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THE CHEMICflL
PROCESSING PMNT
Process Intensification
edited by
flndrzej ftankiewicz
DSM Research
Geleen, and
Delft University of Technology
Delft, The Netherlands
Jacob fl. Moulijn
Delft University of Technology
Delft, The Netherlands
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
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ISBN: 0-8247-4302-4
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Preface
The book you are about to read will introduce you to modern ways of re-
engineering the chemical processing plant by means of Process Intensication (PI).
The story behind this book had begun with the paper Process Intensication:
Transforming Chemical Engineering, which we published in the millennium issue
of Chemical Engineering Progress (January 2000). After a pretty enthusiastic
response to our paper by the chemical engineering community, Marcel Dekker
proposed to us writing a book on that subject. After some discussions we came to
the conclusion that it was not a good idea to write the entire book ourselves
because, as you will see next, Process Intensication is a very broad discipline and
includes many diverse expertise elds. So, instead of writing all chapters on our
own, we have invited a number of prominent experts in various areas of Process
Intensication, both from industry and from academia, to contribute to what now
has become the worlds rst book on that subject.
The principal aim of this highly practice-oriented book is to illustrate the
current developments and the frontline research in the area of Process
Intensication. The book is primarily intended for engineers, technologists and
researchers in chemical, biochemical and engineering companies, who are
involved in process design and development and are interested in learning more
about equipment and techniques that may bring quantum-leap improvements to
their technologies. Also for others working in the forefront of process design and
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
development it is intended to be inspiring, in particular for the chemical engi-
neering community in the universities and the National Laboratories. We hope
that it will contribute to a better image of the chemical industry and even play a
role in attracting more high-quality, motivated students to the discipline. The
book may also be benecial to R&D managerial personnel who wish to have a
broader understanding of the principles and methodology of Process
Intensication and gain the up-to-date knowledge of the emerging novel equip-
ment and processing methods that could help to achieve technological break-
throughs in the processes at their companies.
The book has a certain logical structure that can be inferred from scanning
the individual chapter headings. Chapter 1 introduces the reader into the genesis,
philosophy and principles of Process Intensication and discusses its dimension
and structure. It provides general information on process-intensifying equipment
and methods and gives some examples of their application on the commercial
scale. The three subsequent chapters describe selected types of the PI-equipment.
Most of that equipment have already been successfully implemented on the com-
mercial scale or is ready for implementation. Chapters 2 and 3 are devoted to the
rotating equipment, rotating packed beds and spinning disk reactors, in which the
use of high gravity elds leads to spectacular miniaturization of the processing
units. Chapter 4 in turn describes the technology, design and application of com-
pact and multifunctional heat exchangers. The next three chapters show how
bringing certain structures in various scales of chemical processing environment
can boost process efciency, by dramatically improving mixing, heat and mass
transfer. Various types and scales of such structuring are presented: microreactors
in Chapter 5, large-scale structured catalysts and reactors in Chapter 6 and
inline mixing equipment in Chapter 7. Following that hardware part of the
book, its next four chapters focus on some important methods that can be used for
intensication of chemical processes. Chapter 8 presents the application aspects
of functional integration of reaction and separation into reactive separation sys-
tems, or integration of different separative techniques into hybrid separations. In
Chapter 9 the modeling issues of the reactive separation systems are discussed.
Chapter 10 discusses some aspects of the integration of reaction and heat transfer
in multifunctional reactors, while Chapter 11 focuses on the application of pro-
cess synthesis principles to the optimal design of integrated chemical processing
plants. The nal three chapters of the book address more general issues of Pro-
cess Intensication. Chapter 12, based on the experiences within DSM, shows
how the PI-principles can be applied in the industrial environment for re-
designing and development of process-intensive chemical plants, while Chapters
13 and 14 focus respectively on safety and sustainability aspects of PI.
