Chemical Society: Washington.. f l u i d s w i t h t i m e . 154).ch006 6. we may t r y to summarize the s i t u a t i o n as f o l l o w s : R e s i ­ dence time d i s t r i b u t i o n s are now a w e l l e s t a b l i s h e d t o o l but pro­ gress i s s t i l l d e s i r a b l e f o r m u l t i p l e i n l e t / o u t l e t systems.. or t _ = l/ω or ^ (v/ε) ' . un­ steady s t a t e operations. both i n presence and i n absence of chemical reac­ tions i n order to o b t a i n r e l i a b l e s p e c t r a l data. p e r f e c t l y defined hydrodynamic p a t t e r n s ) and new chemical t e s t r e a c t i o n s would be welcome i n t h i s respect. Comparison between a l l these times allows the determination of the mixing regime.g. et al. 2012 | http://pubs.d i s p e r s i o n ) . C a r e f u l l y designed experiments (no macromixing e f f e c t s . 1983 | doi: 10. e. However. VILLERMAUX 181 Mixing in Chemical Reactors S e c t i o n .

V. Pergamon Press. Maisonneuve. 739-741 Bennani. 2. Tobgy. AIChE Mee­ ting 9-12. National Science Foundation Workshop. D. Eng. Danckwerts". J. J. J. S. Ito. Mathieu..N.C. 23. G.org Publication Date: July 28.S. 1975 Brodkey. Chem. 1981. Comm. August 2126. Eng. 18. 2012 | http://pubs. 1-15 Danckwerts. 31.. Quigley.A. J. P. . 93-99 Zwietering. A. R. 8. 8. Sci. Acad. 1981.H. Villermaux. Chem. 22.acs. Chemical Eng. Nov.. "Application of Turbulence Theory to Mixing Operations". New Orleans Nov 8-12.8. R. Eng. REACTION ENGINEERING Cited Nauman. Gence.H. F. April 27-29. J. W. 1981.L. Α. Commun. Eng. 53-131 Brodkey. Mathieu. Mi­ xing. J. Tokyo.L.. T. Chem.B. Japan 1975. M. Bockelman. Louisiana. Commun. A. Commun. K.W. 24. P. Y. 303-312 Käppel.. S. Alcaraz. Stamatoudis.. DC. Lorraine. 33. Tookey.. Alcatraz E. W. Second Europ. J. Chem. Ser. Kuoppamäki. 27. J. 4. R. 1982. 1979.F.W. 14. Press. 293. J.S. D. S. Paris 1981. Chem. New Orleans.S.R.V. Eng. Oxford 1981 Danckwerts. 341 Ogawa. 1981. Commun. Sci. 1982.N.. Montreal 1981 Oct 4-9.K.J. 1959. II. Selec­ ted papers of P. 8. 5. Eng.571-590 Lehtola. L. 1978. 199-273 Ritchie. ACS Symposium Series. 641-644 Bennani.. 15. BHRA Fluid Engineering Paul.R.197-204 Brodberger. 8. Sci. Acad. Sci. 1981. Conf. Sci. 133-164 Tavlarides. (BHRA Fluid Engineering). 74th Annual AIChE Mee­ ting. Internat.. J.. D.. New-York.13. 15. 1. Chem. 26. 1982. Polytech. Acad. Zuniga-Chaves.V. 10. 185-191 Edwards. Eng. Paper A1. Adv. David.E. Eng. 2.R. (BHRA Fluid Enginee­ ring)... J. on Mixing. Diena. 1-10 Danckwerts. II.148-151 Ogawa. Fund. 25-52 Tavlarides.21. 6. P.324-326 Brodkey. Downloaded by CORNELL UNIV on December 2. Luss. These. 397-401 Villermaux. Rindge. G. R. 11. 293. M. Conference on Mixing.. 1981. Cambridge 1977. Research 1952. Edwards. 8-12. 37. Chem...R. VDI Forschungsheft 578.K.R. J. et al. Acad. Ito. 11. Eng.. Etchells.1021/bk-1983-0226. S.T. 7.. I Fundamen- In Chemical Reaction Engineering—Plenary Lectures. Principles and applications". David.... Α. 791-794 Palepre. Mathieu. 13. W. C. Eng. in press and Proceedings 2nd World Congress Chem. Paris 1981. Eng. Eng. Ser. Commun. K. 1976. 1981. New Orleans. 1983. Eng. Fundam.H. Japan 1980. J. 3. Sci. 29. Nusim. Villermaux.. 4. American Chemical Society: Washington. Conf. Multiphase chemical reactors. Paper 18f. Proceed. R. Internat. M. 3. Matsumura.. 1981 Barthole.. 17. E. New Hampshire Short. Eng.M. R. 249-264 Cheng. Gence. Adler. E.. 11. 1976 Käppel.. 17-26 Patterson. 30. 8. Chem. J.182 CHEMICAL Literature 1. P. April 27-29 1982. Proceedings of the Fourth Europ. S. Chem. 279-298 Nagata. J. Sklarz. C. L. Ser. AIChE 1981 Annual Meeting. Paper J1. J. Mathieu. 32... J. II.P. Nat.G. Ind. 1975 Hiby. Chem. paper 18c.V.W.V. of Chem. Chem. 1-23 Patterson. Paris 1981. Chem. Worley. J.J. Inst.N. Α. Wei. "Mixing.L. "Insights into Chemical Engineering.. C. 1981. Eng. 19 20. R. 25. Chem. R. 293.ch006 9. 21. B.L. 16. J. E.19.. 1983 | doi: 10. Proceedings of the Fourth Europ. 12. Appl.. 28. Vol.J. Kodansha Ltd. Sc. D. R.. 1958. Eng. Paper n° 61c Bennani. Chem. Adler. 1977..

6.

VILLERMAUX

34.
35.
36.
37.
38.
39.

Downloaded by CORNELL UNIV on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch006

40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.

Mixing in Chemical Reactors

183

tals, A.E. Rodrigues, J.M. Calo and N.H. Sweed Editors, Nato
Adv. Study Inst. Series, E-N° 51, Sijthoff and Noordhoff,
1981, 285-362
Mao, K.W.; Toor, H.L. Ind. Eng. Chem. Fund. 1971,10,192-97
Vassiliatos, G.; Toor, H.L. AIChE J. 1965,11,666-673
Bennani, Α.; Mathieu, J. C.R. Acad Sci. Paris 1982, 294, Ser.
II, 933-936
McKelvey, K.N.; Yieh, H.N.; Zakanycz, S.; Brodkey, R.S. AIChE
J., 1975, 21, 1165-1176
Berker, Α.; Whitaker, S. Chem. Eng. Sci. 1978, 33, 889-895
Canon, R.M.; Wall, K.W.; Smith, A.W.; Patterson, G.K. Chem.
Eng. Sci. 1977, 32, 1349-1352
Waggoner, R.C.; Patterson, G.K. ISA Transactions, 1975, 14,
331-339
Bourne, J.R.; Toor, H.L. AIChE J. 1977,23,602-604
Vidal,C.; Roux, J.C.; Rossi, Α.; Bachelart, S. C.R. Acad. Sc.
Paris 1979, t. 289, Série C, 73-76
Marek, M.; Havlicek, J.; Ulcek, J. Proceedings of the fourth
europ. Conf. on Mixing, April 27-29 1982, (BHRA Fluid Engi­
neering) 339-354
Humphrey, J.A.C. Chem. Eng. Commun. 1980, 345-361
Tarbell, J.M.; Petty, C.A. Chem. Eng. Sci. 1977, 32, 1177-88
Pratt, D.T. Prog. Energy Combust. Sci. 1976, 1, 73-86
Gouldin, F.C. Comb. Sci. and Technol. 1973, 1, 33-45
Bilger, R.W. Comb. Sci. and Technol. 1979,19,89-93
Nelson, H.F. Letters Heat and Mass Transfer 1979, 6, 23-33
Spalding, D.B. Combust. Sci. and Technol. 1976,13,3-25
Lockwood, F.C. Combustion and Flame 1977, 29, 111-122
Lockwood, F.C.; Syed, S.A. Comb. Sci. and Technol. 1979, 19,
129-140
Pratt, D.T. J. Energy 1979,3,177-180
Hébrard, P.; Magre, P. 54th AGARD/PEP Conf. Proceedings,
Oct. 1979, Cologne (Allemagne), N° 275
Wen, C.Y.; Fan, L.T. "Models for flow systems and chemical
reactors" Dekker, New-York, 1975
Villermaux, J. "Génie de la Réaction Chimique. Conception et
fonctionnement des réacteurs",
Technique et Documentation,
Paris, 1982
Nauman, Ε.B. Chem. Eng. Sci. 1981, 36, 957-966
Roth, D.P.; Basaran, V.; Seagrave, R.C. Ind. Eng. Chem. Fun­
dam. 1979, 18, 376-383
Rautenbach, R.; Waschmann, M.; Van Gilse, J. Chem. Ing. Technik 1981, 53, 726-728
Treleaven, C.R.; Tobgy, A.H. Chem. Eng. Sci. 1971, 26, 1259
Ritchie, B.W.; Tobgy, A.H. Ind. Eng. Chem. Fund. 1978,17,287
Buffham, B.A.; Kropholler, H.W. Ind. Eng. Chem. Fundam. 1981
20, 102-104
Bourne, J.R.; Giger, G.K.; Richarz, W.; Riesen, W. The Chem.
Eng. Journal 1976, 12, 159-163
Conochie, D.S.; Gray, N.B. Chem. Eng. Sci. 1978, 33, 619-621
Quraishi, M.S.; Fahidy, T.Z. Chem. Eng. Sci. 1982, 37, 775
Castellana, F.S.; Spencer, J.L.; Cartolano, A. Ind. Eng. Chem.
Fundam. 1980,19,222-225
Chen, M.S.K. Chem. Eng. Sci. 1971, 26, 17-28
Spencer, J.L.; Lunt, R.; Leshaw, S.A. Ind. Eng. Chem. Fundam.
1980,19,135-141

