Periodic Operation of Chemical Reactors

769 Pages·2012·27.313 MB·792\769

PERIODIC
OPERATION
OF REACTORS
Editedby
P. L. S
ILVESTON
Waterloo,Ontario,Canada
R. R. H
UDGINS
Waterloo,Ontario,Canada
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Preface
Interestintheperiodicoperation ofreactors Another important aim of this book is to
of all types, chemical, catalytic and biochem- recognize the pioneers, the innovators, and
ical, has expanded rapidly in the last several the synthesizers of process periodic operation.
decades. The time has come to undertake an As authors we have sought to identify the
overview of not only the research activity, but important contributions to the development of
its translation into engineering application. periodicoperations.Undoubtedly,some,regret-
Such an overview, perhaps a summary, is the tably, have been overlooked. In the years to
intent of “Periodic Operation of Reactors”. come, advances will surely follow. It is our
It is our hope that this book will offer an hope that in a decade or two, this book will be
introduction to the large literature, as well superseded by a superioroverview.
as a platform for evaluating both new and This book has been organized to make it
past contributions. As well, it may serve as useful. Your benefit from our effort depends,
a resource for any engineers considering of course, on what you are looking for. If you
utilizingnon-steady-stateoperationinreaction seek to build your general knowledge about
processes they now operate. As authors, the periodic operation of reactors, you should
editors, and researchers, we trust that this begin with Chapter 1 which presents an over-
book may provide direction for planned or view of the subject. If your interest is in
on-going research. For this reason, several a specific reaction, electrochemistry, a specific
chaptersandthefinaloneinparticularidentify modulation process or in the combination of
research needs and challenges. reaction and separation, only a few chapters
Although steady-state operation appears need be consulted. If your interest is limited
to be an industry paradigm, it is one with to a specific reaction or a group of reactions,
many exceptions. A great many metallurgical look over chapters 2 to 12 or consult the
processestakeplaceunderunsteadyconditions. Table of Contents or the Index. The latter is
Steady-state operation is hardly the rule in quite broad and many specific reactions are
biochemical systems, as will be evident in mentioned. If you want to examine the contri-
Chapter 14. Indeed, electrochemical processes butions of a specific researcher, see the bib-
have taken advantage of periodic operation liography. It gives the chapters in which the
(apart from just the use of alternating current) reference appears. Chapters 13 and 14 deal
for more than 60 years, as can be seen in with theory, while Chapters 15 to 18 examine
Chapter 9. Yet whether the standard is steady modulation of a specific operating condition.
or transient operation is not relevant to the Chapter 19 discusses control while Chapters
intent of this book. What we strive to demon- 20to22considercombinedreactionandsepara-
strate is that periodic operation can often tion. As a further convenience, the literature
enhance processperformance. introducedinachapterissummarizedinatable
ix
x
PREFACE
early on. A good starting point for any reader we acknowledge the support of the secretarial
would be to begin with such tables. staff at our various institutions. The editorial
As editors, it is with pleasure and gratitude staff at Elsevier, particularly Fiona Geraghty
thatweacknowledgetheeffortandscholarship and Pauline Wilkinson, have provided useful
the authors of the individual chapters have advice,services,andconstantproddingtowards
contributedtothisbook.Theyhavealsovolun- deadlines.Wearegratefulfortheirengagement.
teered comments, argued interpretations or Finally,weacknowledgethepatienceofspouses
drawn attention to omissions, along with their who have graciously accepted the constraints
written contributions. Both authors and editors borneby thosewho wouldwrite books.
wish to thank our institutional librarians for
their help locating publications. In addition, Peter Silveston, Robert Hudgins
About the Authors
AdesojiAdesina HectorBudman
Adesina obtained a PhD (1986) from the Hector is currently a Professor of Chemical
University of Waterloo, Canada. He taught at Engineering at the University of Waterloo,
theUniversityofPort-Harcourt,Nigeria,before came to Canada from Argentina via Israel. He
joiningtheUniversityofNewSouthWales,Syd- has authored or co-authored over 150 journal
ney, Australia, in 1991 where he is presently publicationsandconferencepapersintheareas
a full professor leading a major research group of process modeling and control with applica-
inCatalysisandReactorEngineering.Hisactiv- tions to biotechnology and reaction systems.
ities are primarily focused on energy and envi- During his career he has undertaken collabora-
ronmental themes. He is credited with over tive work in the pharmaceuticals, water treat-
350technicalpapersandabookinmetalcarbide ment, mineral processing and pulp and paper
catalystsforFischer-Tropschsynthesis.Heison industries. He holds a Mechanical Engineering
the editorial board of Catalysis Communica- doctoratefromtheIsraelInstituteofTechnology
tionsandmemberoftheInternationalAdvisory (Technion).