The chemical industry skyline in the 21st Century is changing. New highly
efcient devices have already begun replacing the tens-of-meters high reactors and
separation columns. In the still denser populated world inhabited by the still more
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
educated and environment-conscious society, there will be no room (literally and
guratively) for the huge, inefcient chemical factories of today, generating tens
of tons of waste per each ton of the useful product. As a part of the society-driven
changes miniaturization and, in general, intensication of chemical and biochem-
ical plants, will become inevitable.
We are well aware that the present book does not cover all developments in
the eld of Process Intensication. It has not had such ambitions. With this col-
lection of contributions by the leading experts in the eld, we have tried to focus
on the main developments and main issues only, hoping that they will give the
reader sufcient avor of PI and will encourage him/her to further studies on how
to re-engineer a chemical processing plant basing on the smaller-cheaper-safer-
slicker principles of Process Intensication. Both contributors and editors will
be very glad to hear from the reader if we indeed have succeeded. Also sugges-
tions for a possible next edition are welcome!
Andrzej Stankiewicz
Jacob A. Moulijn
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Contents
Preface
Contributors
1. Process Intensication: History, Philosophy, Principles
Andrzej Stankiewicz and A. A. H. Drinkenburg
2. Chemical Processing in High-Gravity Fields
David L. Trent
3. The Spinning Disc Reactor
C. Ramshaw
4. Compact Multifunctional Heat Exchangers: A Pathway to
Process Intensication
B. Thonon and P. Tochon
5. Process Intensication Through Microreaction Technology
Wolfgang Ehrfeld
6. Structured Catalysts and Reactors: A Contribution to
Process Intensication
Jacob A. Moulijn, Freek Kapteijn, and Andrzej Stankiewicz
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
7. Inline and High-Intensity Mixers
Andrew Green
8. Reactive and Hybrid Separations: Incentives, Applications,
Barriers
Andrzej Stankiewicz
9. Reactive Separations in Fluid Systems
E. Y. Kenig, A. Grak, and H.-J. Bart
10. Multifunctional Reactors: Integration of Reaction and Heat
Transfer
David W. Agar
11. Process Synthesis/Integration
Patrick Linke, Antonis Kokossis, and Henk van den Berg
12. Process Intensication in Industrial Practice: Methodology and
Application
Remko A. Bakker
13. Process Intensication for Safety
Dennis C. Hendershot
14. Process Intensication Contributions to Sustainable Development
G. Jan Harmsen, Gijsbert Korevaar, and Saul M. Lemkowitz
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Contributors
David W. Agar Lehrstuhl fr Technische Chemie B, University of Dortmund,
Dortmund, Germany
Remko A. Bakker DSM Fine Chemicals Austria, Linz, Austria
H.-J. Bart Institute of Thermal Process Engineering, University of Kaiserslautern,
Kaiserslautern, Germany
A. A. H. Drinkenberg DSM Research, Geleen, The Netherlands
Wolfgang Erhfeld Ehrfeld Mikrotechnik AG, Wendelsheim, Germany
A. Grak Lehrstuhl fr Thermische Verfahrenstechnik, University of Dortmund,
Germany
Andrew Green BHR Group Limited, Craneld, England
G. Jan Harmsen Delft University of Technology, Delft, The Netherlands
Dennis C. Hendershot Rohm and Haas Company, Bristol, Pennsylvania, U.S.A.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Freek Kapteijn Delft University of Technology, Delft, The Netherlands
E. Y. Kenig Lehrstuhl fr Thermische Verfahrenstechnik, University of Dortmund,
Dortmund, Germany
Antonis Kokossis University of Surrey, Surrey, England
Gijsbert Korevaar Delft University of Technology, Delft, The Netherlands
Saul M. Lemkowitz Delft University of Technology, Delft, The Netherlands
Patrick Linke University of Surrey, Surrey, England
Jacob A. Moulijn Delft University of Technology, Delft, The Netherlands
C. Ramshaw Department of Chemical and Process Engineering, University of
Newcastle upon Tyne, Newcastle upon Tyne, England
Andrzej Stankiewicz DSM Research, Geleen, and Delft University of Technology,
Delft, The Netherlands
B. Thonon Greth, CEAGrenoble, Grenoble, France
P. Tochon Greth, CEAGrenoble, Grenoble, France
David L. Trent The Dow Chemical Company, Freeport, Texas, U.S.A.