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

Downloaded by CORNELL UNIV on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch006

184

C H E M I C A L REACTION

ENGINEERING

69. Weinstein, H.; Adler, J. Chem. Eng. Sci. 1967, 22, 65-75
70. Villermaux, J.; Zoulalian, A. Chem. Eng. Sci. 1969, 24, 1513
71. Plasari, E.; David, R.; Villermaux, J. A.C.S. Symp. Series,
Chem. React. Eng. Houston 1978, 65, 126-139
72. NG, D.Y.C.; Rippin, D.W.T. 3rd Europ. Symp. Chem. React. Eng.
Amsterdam 1964, Pergamon Press, Oxford 1965, 161-165
73. Valderrama, J.L.; Gordon, A. Chem. Eng. Sci. 1979, 34, 1097
74. Valderrama, J.L.; Gordon, A. Chem. Eng. Sci. 1981, 36, 839-44
75. Chien-Ping Chai; Valderrama, J.L. Chem. Eng. Sci. 1982, 37,
494-496
76. Ritchie, B.W. Chem. Eng. Sci. 1982, 37, 800
77. Treleaven, C.R.; Tobgy, A.H. Chem. Eng. Sci. 1972, 27, 1497
78. Ritchie, B.W. The Canad. J. of Chem. Eng. 1980, 58, 626-633
79. Ritchie, B.W.; Tobgy, A.H. The Canad. J. Chem. Eng. 1977, 55,
480-483
80. Ritchie, B.W.; Tobgy, A.H. Adv. Chem. Ser. Am. Chem. Soc.
1974, 133, 376-392
81. Nauman, E.B. Chem. Eng. Sci. 1975, 30, 1135-1140
82. Spielman, L.A.; Levenspiel, O. Chem. Eng. Sci. 1965, 20, 247
83. Kattan, Α.; Adler, R.J. Chem. Eng. Sci. 1972, 27, 1953
84. Villermaux, J. to be published
85. Treleaven, C.R.; Tobgy, A.H. Chem. Eng. Sci. 1972, 27, 1653
86. Treleaven, C.R.; Tobgy, A.H. Chem. Eng. Sci. 1973, 28, 413-25
87. Ritchie, B.W.; Tobgy, A.H. The Chem. Eng. J. 1979,17,173
88. Mehta, R.V.; Tarbell, J.M. Private communication
89. Makataka, S.; Kobayashi, J. Int. Chem. Eng. 1976,16,148-154
90. Dudukovic, M.P. Ind. Eng. Chem. Fundam. 1977,16,385-388
91. Dudukovic, M.P. Chem. Eng. Sci. 1977, 32, 985-994
92. Dudukovic, M.M. AIChE Journal, 1977, 23, 382-385
93. Takao, M.; Murakami, Y. J. Chem. Eng. Japan 1976, 9, 336-338
94. Takao, M.; Nomoto,O.;Murakami, Y.; Sato, Y. J. Chem. Eng.
Japan 1979,12,408-410
95. Parini, K.; Harris, T.R. The Canad. J. Chem. Eng. 1975, 53,
175-183
96. Wood, T.; Hop, N.H. Proceed. Second Europ. Conf. Mixing,
Cambridge, 1977, BHRA Fluid Engineering
97. Spencer, J.L.; Lunt, R.R. Ind. Eng. Chem. Fund. 1980, 19, 142
98. Beek Jr, J.; Miller, R.S. Chem. Eng. Prog. Symp. Series 1959
55, 23-28
99. Ottino, J.M.; Ranz, W.E.; Macosko, C.W. Chem. Eng. Sci. 1979
34, 877-890
100. Ottino, J.M. Chem. Eng. Sci. 1980, 35, 1377-1391
101. Ranz, W.E. AIChE Journal, 1979, 25, 41-47
102. Ottino, J.M. AIChE Journal 1981, 27, 184-192
103. Ottino, J.M.; Ranz, W.E.; Macosko, C.W. AIChE Journal, 1981
104. Ranz, W.E. AIChE Journal 1982, 28, 91-96
105. Ottino, J.M. J. Fluid Mech. 1982, 114, 83-103
106. Chella, R.; Ottino, J.M. To be presented at ISCRE 7
107. Ottino, J.M.; Macosko, C.W. Chem. Eng. Sci. 1980, 35, 1454-57
108. Klein, J.P. David, R.; Villermaux, J. Ind, Eng. Chem. Fundam.
1980,19,373-379
109. Zoulalian, Α.; Villermaux, J. Adv. Chem. Series. Chem. React.
Eng. II Evanston, 1974, 133, 348-361
110. Villermaux, J. to be published
111. Belevi, H.; Bourne, J.R.; Rys, P. Helv. Chem. Acta, 1981, 64,
1618-1629

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

Downloaded by CORNELL UNIV on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch006

6.

VILLERMAUX

Mixing in Chemical Reactors

112. Belevi, H.; Bourne, J.R.; Rys, P. Chem. Eng. Sci. 1981, 36,
1649-1654
113. Bourne, J.R.; Kozicki, F.; Moergeli, U.; Rys, P. Chem. Eng.
Sci. 1981, 36, 1655-1663
114. Angst, N.; Bourne, J.R.; Sharma, R.N. Chem. Eng. Sci. 1982
585-590
115. Bourne, J.R.; Rohani, S. Proceedings of the Fourth Europ.
Conf. on Mixing, April 27-29 1982, PaperJ2,313-325
116. Bourne, J.R.; Schwartz, G.; Sharma, R.N. Proceedings of the
fourth Europ. Conf. on Mixing, April 27-29 1982, (BHRA Fluid
Engineering), Paper J1, 327-338
117. Pohorecki, R.; Baldyga, J. Third Internat. Summer School. Mo­
delling of heat and mass transfer processes and chemical
reactors, Varna, May 21-30 1979.
118. Miyawaki, O.; Tsujikawa, H.; Uraguchi, Y. J. Chem. Eng. Japan
1975, 8, 63-68
119. Rys, P. Angew. Chem. Int. Ed. Engl. 1977,16,807-817
120. Nabhotz, F.; Ott, R.J.; Rys, P. Helv. Chim. Acta 1977, 60, 2926
121. Belevi, H.; Bourne, J.R.; Rys, P.; Helv. Chem. Acta, 1981,
64, 1630-1644
122. Bourne, J.R. AIChE 1981 Annual Meeting, New Orleans, Nov 8-12
Paper n° 61a
123. Spalding, D.B. Levich Birthday Conf. on phys. chem. hydrody­
namics, Oxford, 11-13 July 1977
124. Bourne, J.R.; Rys, P.; Suter, K. Chem. Eng. Sci. 1977, 32, 711
125. Nabholtz, F.; Rys, P. Helv. Chem. Acta 1977, 60, 2937-43
126. Bourne, J.R.; Kozicki, F. Chem. Eng. Sci. 1977, 32, 1538-39
127. Belevi, H.; Bourne, J.R.; Rys, P. Helv. Chem. Acta 1981, 64,
1599-1617
128. Barthole, J.P.; David, R.; Villermaux, J. Proceedings ISCRE 7
Boston 1982, Oct. 4-6
129. Bourne, J.R.; Kozicki, F.; Rys, P. Chem. Eng. Sci. 1981, 36,
1643-1648
130. Takao, M.; Yamato, T.; Murakami, Y.; Sato, Y. J. Chem. Eng.
Japan, 1978,11,481-486
131. Murakami, Y.; Takao, M.; Nomoto,O.;Nakayama, K. J. Chem.
Eng. Japan 1981,14,196-200
132. Hanley, T.R.; Call M.L. 74th Annual AIChE Meeting, New Orleans
Nov 8-12, 1981, paper 18d
133. Ghodsizadeh, Y.; Adler, R.J. 74th Annual AIChE Meeting, New
Orleans, Nov. 8-12, 1981 paper 6li.
134. Bhatt, B.L.; Ziegler, E.N. AIChE Journal, 1977, 23, 217-224
135. Bryant, J. Adv. in Biochem. Eng. 1977, 5, 101-123
136. Costa, P.; Lodi, G. The Canad. J. Chem. Eng. 1977,55,477-79
137. Bourne, J.R.; Crivelli, E.; Rys, P. Helv. Chem. Acta, 1977,
60, 2944-2957
138. Sasakura, T.; Kato, Y.; Yamamuro, S.; Ohi, N. Internat. Chem.
Eng. 1980, 20, 251-258
139. Rachez, D.; David, R.; Villermaux, J. Entropie, 1981, N° 101,
72, 32-39
140. Bryant, J.; Sadeghzadeh, S. Proceed. Third Europ. Conf. on
Mixing, April 4-6th 1979, York, BHRA Fluid Eng. paper F3, 325
141. Bryant, J.; Sadeghzadeh, S. Proceed. Fourth Europ. Conf. on
Mixing, April 27-29 1982, BHRA Fluid Eng., Paper B4, 49-56
142. Brennan, D.J.; Lehrer, I.H. Trans. I. Chem. Eng. 1976,54, 139
143. Khang, S.J., Levenspiel, O. Chem. Eng. Sci. 1976,31,569-77