Board for Environmental Catalysis. He enjoys
playing soccer. GrigoriBunimovich
Grigori is a key engineering specialist at
Juergen Brandner Matros Technologies, Inc. St. Louis, Missouri.
Currently heads the Thermal Processes Aftergraduating from the Technical University
Department and Heat Exchange Group of the of Tomsk, he obtained a Ph. D. in Chemical
Institute for Micro Process Engineering at Engineering from and worked at the Boreskov’
the Karlsruhe Institute of Technology (KIT), Institute of Catalysis (Novosibirsk, Russia).
Germany.HeisalsoalecturerforMicroProcess In 1993 he joined Matros Technologies Inc.
Engineering at the Dresden Technical Univer- where he serves as the Director of Catalyst
sity. Brandner is author or co-author of some Applications. Grigori co-authored more than
260 technical articles and 7 technical books. 50 technical publications concerning various
After studies in Chemistry he obtained applications of periodic reverse-flow reactors
a Diploma in Electrical Engineering and an andcatalyticprocessesforairpollutioncontrol.
Engineering Doctorate in Mechanical Engi-
neering,bothfromKIT,aswellasahabilitation William Epling
degree from the Dresden Technical University. Bill Epling is an Associate Professor in the
Living close to Heidelberg, Germany, he Department of Chemical and Biomolecular
also teaches several martial arts courses as EngineeringattheUniversityofHoustonwhere
recreation. his research focuses on Environmental
xi
xii
ABOUTTHEAUTHORS
Catalysis. He has authored over 80 peer- Patricia Haure
reviewed papers in archival journals and given Patricia is currently a Professor of Chemical
over 100 presentations or seminars. He won Engineering at the Universidad Nacional of
the Early Researcher Award from the Province Mar del Plata in Argentina. She graduated in
of Ontario in 2007. Bill graduated with a B.S. 1981 from that University and in 1989 obtained
in Chemical Engineering from Virginia Tech aPhDfromtheUniversityofWaterloo,Canada,
and a PhD in Chemical Engineering from the where she pioneered research on the periodic
University of Florida. Outside of work, Bill operation of trickle bed reactors. Haure
fosters stray dogs, pretending to find them continues exploring the effect of liquid flow
homes althoughfew seem to ever leave. modulation on reactor performances and has
expandedherresearchtodetoxificationofwaste
Jiri Hanika waters. Her many publications are on those
subjects.She isapet lover involvedasavolun-
Currently a “Director Emeritus” of the Insti-
teer in rescue actions. She also enjoys painting,
tute of Chemical Process Fundamentals, Czech
gardening andoutsideactivities.
Academy of Sciences and a Professor of the
Institute of Chemical Technology Prague (ICT),
Ji(cid:1)r´ı retired in 2012 after a 40 years carrier. Robert Hudgins
However he still continue teaching, research A graduate of University of Toronto and
andscholarlywriting.Hehaswrittenanumber Princeton University, Bob met Pete Silveston,
oftechnical and/or text booksand co-authored his co-editor of this book, at University of
severalchaptersinmonographsaswellasmore Waterloo where they were faculty members in
than 150 technical papers. He is a graduate of its fledgling Department of Chemical Engi-
ICT and holds an Engineering Doctorate and neering. A common interest in teaching and
“Doctor of Sciences” degree from ICT as well. research on reaction engineering led to a close
He has resided nearly his whole life in Prague collaboration on several topics, primary among
where he regularly attends cultural and/or themanexaminationofcatalyticreactorsunder
musicalevents. periodic operation lasting over three-decades.
Currently, Bob is a professor emeritus, living
Kenji Hashimoto in Kitchener-Waterloo, Canada, where he also
plays piano and rings bells, helps spouse Vir-
Currently a Professor Emeritus of Kyoto
ginia in the garden, and (too seldom) visits his
University, Kenji retired from the University in
Vancouver-basedgrandchildren.
1999, but he has continued teaching and
research at Fukui University of Technology. He
has published some 210 technical papers on Motoaki Kawase
chemical reaction engineering and chromato- Motoaki is currently a Professor in the
graphic separation and written and /or edited Department of Chemical Engineering, Kyoto
7technicalbooks.Kenjihasservedasthepresi- University, wherehe supervisesthe Laboratory
dent of the Japanese Society of Chemical Engi- of Chemical Reaction Engineering. He gradu-
neering and received the highest Society ated from that department in 1987 and later
award for his academic achievements. He is obtained an Engineering Doctorate from the
a graduate of Kyoto University and holds an University. He is an early pioneer of simulated
Engineering Doctorate from that University. moving bed chromatographic reactors. He has
He now resides in Kobe, where he enjoys golf- authored or co-authored about 100 technical
ing andwatercolor painting. publications or conference papers in the field
xiii
ABOUTTHEAUTHORS
ofChemicalReactionEngineering.Hehaslived themathematicalmodelingandcontrolofpoly-
in Kyoto since birth. merizationreactors,andonthecharacterization
of polymers by size exclusion chromatography
Cheng-Yue Li and other analytical techniques.