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

Downloaded by CORNELL UNIV on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch006

186

C H E M I C A L REACTION

ENGINEERING

144. Okamoto, Y.; Nishikawa, M.; Hashimoto, K. Int. Chem. Eng.
1981, 21, 88-94
145. Van der Molen, K.; Van Maanen, H.R.E. Chem. Eng. Sci. 1978,
33, 1161-68
146. Nishikawa, M.; Okamoto, Y.; Hashimoto, K.; Nagata, S. J.
Chem. Eng. Japan 1976,6,489-494
147. Fort, I.; Placek, J.; Kartky, J.; Durdil, J.; Drbohlav, J.
Collect. Czechoslov. Chem. Comm. 1974,39,1810-1822
148. Mann, R.; Mavros, P.P.; Middleton, J.C. Trans. I. Chem. Eng.
1981, 59, 271-278
149. Mann, R.; Mavros, P. Proceedings of the Fourth Europ. Conf.
on Mixing, April 27-29, 1982, BHRA Fluid Eng. Paper B3, 35-47
150. Joshi, J.B.; Pandit, A.B.; Sharma, M.M. Chem. Eng. Sci. 1982,
37, 813-844
151. Rod, V.; Misek, T. Trans. Inst. Chem. Eng. 1982, 60, 48-53
152. Oldshue, J.Y. A.C.S. Symp. Series, 1977, 55, 224-241
153. Oldshue, J.Y. Chemtech. September 1981, 554-561
154. Kipke, K. Chem. Ing. Tech. 1982, 54, 416-425
155. Quraishi, A.Q.; Mashelkar, R.A.; Ulbrecht, J.J. AIChE Journal
1977, 23, 487-492
156. Ulbrecht, J.J.; Sema Baykara; Z.; Chem. Eng. Commun. 1981, 10
165
157. Lane A.G.C.; Rice, P. Trans. I. Chem. E. 1982, 60, 171-176
158. Okamoto, Y.; Nishikawa, N.; Hashimoto, K. Int. J. Chem. Eng.
1981, 21, 88-94
159. Pahl, M.H.; Muschelknautz, E. Int. Chem. Eng. 1982, 22, 197
160. Boss, J.; Czastkiewicz, W. Int. Chem. Eng. 1982, 22, 362-367
161. Matsumara, K.; Morishima, Y.; Masuda, K.; Ikanaga, H. Chem.
Ing. Tech. 1981, 53, 51-52
162. Henzler, H.J. Chem. Ing. Tech. 1979,51,1-8
163. Gross-Röll,
F. Int. Chem. Eng. 1980, 20, 542-549
164. Bürgi, R.; Tauscher, W.; Streiff, F. Chem. Ing. Tech. 1981,
53, 39-42
165. Nauman, E.B. The Can. J. Chem. Eng. 1982, 60, 136-140
166. Nauman, E.B. AIChE Journal, 25 (1979), 246-258
167. Murakami, Y.; Hirose, T.; Ono, S.; Eltoku, H.; Nishijima, T.
Ind. Eng. Chem. Process Pes. Dev. 1982,21,273
168. Brauer, H. Chem. Ing. Tech. 1980, 52, 992-993
169. Le Goff, P. Proceed. 2nd Europ. Conf. on Mixing, Cambridge,
March 1977
170. Ries, Η.Β. Int. Chem. Eng. 1978,18,426-442
171. Müller, W. Chem. Ing. Tech. 1981, 53, 831-844
172. Sommer, Κ. Fortschritte der Verfahrenstechnik 1981, 18, 189
173. Nauman, E.B. J. Macromol. Sci. Revs. Macromol. Chem. 1974,
CIO, 75-112
174. Gerrens, H. Proceed. 4th Int. Symp. Chem. React. Eng. Heidelberg, 1976, 584-614
175. Villermaux, J. Colloquium of the Working Party C.R.E. Novare,
may 25-26, 1981
176. Sahm, P. Thèse, Inst. Nat. Polytech. Lorraine, 1978
177. Olson, J. H.; Stout, L. E. In "Mixing--Theory and Practice,"
Vol. II, Uhl and Gray, Eds.; Academic: New York, 1967.
RECEIVED April 15, 1983

In Chemical Reaction Engineering—Plenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.

design. 2012 | http://pubs. carbon combustion e f f i c i e n c y . methanol conversion products 23 Ash d i f f u s i o n c o n t r o l in atmospheric pressure f l u i d bed combustor 87 Atmospheric pressure f l u i d bed combustor bed height and pressure drop 67-69 bed temperature 69-73 carbon combustion efficiency 80-87 Atmospheric pressure f l u i d bed combuster—Conti nued c o n t r o l l i n g parameters 65-93 flow regimes and immersed tubes 92-93 f l u i d mechanics and flow regime 72-78 p a r t i c l e s i z e and s u l f u r capture 69-73 v o l a t i l e evolution 87-92 A t t r i t i o n r a t e . f l u i d i z e d bed combustor cross-sectional 69. .s c a l e cold flow model design 44 Band-aging in methanol-togasol ine process 25-27 Batch s t i r r e d tank. . world capacity and expected growth 1021 A c t i v a t i o n energy in s t i r r e d tank r e a c t o r 14 Adiabatic r e a c t o r s 28f Age d i s t r i b u t i o n . homogeneous i s o t r o p i c turbulence 138-41 Β Background. band. ACS Symposium Series. 40f f u l l .org Publication Date: July 28.acs. . instantaneous i n t e r n a l . mixing theory 154 A c r y l o n i t r i l e . h i s t o r i c a l survey of mathematics 1-15 Baffles f l u i d bed r e a c t o r . DC.. 1983 | doi: 10.s e c t i o n a l area 68. polymerization r e a c t i o n s .. American Chemical Society: Washington. heats of polymerization 1061 AeryIon i t r ile-butadienestyrene polymer.Downloaded by ILLINOIS STATE UNIV on December 2. polymerization mechanism 105t Anionic polymerization reactions 103-7 Area. methanol-togasoline process 25-27 A i r a d d i t i o n and nitrogen oxide emission 90-92 Air flow r a t e in atmospheric pressure f l u i d i z e d bed combustor 67-69 A l k y l a t e . . population balance method 147-48 Age domain.72-78 distributor plate 77 tube 78-80 Aromatics. .. in f l u i d bed r e a c t o r c r o s s . homogeneous i s o t r o p i c turbulence 138-41 Bead polymerization 109t Bed—See also F l u i d bed Bed. Wei. 143 B i f u r c a t i o n . et al.ix001 INDEX Accumulator volume. Hopf 13-14 B i f u r c a t i o n diagrams 11-12 189 In Chemical Reaction Engineering—Plenary Lectures. 110-14 A u t o c o r r e l a t i o n . 109t Batchelor microscale. . 83-85 Autocatalytic kinetics. . . 1983. J.1021/bk-1983-0226.. product y i e l d s from methanol-to-gasoline processes 42t Amides.72-78 density of s o l i d s 67-69 height 50-55. s o l u t i o n polymerization in a continuous flow s t i r r e d tank r e a c t o r .. 67-69 length and gas r e c y c l e system 34 temperature 69-73 weight 67-69 Belousov-Zhabotinsky r e a c t i o n in continuous flow s t i r r e d tank r e a c t o r . mixing earliness 151-63 Aging.

65-93 bed c r o s s . f u l l .s t y r e n e polymer..190 CHEMICAL REACTION Downloaded by ILLINOIS STATE UNIV on December 2.. 72-78 bed height and pressure drop 67-69 bed temperature 69-73 carbon combustion efficiency 80-87 f l u i d mechanics 72-78 heat of r e a c t i o n 69 immersed tubes and flow regimes 92-93 particle size 69-73 reactions 66 reactors 55-56 In Chemical Reaction Engineering—Plenary Lectures. using f l u i d bed atmospheric pressure c o n t r o l l i n g parameters. DC. scaled-up f i x e d bed r e a c t o r 35t. . f l u i d bed 56 for propylene polymerization 120-24 z e o l i t e .. mixing theory 156-64 Coke formation in methanolto-gasoline conversion 25-27.s e c t i o n a l area and flow regime.s c a l e cold flow model 44 in s t i r r e d tanks. product y i e l d s from methanol-to-gasoline processes 42t Cascade. American Chemical Society: Washington.s c a l e . 80-87 feed l o c a t i o n 87-90 f l u i d mechanics 66. conversion of limestone 69-73 CaIderbank-Moo-Young c o r r e l a t i o n f o r small p a r t i c l e s immersed in turbulent media 167 Carbon combustion e f f i c i e n c y in atmospheric pressure f l u i d bed combustor 80-87 Carbon dioxide and monoxide. 103-7 Chaotic behavior 13 Chemical r e a c t i o n and mixing 169-70 Chemical r e a c t o r s — S e e Reactors Circulation of c a t a l y s t f o r f u l l . i n t e r n a l pattern 176-77 Closure problem 141 Coal 19 Coal combustion reactions 66. 109t Catalysis s o l i d polymerization. f o r methanol-to-gasoline process 19-23 C a t a l y s t bed length in commercial plant 34 C a t a l y s t d e a c t i v a t i o n in methanol-to-gasoline process 25-27 C a t a l y t i c reactors durene conversion 37 f l u i d i z a t i o n and heat transfer 67 ENGINEERING C a t i o n i c polymerization reactions 103-7 C e l l models. shape-selective. f i r s t c y c l e y i e l d . 1983 | doi: 10..74-78.87-90 r e a c t o r s . et al. random model.s c a l e cold flow model 44 cracking.42t C Calcium carbonate—See Limestone Calcium s u l f a t e . f l u i d bed 55-56 atmospheric pressure controlling parameters 65-93 feed diameter s e l e c t i o n . 2012 | http://pubs. f u l l .72-78 heat t r a n s f e r 66. olefin 120-24 s o l u t i o n polymerization k i n e t i c s in a continuous flow s t i r r e d tank reactor 110-14 Catalyst c i r c u l a t i o n . . 1983. .92 Bundle o f p a r a l l e l tubes model 145-57 Butadiene.org Publication Date: July 28.75-77 rise velocity 66-67. 103-7 Combustion. b a f f l e design and c a t a l y s t circulation 44 Combination termination in polymerization r e a c t i o n s .42t Cold flow model. world capacity and expected growth 1021 η-Butane and butènes. ACS Symposium Series. .. s t i r r e d tank polymerization r e a c t i o n s . c o a l . . . Wei. . J.78-87 Coal-to-gasoline v i a methanol 20f Coalescence-dispersion process 142 Coalescence-dispersion process.ix001 Bubbles in f l u i d bed reactor diameter 50-55.acs.1021/bk-1983-0226. heats of polymerization 106t Butad iene-acryIon i t r i l e . mixing theory 176 Chain t r a n s f e r in polymerization r e a c t i o n s ..

mixing theory 178-79 Convective f l u x e s . mixtures with v a r i a b l e density 148-49 s t i r r e d tank 49 Belousov-Zhabotinsky reaction 143 polymerization r e a c t i o n s . American Chemical Society: Washington. 1983. r e c y c l e operation in f i x e d bed reactors 27 Cracking c a t a l y s t in f l u i d bed 56 Cross!inking in polymerization reactions 103-7 Cross-sectional area of f l u i d bed 69. reactor residence time in s o l u t i o n polymerization 113f Conversion of energy.72-78 CSTR—See Continuous flow reâcTor. DC. methanol-to-gasoline process 25-27 Dealkylation of durene 37 Deethanizer 38f Degree of homogeneity. in polymerization reactions 110-15 Concentration d i s t r i b u t i o n 136 Concentration f l u c t u a t i o n s . and carbon combustion efficiency 82-83 propylene.1021/bk-1983-0226. steady-state monomer. polymerization.. atmospheric pressure f l u i d bed combustor 78-80 Convective mixing 165-66 Convergence and i n f i n i t e s i m a l numbers 8 Conversion. vs. 109t Concentration oxygen. . mixing theory 137 Dehydration r e a c t i o n . 122f Corrsin equation 141-41 C o r r s i n microscale. p r o f i l e s in the m u l t i g r a i n model f o r c a t a l y t i c polymerization 120-24 solvent. using f l u i d bed—Continued s u l f u r capture 69-73 volatile evolution 87-90 Commercialization of methanolto-gasol ine process 32-44 of. methanol conversion products 23 D Damkohler numbers mixing models 170f for s t i r r e d tank r e a c t o r 14 Danckwert segregation index 136-38.. s t i r r e d tank Cyclohexane s o l u t i o n . polymerization mechanism. 1983 | doi: 10. homogeneous i s o t r o p i c turbulence 138-41 Cost. 32 Cooling in f i x e d bed reactor 27 in s t i r r e d tank r e a c t o r 14 Coordination polymerization reactions. 105t Core model. Wei.. turbulence theory 138-40 Concentration macroscale 137 Condensation polymerization. . scaled-up f i x e d bed reactor 35ti.42t Coolant f o r tubular r e a c t o r s .. .ix001 INDEX 191 Combustion. 103-7 Conductive f l u x e s and heat t r a n s f e r in atmospheric pressure f l u i d bed combustor 78-80 Configuration of z e o l i t e c a t a l y s t f o r methanolto-gasol ine process 21-23 Constructive theory of p a r t i t i o n s .org Publication Date: July 28. et al.. 23-25 Conversion reactor o u t l e t and i n l e t temperature. 2012 | http://pubs... heat t r a n s f e r . 103-7 Copolymers. ethylene-propylene..acs. . c o a l . ACS Symposium Series. e f f e c t of segregation on polymeri z a t i o n of styrene 178-79 C y c l o p a r a f f i n s . of methyl methacrylate 113f solution 110-14 Continuous f r e e r a d i c a l polymerization. 109t emulsion 114-20 free r a d i c a l 178-79 isothermal. e f f i c i e n c y in atmospheric pressure f l u i d bed combustor 69 Conversion r e a c t i o n of limestone to calcium carbonate 69-73 of methanol to hydrocarbons. polymerization r e a c t o r s . J.161 Deactivation. thermal to e l e c t r i c a l .Downloaded by ILLINOIS STATE UNIV on December 2.. . methanol-to-gasoline process 23 In Chemical Reaction Engineering—Plenary Lectures. c a t a l y s t . . Sylvester 3 Continuous fermentor 12 Continuous flow reactor steady s t a t e ..