Li recently retired from the Chemical Engi-
neering Department of the Beijing University Menka Petkovska
of Chemical Technology where he served as Currently a full professor at the Department
a Professor for some twenty years. He was ofChemicalEngineeringoftheFacultyofTech-
also a member of the State Key Laboratory of nologyandMetallurgyattheUniversityofBel-
Catalysis. With over 200 authored or co-auth- grade, in Belgrade, Serbia. She received her
ored journal publications, he is a Chinese Diploma, Master and Ph.D. degrees from the
pioneer of the study of reactor transient opera- same department. During her 28-years long
tion. Cheng-Yueand his wife residein Beijing. academic career, she was a visiting researcher
in France, Germany and Australia. She teaches
Yurii Matros courses in the area of process dynamics and
control and process intensification. She is an
Anengineer,ascientistandanentrepreneur,
author or co-author of two textbooks and
YuriioriginatesfromOdessaintheUkraine.He
about 50 scientific and technical papers. Her
is currently president of Matros Technologies
main areas of scientific interest are: nonlinear
Inc. located in St. Louis, Missouri, a design
dynamicsandnon-stationaryprocesses,adsorp-
and engineering company he founded in 1992.
tion and processintensification.
He completed an engineering degree at the
Technical University in Odessa. After a few
Mark Pritzker
years in the Russian chemical industry, he
joinedtheBoreskovInstituteofCatalysis(Novo- From Montreal, Mark is a McGill University
sibirsk, Russia) where he spent 28 years and graduateandholdsaPh.D.fromVirginiaPoly-
won a doctorate degree. He is a pioneer of the technicInstitute (1984). After a fewyears atthe
application of periodic operation, particularly University of Arizona, he joined the University
periodic flow reversal, to chemical processes. of Waterloo where he is now a Full Professor
Hehaswrittenand/oredited6technicalbooks, directing research on a wide variety of electro-
and authored or co-authored more than 300 chemical systems. Currently he works on high
technical papers. frequency pulse electroplating, modeling and
experimental studies of PEM and SOFC fuel
GregorioMeira cells, use of electrochemical methods for nano
materials fabrication and on process modeling
Greg Meira is a Chemical and Petroleum
of leaching and adsorption, and strand board
Engineer (University of Buenos Aires), and
manufacturing processes. Mark is the author/
holds M.Sc.and Ph.D. degreesinControlEngi-
co-author of more than 100 technical
neering (University of Bradford, UK). Since
publications.
1981,hehasbeenaFullProfessorattheUniver-
sidad del Litoral (Santa Fe, Argentina); and
Director of the Polymer Group at the “Institute Albert Renken
for the Technological Development of the Albert obtained his academic degrees at the
Chemical Industry” (INTEC, CONICET), also Technical University of Hanover, Germany. In
in Santa Fe. He is an author of over 100 1977hebecameProfessorofChemicalReaction
scientific publications and book chapters on Engineering at the Swiss Federal Institute of
xiv
ABOUTTHEAUTHORS
Technology, Lausanne. He is currently an Canadian Public Service Award for Excellence
Honorary Professor at that institution. He is in 2002 and Natural Resources Canada Depart-
author of over 450 scientific publications, mentalMeritAwardin 2001.
numerouspatentsandauthor/editorof5tech-
nicalbooks.From1992to2000,hewasascience Jeno Scharer
counciloroftheSwissNationalScienceFounda-
Jeno (BSc, PhD, Chemical Engineering,
tion, and from 1996 to 2002 he served as
UniversityofPennsylvania)isaProfessorEmer-
chairman oftheEuropeanFederationofChem-
itus in the Department of Chemical Engi-
ical Reaction Engineering Working Party. He is
neering, University of Waterloo, Canada.
also member of the Swiss Academy of Engi-
Although retiredin2004,hecontinues research
neering Sciences. Albert is widely recognized
that combines engineering , biological and
asapioneeroftheapplicationofperiodicoper-
biochemical concepts to the study of biological
ations to chemical processes.