... .. .147-48 r e a c t i o n time.1021/bk-1983-0226. DC. .. e f f i c i e n c y of conversion in an atmospheric pressure f l u i d bed combustor 69 E l u t r i a t i o n constant f o r p a r t i c l e s and carbon combustion e f f i c i e n c y 80-82 In Chemical Reaction Engineering—Plenary Lectures. mechanism in coal combustion 88-90 Dispersive mixing 166-67 D i s p r o p o r t i o n a t e in polymerization 103-7. Wei.. in mixing 166-69 of oxygen and carbon combustion e f f i c i e n c y . American Chemical Society: Washington...s c a l e r e a c t o r 58 Dolomite. k i n e t i c s in carbon combustion 85 molecular. . population balance method 145. .org Publication Date: July 28... .... ... ..34.. 44 f o r f l u i d i z e d bed r e a c t o r ... .. vs. 117f of dehydration r e a c t o r 37-39 of f i x e d bed r e a c t o r s . 67-93 of b a f f l e s f o r f u l l ... . 69 E l e c t r i c a l energy from thermal energy. 2012 | http://pubs. thermal to e l e c t r i c a l .. . mixing theory 170-71 Durene formation in methanolto-gasol ine process 25-27.. . s u l f u r capture 69-73 D r o p l e t . product yields 42t Density of atmospheric pressure f l u i d bed combustors... . ... ...37 E a r l i n e s s mixing in the age domain 151-64 E f f i c i e n c y in an atmospheric pressure f l u i d bed combustor of carbon combustion 80-87 of energy conversion.. 178-80 s o l i d .. s e l e c t i o n . 27. 1983 | doi: 10... convective and r a d i a t i v e c o n t r i b u t i o n s to heat transfer 78 of pores in s u l f a t i o n of limestone 70-73 D i f f e r e n t i a l equations in chemical r e a c t o r theory.d i f f u s i o n model. 69 of fans. gasoline 25-27 Distribution function instantaneous internal and l o c a l age. 4 0 f of bed s o l i d s in atmospheric pressure f l u i d i z e d bed combustor 67-69 of continuous flow s t i r r e d tank emulsion polymerization r e a c t o r .36f. .. 122f Dispersion index f o r polymerization..... .. J.ix001 192 CHEMICAL REACTION Dehydration r e a c t o r commercial f i x e d bed plant design 37-39 in methanol-to-gasoline processes. 82-83 ENGINEERING Dimethyl ether formation in methanol-to-gasoline process 23-25 Dirac d e l t a f u n c t i o n 8 D i s i n t e g r a t i o n of p a r t i c l e s and postulated morphological models f o r polymerization. mixing theory 149 Distributor plate in an atmospheric pressure f l u i d bed combustor 77 in a f u l l ... 80-87 of p a r t i c l e s in f l u i d bed r e a c t o r s 55 in f l u i d bed r e a c t o r s . ACS Symposium Series. 13 Diffusion of ash.. 1983.... c o n t r o l i n atmospheric pressure f l u i d bed combustor 87 e x t e r n a l .178-80 D i s s i p a t i o n of energy and carbon combustion efficiency 83-85 and homogeneous i s o t r o p i c turbulence 138-41 D i s t i l l a t i o n range..37-39 of methanol-to-gasoline reactor 23-32 of multibed r e a c t o r 29f of polymer r e a c t o r 103-7 probability functions 141-42 and residence time d i s t r i b u t i o n theory 145t and steady-state continuous r e a c t o r s . et al..Downloaded by ILLINOIS STATE UNIV on December 2.. 148-49 of v a r i a b l e s in f l u i d i z e d bed r e a c t o r 62 Diameter of bubbles in atmospheric pressure f l u i d bed combustor 75-77 of coal feed in atmospheric pressure f l u i d bed combustor...acs... .s c a l e cold flow mode1.

. 105t E u l e r i a n approach t o mixing and turbulence 138-44 Exotherm.193 Downloaded by ILLINOIS STATE UNIV on December 2.. 50-55. . s t i r r e d tank reactor 14 conversion. polymerization mechanism.ix001 INDEX Emmissions of nitrogen oxides.. 40f bubble models 50-62 catalyst 56 c a t a l y t i c d i f f e r e n c e s in f l u i d i z a t i o n and heat transfer 6 coal combustion 55-56 coal combustion a t atmospheric pressure bed height and pressure drop 67-69 bed temperature 66-73 In Chemical Reaction Engineering—Plenary Lectures. 2012 | http://pubs. in a scaled-up f i x e d bed r e a c t o r 35t.42t Ethylene oxide. . 1983..org Publication Date: July 28.. 141-42 F l u i d bed r e a c t o r s 49-62 b a f f l e s . . 69 Feed diameter. . unc o n t r o l l e d nonadiabatic s t i r r e d tank r e a c t o r 13-14 Expansion type A powders in a f l u i d bed r e a c t o r 57f Extruder.. mixing theory 151-64 Entropy of a mixture 138 Erosive mixing 166-67 Ethane. atmospheric pressure f l u i d bed combustors vs. et al. in an atmospheric pressure f l u i d bed combustor 69 dissipation carbon combustion efficiency 83-85 molecular d i s p e r s i o n 167 turbulent. American Chemical Society: Washington. 28f.67-69 Fluctuation mean square and homogeneous i s o t r o p i c turbulence.. design. polymerization reactions 109t Fans f o r an atmospheric pressure f l u i d bed combustor. . thermal to e l e c t r i c a l . ... y i e l d in methanol-togasol ine processes 42t Ethylene heats of polymerization 106t production from methanol 40f y i e l d in a scaled-up f i x e d bed r e a c t o r 35t. . ACS Symposium Series.. and heat t r a n s f e r in an atmospheric pressure f l u i d bed combustor 78-80 Emulsion phase. . .acs. . homogeneous isotropic turbulence 138-41 Entering environment.. . 90-92 Emissivity. c o a l . f l u i d c a t a l y t i c crackers 66-67 Emulsion polymerization in a continuous flow s t i r r e d tank r e a c t o r 105t. Wei.1021/bk-1983-0226. f o r an atmospheric pressure f l u i d bed combustor 80-87 Feedstreams See a l s o I n l e t ( s ) in the bundle of p a r a l l e l tubes model 150-57 mixing.29f in carbon combustion 84-85 in a f l u i d bed r e a c t o r 50-62 in a f l u i d bed r e a c t o r a t atmospheric pressure f l u i d mechanics 72-78 and immersed tubes 92-93 mixing with two unmixed feedstreams 158f polymerization 122f and residence time d i s t r i b u t i o n theory 145t Flow r a t e 135-80 in bundle of p a r a l l e l tubes model 145-46 in a f l u i d bed r e a c t o r of a i r and f u e l . . .. J. 158f Fermentor. 138-41 probability density f u n c t i o n s . . . . 114-21 Emulsion v e l o c i t y in an atmospheric pressure f l u i d bed combustor 77 Energy a c t i v a t i o n .42t Ether. . .. polymerization mechanism 105t Ethylene-propylene copolymers. 1983 | doi: 10. from an atmospheric pressure f l u i d bed combustor. . . . DC.33-39 Flow in a d i a b a t i c r e a c t o r s . continuous 12 Fixed bed r e a c t o r s f o r methanol-to-gasoline conversion 27-30.. tube w a l l .. methanol-to-gasoline process 23-24 Exothermic r e a c t i o n . ..

.72-78 heat t r a n s f e r 66. methanol-to-gasoline processes 42t n a t u r a l .s e c t i o n a l area and flow regime in atmospheric pressure f l u i d bed combustor 72-78 F l u i d p a r t i c l e s ..acs. polymerization reactions 106 Heat sink.ix001 194 CHEMICAL REACTION F l u i d bed r e a c t o r s — Continued carbon combustion efficiency 80-87 c o n t r o l l i n g parameters. 1983.. carbon. 20f Gas phase alchemy 3-4 c i r c u l a t i o n . American Chemical Society: Washington. B a s i l Lanneau. atmospheric pressure f l u i d bed combustor 69 conversion.55-56 G a s i f i c a t i o n .. tubular reactors 32 Heat t r a n s f e r in an atmospheric pressure f l u i d bed combustor. determination of bed c r o s s . isothermal.. in f l u i d bed combustors 85 Gasoline manufacture from methanol. atmospheric pressure f l u i d bed combustor 74-78 mixing.. 2012 | http://pubs. 1983 | doi: 10.72-78 Fluxes. heat t r a n s f e r in an atmospheric pressure f l u i d bed combustor 78-80 Formaldehyde.. DC. atmospheric pressure f l u i d bed combustors vs.78-80 In Chemical Reaction Engineering—Plenary Lectures. .1021/bk-1983-0226. . calcium oxide.30-32. atmospheric pressure f l u i d bed combustor 77-78 r e c y c l e system and bed length 34 v e l o c i t y . mechanism o f interaction 164-75 F l u i d i z a t i o n and heat t r a n s f e r d i f f e r e n c e s of atmospheric pressure f l u i d bed combustors and f l u i d catalytic reactors 67 F l u i d i z a t i o n v e l o c i t y in f l u i d bed r e a c t o r s 52-56.78-87 particle size 69-73 s u l f u r capture 69-73 volatile evolution 87-90 for methanol-to-gasoline process 28f...38f y i e l d in scaled-up f i x e d bed reactor 35t. et al. 2-3 Grain model. conductive and convective. f l u i d i z e d c a t a l y t i c crackers 66-67 v e l o c i t y .. x-ray photograph 58-60 of durene in methanol-togasol ine process 25-27 of n i t r i c oxide in coal combustion 66 Formation k i n e t i c s o f methanol-to-gasoline process 23-25 Fragmentation of p a r t i c l e s in an atmospheric pressure f l u i d bed combustor 87 Free r a d i c a l polymerization mixing theory 178-79 reactions 103-7 Freeboard r e a c t i o n s in an atmospheric pressure f l u i d bed combustor 92 Fuel flow r a t e in an atmospheric pressure f l u i d bed combustor 69 ENGINEERING Gas l i g h t . heats of polymerization 106t Formation of bubbles in f l u i d bed reactor. . f l u i d i z e d bed reactor 50-62 Corrsin microscale. f l u i d bed reactors 52. 19-46 treating 37. 14 Heat removal... limestone to calcium s u l f a t e 69-73 polymerization 106t in a s t i r r e d tank r e a c t o r . ACS Symposium Series.Downloaded by ILLINOIS STATE UNIV on December 2..40-44 p i l o t plant scale-up 40-43 F l u i d mechanics.org Publication Date: July 28. 65-93 flow regimes and immersed tubes 92-93 f l u i d mechanics 66.. . 67. 70-72 H Heat exchange in c a t a l y t i c r e a c t o r s 67 in tubular r e a c t o r s in a methanol-to-gasoline process 32 Heat of r e a c t i o n combustion.. Wei..42t G i l d e r s l e e v e . conversion to gasoline v i a methanol. mixing theory 139-41 flow.. J.

models 156-75 I n t e r f a c i a l polycondensation..1021/bk-1983-0226... American Chemical Society: Washington.177-79 Inlet(s) number and mixing 149 temperature f i x e d bed reactor 35t. non-. 156-64... 1983 | doi: 10..195 Downloaded by ILLINOIS STATE UNIV on December 2. 28f.140t I n t e r a c t i o n by exchange with the mean model. design in f l u i d bed r e a c t o r 40f Internal c i r c u l a t i o n patterns in s t i r r e d tanks 175-76 Ionic polymerization reactions 103-7 Isobutane.... .121f reactor conditions Ill Isothermal. .42t product y i e l d s from methanol-to-gasoline processes 42t residence time d i s t r i b u t i o n theory 145t Instantaneous i n t e r n a l age d i s t r i b u t i o n . J.114.... ACS Symposium Series.. Wei. .. . polymerization 105t Heterogeneous r e a c t o r s .169-71 Interaction of p a r t i c l e s . definition 136-37.. polymerization 105t Hopf b i f u r c a t i o n 13-14 Horizontal scale-up of f l u i d bed r e a c t o r s 40-42 Hydrocarbons conversion r e a c t i o n of methanol 23-25 y i e l d in scaled-up f i x e d bed reactor 35t.42t Hyperreal numbers 8 I Immersed tubes and flow regimes in an atmospheric pressure f l u i d bed combustor 92-93 Indices mixing 136-44 segregation. population balance method 147-48 Internal b a f f l e s . 14 Heavy gasoline t r e a t i n g technology 37.. 109t Internal age d i s t r i b u t i o n . .acs. population balance method 147-48 Integers. mixing theory 137 Homogeneous isothermal reactors 149 Homogeneous i s o t r o p i c turbulence 138-40 Homogeneous media. 32 Isothermal heterogeneous and homogeneous r e a c t o r s 149 Isothermal polymerization of methyl methacrylate in a continuous flow s t i r r e d tank r e a c t o r .ix001 INDEX Heat t r a n s f e r — C o n t i n u e d in an atmospheric pressure f l u i d bed combustor vs.. hyperreal 8 I n t e n s i t y of segregation..42t Isocyanates.. tubular reactors. f i r s t c y c l e y i e l d in a scaled-up f i x e d bed reactor 35t.. m u l t i p l i c i t y . 113f. world c a p a c i t y and expected growth 102t Isomerization of durene 37 Isothermal heat sink.29f in a s t i r r e d tank reactor.38f Height bed and bubble s i z e in a f l u i d bed r e a c t o r 50-55 and pressure drop in an atmospheric pressure f l u i d bed combustor.... Danckwerts. 2012 | http://pubs. isothermal 149 H i s t o r i c a l survey of mathematics 1-15 Homogeneity degree.. fluidized catalytic reactors 67 in a f l u i d bed 30 in nonadiabatic r e a c t o r s ... uncontrolled nonadiabatic s t i r r e d tank reactor with a s i n g l e exothermic r e a c t i o n 13-14 I s o t r o p i c homogeneous turbulence 138-40 In Chemical Reaction Engineering—Plenary Lectures... DC...org Publication Date: July 28. et al. 136-38 Industry—See Commercialization Inert t r a c e r and mixing 161-64 I n f i n i t e and i n f i n i t e s i m a l numbers 7-8 I n i t i a t i o n of polymerization reactions 103-7. 1983. instantaneous.118f... 67-69 freeboard. in an atmospheric pressure f l u i d bed combustor 92 Heterogeneous media..

Hopf b i f u r c a t i o n 14 M Macroscale homogeneous i s o t r o p i c turbulence 138-41 mixing and residence time distributions 144-51 Magnesium limestone. homogeneous i s o t r o p i c turbulence 138-41 Kinetics of carbon combustion 85 of methanol-to-gasoline process 23-25 of mixing 169-71 of polymerization. 91 as sorbent in atmospheric pressure f l u i d bed combustor 69-73 L i q u i d phase and C o r r s i n microscale f o r mixing theory 139-41 Local age d i s t r i b u t i o n function 145. r e a c t i o n . Wei. DC. 1983. .42t zeolite catalysts 19-23 Methyl a c r y l a t e .118 M e t r i c a l theory of "phonetic syzygy. 72-78 Mechanisms coal combustion 66 i n t e r a c t i o n . in a scaled-up f i x e d bed reactor 35t. et al.acs. .. kinetics 105t of s o l i d d i s p e r s i o n . J. micromixing in the p h y s i c a l space 164-75 methanol-to-gasoline process 23-25 in polymerization r e a c t o r s . coal combustion 88-90 s u l f a t i o n of limestone 69-73 Media. 151 Mean square f l u c t u a t i o n .178-80 of s u l f a t i o n of limestone. . d e f i n i t i o n . 151 Mixing 135-81 d e f i n i t i o n and c h a r a c t e r i z a t i o n of degree 136-38 e a r l i n e s s in the age domain 151-64 entropy 138 Eulerian approach 138-44 in a f l u i d bed r e a c t o r 52 of gas in an atmospheric pressure f l u i d bed combustor 77-78 macro-... homogeneous i s o t r o p i c turbulence 138-41 ENGINEERING Mechanics. d e f i n i t i o n ." S y l v e s t e r 2 Microscale. 2012 | http://pubs.164-75 Minimum mixedness.ix001 196 CHEMICAL REACTION K i n e t i c energy of turbulent motion.. ACS Symposium Series. f i r s t c y c l e y i e l d . 103-7.. .114.147 L o c i . and residence time distributions 144-51 by molecular d i f f u s i o n 167-70 In Chemical Reaction Engineering—Plenary Lectures.. heats of polymerization 106t Methyl methacrylate heats of polymerization 106t isothermal polymerization in a continuous flow s t i r r e d tank reactor 113f. scaled-up f i x e d bed reactor 35t.1021/bk-1983-0226. f l u i d . . 69-73 Kolmogorov microscale. .Downloaded by ILLINOIS STATE UNIV on December 2. product y i e l d s from methanol-to-gasoline processes 42t Limestone reduction of nitrogen oxide. homogeneous i s o t r o p i c turbulence 138-41 L Lagrangian approach and mixing theory 164-75 Leaving environment and mixing theory 151-64 Length of bed and gas r e c y c l e system.42t Methanol-to-gasoline process reactor design 23-32 scale-up and commercialization 32-44 space v e l o c i t y . 1983 | doi: 10. American Chemical Society: Washington. sulfation 69-73 Mass t r a n s f e r models f o r carbon combustion 84-85 Mathematics.. 105t Melt polycondensation 109t Methane. i n atmospheric pressure f l u i d i z e d bed combustor.. employed in polymerization r e a c t o r s . h i s t o r i c a l survey 1-15 Maximum mixedness.. .. mixing phenomena 137. 34 Light gas.org Publication Date: July 28.