processesrangingfrommammaliancellculture,
to recombinant microbial fermentations for
Alirio Rodrigues producing therapeutic agents andto diagnostic
Currently a Full Professor at the Chemical tools for the microbial oxidation of sulfide
Engineering Department of the University of mineralsoracidminedrainage.Hehasco-auth-
Porto in Portugal, Al´ırio is the Director of the ored a large number of research papers as well
Laboratory of Separation and Reaction Engi- as two books. For leisure, he trains champion-
neering (LSRE). Over a 40+ year career, he has shipdogs.
supervised over 50 PhD students and edited
and/or written 7 technical books and authored Andreas Seidel-Morgenstern
or co-authored some 450 technical papers and Andreas studied Process Engineering at the
5patents.HeisagraduateofUniversityofPorto Technische Hochscule Leuna, graduating in
and holds an Engineering Doctorate from the 1982; his doctorate in science is from the
University of Nancy (France). His research German Academy of Science in Berlin (1987)
focusesoncyclicadsorption/reactionprocesses, with a later Habilitation in 1994. Since 1995, he
perfume engineering and microencapsulation, has been a Professor of Chemical Process Engi-
CO2 capture and utilization and lignin neering at the University of Magdeburg. In
valorization. addition, he heads a large research team on
the physical and chemical foundations of
Hristo Sapoundjiev processengineeringfortheMaxPlanckInstitute
in Magdeburg. Andreas is now Managing
Hristo is a senior researcher at CanmetE-
Director of the Max Planck Institute for
NERGY, the Natural Resources Canada
Dynamics of Complex Systems. He is the
Research Centre in Varennes, Quebec, and
author/coauthor of over 350 journal papers
adjunct professor at the University of Alberta,
and editor/coauthor of 6 technical books. His
Canada. He has authored or co-authored some
special interests are in system dynamics, chro-
75 technical papers and he holds about 15
matography and reactionþ separation.
patents on development of environmentally
friendly and energy saving technologies. He is
a graduate of Sofia Technological University PeterSilveston
(Bulgaria) and holds an engineering doctorate Currently a “Distinguished Professor Emer-
from the Boreskov Institute of Catalysis, Novo- itus” of the Chemical Engineering Department
sibirsk, Russia. Hristo received the prestigious of the University of Waterloo in Canada, Pete
xv
ABOUTTHEAUTHORS
retired in 1997 after 35 years, but he has isagraduateofM.I.T.andholdsanEngineering
continued teaching, research and scholarly Doctorate from the Technical University of
writing. Over a 50+ year career, he has written Munich (Germany). He currently resides on
and/or edited 4 technical books and authored theCarolinacoastintheU.S.whereheindulges
or co-authored some 280 technical papers. He in hiking,bicycling and water sports.
C H A P T E R
1
Introduction
y
Robert Ross Hudgins*, Peter Lewis Silveston*, Albert Renken ,
Yurii Sh. Matros**
*Waterloo, Ontario, Canada, yLausanne, Switzerland and **Springfield, Missouri, U.S.A
O U T L I N E
1.1 Periodic Operation 1 1.10 Reaction Systems Examined 16
1.2 Originsof Periodic Operation 3 1.11 New Directions 17
1.11.1 Applicationsto Systems with
1.3 Variables inPeriodic Operation 4
MultipleObjectives 17
1.4 Cycle Structure inPeriodic Operation 6 1.11.2 Control of Carbon Deposition 17
1.11.3 Modulation of Multiple
1.5 Measuring Improvement 8
Reactor Inputs 18
1.6 Inherently Periodic Processes 9 1.11.4 Improvement of Photocatalysis 18
1.7 Objectives ofPeriodic Operation 10 1.12 A Brief History ofthe Study of
Periodic Operation 19
1.8 StrategiesinPeriodic Operation 10
1.12.1 Pioneers 19
1.9 EquipmentforPeriodic Operation 13 1.12.2 Research Groups 20
1.9.1 Laboratory Reactors 13 1.12.3 IndustrialApplications 21
1.9.2 Industrial-Scale Equipment 14
The objective of this monograph is to simulated moving bed chromatographic reac-
summarize the large and growing literature tors and swing reactors.
on the periodic operation of chemical reactors.
Research on such reactors is worldwide and
the subject continues to attract new investiga- 1.1 PERIODIC OPERATION
tors, even though penetration of the tech-
nology into industry has been limited Periodic operation is a technique for
primarily to flow direction switching, enhancingtheperformanceofacatalyticreactor,
PeriodicOperationofReactors
1
http://dx.doi.org/10.1016/B978-0-12-391854-3.00001-2 Copyright(cid:1)2013ElsevierInc.Allrightsreserved.