42t O l e f i n polymerization. hyperreal. .acs. solid-catalyzed 120-24 Operating conditions of reactor and residence time d i s t r i b u t i o n theory 1451 Oscillatory solution.78-80 flow in f l u i d bed r e a c t o r . with a s i n g l e exothermic r e a c t i o n .20f 165-66 153-64 66 90-92 28f 13-14 7-8 105t 0 Octane blending q u a l i t y . 50-62 fragmentation in atmospheric pressure f l u i d bed combustor 87 heating in atmospheric pressure f l u i d bed combustors vs. carbon combustion 85 Oxidation of bound nitrogen in coal 90-92 Oxygen atom c o n f i g u r a t i o n in a s i l i c e o u s framework. coal combustion Nitrogen oxide emissions.. multiphase s t i r r e d tank reactor. . DC.. mixing theory 156-59 Morphological models and particle disintegration. Sylvester 3 Phase behavior c o m p a t i b i l i t y in f l u i d bed reactor 59-62 In Chemical Reaction Engineering—Plenary Lectures. .. k i n e t i c energy and homogeneous i s o t r o p i c turbulence 138-41 Multibed designs 29f M u l t i g r a i n model.ix001 INDEX 197 Mi xi n g — Continued for polymerization reactions 106 and segregation at the microscopic level 164-75 static 176-78 in s t i r r e d tank r e a c t o r s . . 14. . disintegration 122f Partitions. f l u i d i z e d c a t a l y t i c crackers 66-67 mixing in f l u i d bed reactors 52 models of i n t e r a c t i o n 156-64 of polymerization. constructive theory. mixing. 1983 | doi: 10. NG and Rippin model N i t r i c oxide formation. polymerization 122f Motion.Downloaded by ILLINOIS STATE UNIV on December 2. mixing theory.. polymerization 122f M u l t i p l i c i t y . J.175-76 Ν Natural gas and natural gas-to-gasoline v i a methanol Newtonian f l u i d s . methanol conversion products 23 P a r a l l e l model of Weinstein and Adler 154f Particles definition 163 diameter 55. American Chemical Society: Washington. .. . carbon combustion e f f i c i e n c y .1021/bk-1983-0226. Wei.42t Oxidant.. et al.org Publication Date: July 28. ACS Symposium Series. atmospheric pressure f l u i d bed combustor Nonadiabatic reactors Nonadiabatic s t i r r e d tank r e a c t o r . stirred tank r e a c t o r 14 Outlet for methanol-to-gasoline dehydration r e a c t o r 42t residence time d i s t r i b u t i o n theory 145t temperature. 82-83 Ρ 19. dominant. polymerization mechanism Octane—Continued y i e l d in scaled-up f i x e d bed reactor 35t. 175-77 times 137 Molecular d i f f u s i o n . 1983..69-73. turbulent. 167-70 Molten s a l t c o o l i n g 32 Moment equation. population balance method 147-48 Monomers heats of polymerization 106t linkage 109t Monte Carlo method. 2012 | http://pubs. zeolite catalyst 21-22 concentration and d i f f u s i v i t y ... in a scaled-up f i x e d bed r e a c t o r 35t. uncontrolled. i n f i n i t e . non isothermal system Numbers. durene. and i n f i n i t e s i m a l Nylon. 25-27 P a r a f f i n s .

nonisothermal system 13-14 In Chemical Reaction Engineering—Plenary Lectures. 2012 | http://pubs. mixing theory 156-64 Rate of a t t r i t i o n and carbon combustion e f f i c i e n c y 83-85 Rate of c o o l i n g in a s t i r r e d tank r e a c t o r 14 Rate of flow See a l s o Flow r a t e in an atmospheric pressure f l u i d bed combustor 67-69 in the bundle of p a r a l l e l tubes model 145-46 in a f l u i d bed r e a c t o r 50-55 Rate of heat t r a n s f e r . in a continuous flow s t i r r e d tank reactor 114-20 engineering 101-24 heat of r e a c t i o n 106t isothermal. atmospheric pressure f l u i d bed combustors vs. 91 s u l f a t i o n of limestone 70-73 Rate of s o l i d ( s ) withdrawal and carbon combustion efficiency 80-82 Reactant mixing 135-80 Reaction. in a continuous s t i r r e d tank r e a c t o r ..ix001 198 CHEMICAL REACTION Phase behavi o r — C o n t i nued and polymerization r e a c t i o n kinetics 106 Phonetic syzygy.29f 27 Radial flow in a d i a b a t i c reactors 28f.. uncontrolled nonadiabatic s t i r r e d tank r e a c t o r . of methyl methacrylate in a continuous flow s t i r r e d tank r e a c t o r 113f k i n e t i c s and mechanisms 103-7 r e a c t o r design 103-7.org Publication Date: July 28.117f solid-catalyzed olefin 120-24 s o l u t i o n ..177-79 Propane.1021/bk-1983-0226.29f Random coalescence-dispersion model.109t Pressure atmospheric. 1983. 1983 | doi: 10. s i n g l e .43f P l a s t i c s . J. ACS Symposium Series. fluidized catalytic crackers 66-67 Rate of r e a c t i o n b i f u r c a t i o n diagrams 11-12 carbon g a s i f i c a t i o n 85 reduction of nitrogen oxide..42t in f l u i d bed reactors 55. expansion in f l u i d bed r e a c t o r 57f P r e c i p i t a t i o n polymerization 105t. . mixing theory 178-79 core model 122f emulsion.42t Propylene polymerization concentration p r o f i l e s i n the m u l t i g r a i n model for a high a c t i v i t y catalyst 120-24 heats of r e a c t i o n 106t y i e l d in scaled-up f i x e d bed reactor 35t. DC. 107-8 Propagation. type A. scaled-up 35t.Downloaded by ILLINOIS STATE UNIV on December 2... exothermic. 70-73 Powders. world c a p a c i t y and expected growth 102t Population balance method in residence time d i s t r i b u t i o n theory 145-48 Pore s i z e of z e o l i t e c a t a l y s t for methanol-to-gasoline process 21-23 Pore-plugging model f o r s u l f a t i o n of limestone. c o n t r o l l i n g parameters 65-93 in f i x e d bed r e a c t o r .60-62.42t P y r o l y s i s of coal 87-90 Q Quenching in a d i a b a t i c r e a c t o r s in f i x e d bed r e a c t o r s 28f. y i e l d in scaled-up f i x e d bed r e a c t o r 35t.acs. et al. polymerization reactions 103-7. . Wei. . world c a p a c i t y and expected growth 102t Polymerization r e a c t i o n s classes 104t condensation 103-7 continuous f r e e r a d i c a l . American Chemical Society: Washington. Sylvester's metrical theory 2 P h y s i c a l space and mechanism of micromixing 164-75 Plants f i x e d bed r e a c t o r s 33 f l u i d bed r e a c t o r s 41f. in f l u i d bed coal combustion. 110-14 Polymers...67-69 Probability density functions f o r the f l u c t u a t i n g components 141-42 ENGINEERING Product q u a l i t y of polymer..

mixtures with v a r i a b l e density 148-49 s t i r r e d tank. full-scale 58 f o r emulsion polymerization. 49-62 b a f f l e s .. . 91-92 Residence time d i s t r i b u t i o n s and macromixing 144-51 Reynolds number. mixing theory 149 Reactor. i n f i n i t e sequences 7-8 Recycle operation and bed length 34 in f i x e d bed r e a c t o r s . methanol-to-gasoline process 27-30.1021/bk-1983-0226.166-67 S i l i c e o u s framework.161 intens i t y .141-43 two-inlet 156-64 Real numbers.Downloaded by ILLINOIS STATE UNIV on December 2.42t Shape. 27-30. durene conversion 37 continuous flow s t i r r e d tank Be1ousov/Zhabotinsky reaction 143 design f o r emulsion polymerization 117f dehydration 37-39 d e s i g n — S e e Design distributor plate. Bertrand 9 S S a l t .40-44 isothermal 149 mixing 135-81 nonadiabatic 28f semibatch.140t and mixing at the microscopic l e v e l 164-75 and polymerization of styrene in cyclohexane solution 178-80 Semibatch r e a c t o r m u l t i g r a i n model p r e d i c t i o n s for propylene polymerization 120-24 polymerization r e a c t i o n s 109t residence time d i s t r i b u t i o n theory 145t Separations i n f i x e d bed methanol-to-gasoline process 38f Separator temperature in scaled-up f i x e d bed reactor 35t. 109t Segregation by chemical methods. f l u i d bed. polymerization 110-15 Reactors adiabatic 28f c a t a l y t i c ... f i x e d bed..33-39 f l u i d bed.acs. Danckwerts 136-38. h o r i z o n t a l and vertical 40-42 of methanol-to-gasoline process 32-44 of polymerization r e a c t o r s . def in i t ion. Wei. and residence time d i s t r i b u t i o n theory 145t steady-state c o n d i t i o n s . mixing theory 158 Reaction h e a t — S e e Heat of reaction Reaction media employed in polymerization r e a c t o r s . c o o l i n g 32 Scale-up See a l s o Commercialization of f i x e d bed r e a c t o r s 27 of f l u i d bed r e a c t o r s . J. . . .30-32. methanol-to-gasoline process 28f.33-39 Reactor. design 40f bubble models 50-62 f o r coal combustion at atmospheric pressure 65 f o r methanol-to-gasoline process 28f.. identification 170-75 index. molten. 27. p a r t i c l e 66 R u s s e l l .35t. 105t Reaction order. uncontrolled nonadiabatic nonisothermal 13-14 tubular 32. molecular.. oxygen atoms in z e o l i t e catalyst 21-22 S i n g u l a r i t y theory 11-12 In Chemical Reaction Engineering—Plenary Lectures.ix001 INDEX 199 Reaction/diffus ion model. f o r methanol-togasol ine process..30-32. 2012 | http://pubs.40-44 Reactor temperature.. . 1983 | doi: 10.org Publication Date: July 28. American Chemical Society: Washington.136-37. ACS Symposium Series.42t Reduction of nitrogen oxide. et al. . . and mixing theory 167-70 Shape-selective z e o l i t e catalysts for a methanol-to-gasoline process 19-23 Sherwood number and carbon combustion e f f i c i e n c y 82-83 Shrinking aggregate model 159. 117f f i x e d bed. carbon combustion 85 Reaction time d i s t r i b u t i o n . 1983. DC..

.. . metrical theory 1-3 Τ Tank reactor See a l s o S t i r r e d tank reactors uncontrolled nonadiabatic nonisothermal system with a s i n g l e exothermic reaction 13-14 Taylor microscale.148-49 Steam d e a c t i v a t i o n of the c a t a l y s t in methanol conversion 23 S t i r r e d tank reactors 13-14 and mixing theory 175-77 multiphase 176-78 f o r polymerization reactions 109t. polymerization 103-7.Downloaded by ILLINOIS STATE UNIV on December 2. 105t S y l v e s t e r .117f turbulent k i n e t i c energy and segregation dissipation 139-41 Structure of a z e o l i t e c a t a l y s t f o r a methanolto-gasol ine process 21-23 Styrene emulsion polymerization in a continuous flow s t i r r e d tank reactor 117f ENGINEERING Sty r e n e — C o n t i nued heats of polymerization 106t segregation e f f e c t on polymerization 179-80 Styrene-acry Ion i t r i l e butadiene polymer. 80-82 S o l u b i l i t y and polymerization reactions 106 Solution polymerization in a continuous flow s t i r r e d tank r e a c t o r 110-14 Solvent concentration in polymerization 110-15 Spectra and homogeneous i s o t r o p i c turbulence 138-41 Spencer and Leshaw model. James Joseph.4. in f l u i d bed reactor 50 coal feed. and polymerization r e a c t i o n s . f o r optimum carbon combustion efficiency 84-85 p a r t i c l e . and alchemy 3-4 S t a t i c mixers 176-78 Steady state conditions i n continuous s t i r r e d tank reactors 14..5-Tetramethylbenzene formation.. . density. 32 Terminal v e l o c i t y in an atmospheric pressure f l u i d bed combustor 72-78 Termination. product y i e l d s from methanol-to-gasoline processes 42t reactor and f l u i d i z a t i o n 60-62 methanol-to-gasoline process 26f. .158f S t a b i l i t y regions in a s t i r r e d tank reactor 14 State of matter. Sylvester.. 3 Thermal to e l e c t r i c a l energy. 69 Thermal time d i s t r i b u t i o n 149 In Chemical Reaction Engineering—Plenary Lectures.. et al. .43f polymerization 110-15 tubular. . 88-90 mixing 178 o l e f i n polymerization catalysis 120-24 polycondensation 109t withdrawal rate and carbon combustion e f f i c i e n c y .2. e f f i c i e n c y of conversion. in an atmospheric pressure f l u i d i z e d bed combustor 66-73 pore 70 Solid(s) bed. Wei. 106 Suspension in polymerization. c o n t r o l . .. homogeneous i s o t r o p i c turbulence 138-41 Temperature bed in an atmospheric pressure f l u i d bed combustor 69-73 o u t l e t and i n l e t .. 2012 | http://pubs..69-73 Surface of r e a c t o r s . constructive. American Chemical Society: Washington.110-14.1021/bk-1983-0226. 1983 | doi: 10. 1983. J.. methanol-togasol ine process 25-27 Theory of p a r t i t i o n s .153f. .. world c a p a c i t y and expected growth 102t S u l f a t i o n and s u l f u r capture in an atmospheric pressure f l u i d i z e d bed combustor 66.ix001 200 CHEMICAL REACTION Size bubble. gas.178-80 1. .. ACS Symposium Series. atmospheric pressure f l u i d i z e d bed combustor 67-69 d i s p e r s i o n mechanism f o r coal combustion.org Publication Date: July 28. atmospheric pressure f l u i d i z e d bed combustor. DC.acs.

. mixing theory 159 Time constant.201 Downloaded by ILLINOIS STATE UNIV on December 2. and turbulence theory .72-78 W Water formation in a methanol-togasol ine process 23-25 y i e l d in a scaled-up f i x e d bed r e a c t o r 35t.141-43 Turbulence E u l e r i a n approach 137-44 s t i r r e d tanks 175-76 Two-phase bubble model 53-58 Two-stage f i x e d bed r e a c t o r s . 42t . 2012 | http://pubs. .. 66-67.138-40 of f l u i d i z a t i o n . Taylor.acs. 3If U Uncontrolled nonadiabatic s t i r r e d tank r e a c t o r with a s i n g l e exothermic reaction Unsaturated p o l y e s t e r s . s u l f u r capture 69-73 Volumetric f l o w r a t e . ACS Symposium Series. and flow regimes. residence. tubular reactors 142 Trommsdorf e f f e c t 114 Tube(s) area s e l e c t i o n f o r an atmospheric pressure f l u i d bed combustor 78-80 bundle of p a r a l l e l . 145-57 e x t r e m i t i e s . in a scaled-up f i x e d bed r e a c t o r 35t. atmospheric pressure f l u i d bed combustor 92-93 Tubular r e a c t o r s 32. et al. J.. and mixing. polymerization reactions 109t Tracer.1021/bk-1983-0226. DC. and mixing theory 154 Volumetric expansion. 1983.. homogeneous i s o t r o p i c turbulence 138-41 V o l a t i l e e v o l u t i o n in an atmospheric pressure f l u i d bed combustor 87-92 Volume and residence time d i s t r i b u t i o n theory 145t Volume... American Chemical Society: Washington.org Publication Date: July 28. and viscous d i s s i p a t i o n . 78-80 Transfer models mass.. and mixing theory. and carbon combustion 84-85 po lymer i z a t ion 178-80 Transversal d i s p e r s i o n c o e f f i c i e n t .ix001 INDEX Three-envîronment model. . 164 methanol.. polymerization mechanism 105t. 92 in the bundle of p a r a l l e l tubes model 145-46 x-Ray photograph of bubble formation in a f l u i d bed reactor 58-60 Y Y i e l d s of products from methanol-to-gasoline processes In Chemical Reaction Engineering—Plenary Lectures. in an atmospheric pressure f l u i d bed combustor 77 f l u c t u a t i o n s . accumulator. Wei. C o r r s i n . model..106t. i n e r t .115t Viscous d i s s i p a t i o n . 160-63 Transfer of heat in an atmospheric pressure f l u i d i z e d bed combustor. .42t Weight of bed in an atmospheric pressure f l u i d i z e d bed combustor. .72-78 gradient.42t V e r t i c a l scale-up of f l u i d bed r e a c t o r s 40-42 Villermaux and Z o u l a l i a n model 154f V i n y l polymers. 52-56. and macromixing 144-51 Times of mixing 137 Tower and s t i r r e d tank cascade.. world c a p a c i t y and expected growth Veloci t y — C o n t i n u e d of emulsion. locus 146f immersed. atmospheric pressure f l u i d bed combustor 69. freeboard r e a c t i o n s . homogeneous i s o t r o p i c turbulence 138-41 Time d i s t r i b u t i o n s . 1983 | doi: 10. 67-69 Weinstein and Adler p a r a l l e l model 154f 13-14 102t Valderrama and Gordon model 154f Velocity bubble..

.org Publication Date: July 28..ix001 Z e o l i t e c a t a l y s t s .CHEMICAL REACTION 202 ENGINEERING Ζ Zwietering equation and mixing theory Downloaded by ILLINOIS STATE UNIV on December 2. 152 . Baltimore. shapes e l e c t i v e . et al. in a methanolto-gasoline process.. 2012 | http://pubs.. York.. American Chemical Society: Washington. Wei. 1983...1021/bk-1983-0226. 1983 | doi: 10.. DC. J.acs. ACS Symposium Series. PA In Chemical Reaction Engineering—Plenary Lectures. MD Printed and bound by Maple Press Co.. 19-23 Jacket design by Kathleen Schaner Indexing and production by Florence Edwards and Paula Bérard Elements typeset by Service Composition Co.