Henk van den Berg Faculty of Chemical Technology, University of Twente,
Enschede, The Netherlands, and Ghent University, Ghent, Belgium
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
1
Process Intensication:
History, Philosophy, Principles
Andrzej Stankiewicz and
A. A. H. Drinkenburg
DSM Research, Geleen, The Netherlands
1. INTRODUCTION
Process intensication (PI) is currently one of the most signicant trends in chem-
ical engineering and process technology. It is attracting more and more of the
attention of the research world. Four international conferences, several smaller
symposia/workshops every year, and a number of dedicated issues of professional
journals are clear proof of it. A number of commercial-scale applications of the
PI principles have already taken place. But how did it all begin?
2. A BIT OF HISTORY
According to Miriam-Websters Collegiate Dictionary, the word intensive has prob-
ably its origins somewhere in 15th century. And it was not many years later, right
at the peak of the Renaissance, when Georgius Agricola published his famous book
De Re Metallica (1), the book that is commonly regarded as the rst comprehen-
sive textbook on the engineering of mining and metallurgy. De Re Metallica is
richly illustrated with woodcuts showing equipment and processing methods used
in the times of Agricola. In many of those woodcuts clear elements of process
intensicationoriented thinking can be found. One example is shown in Figure 1,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 1 Sixteenth century technology of gold retrieval from gold ore. (From
Ref. 1.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
which illustrates the process of retrieving gold from gold ore. The technology is
pretty simple. The ore is crushed by the stamp, C, ground in the mill, F, and
mixed with mercury in vessels O. Gold is extracted from the ore by mercury and
is later separated from it by pressing the mixture through a leather or cloth lter
bag (not shown in the drawing). Taking a closer look at the woodcut, one notices
that the stamp, the mill and the stirrers for mixing the ore with mercury are all
driven by the same water wheel, A, via the common axle, B, and a number of
various gears. Speaking the language of the 21st century, one could say, A mar-
velous example of a green, energy-based, highly integrated processing plant! (One
dare not, however, call it a sustainable technology. Not only are the gold reserves
unsustainable, but the operations involving mercury are not environmentally
friendly, as we all know today.)
Yet there is another aspect to Agricolas woodcut. As one may have noticed,
some of the equipment shown (OS) exhibits a striking resemblance to the
equipment used in the chemical process industry almost 450 years later (see
Figure 2). Were the contemporaries of Agricola so ingenious, or are we merely
satised with the inventions of past centuries? At the dawn of the third millennium,
in-series stirred tanks still remain the most common chemical processing system.
An attempt to break this domination of the stirred-tank technology by the invention
and introduction of the static mixer (2,3), is one of the nest and earliest modern
examples of process intensication. Here, the technological leap was achieved
not by the improvement of the stirring itself but, quite the opposite, by abandoning
the mechanical stirring as a method of mixing uids! This reveals one of the most
important features of PIthe changes it brings are drastic in nature, revolutionary
rather than evolutionary.
In the scientic literature, the term process intensication started to appear
in the mid-1960s and early 70s, mostly in East European publications concerning
FIGURE 2 Four and half centuries have passed, yet almost no fundamental
differences can be seen between the technology of 1556 and that of 2002.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
metallurgical processing (47) (an interesting coincidence, considering that
Agricolas book was also on metallurgy, not on chemical processing). Of course,
all of those papers understood process intensication as simply equivalent to
process improvement. Also, in the rst chemical industryoriented articles (all of
East European origin, by the way), the term process intensication had that same
meaning (810).
The birth of process intensication as a chemical engineering discipline came
several years later in the United Kingdom and was marked by the paper published
in 1983 by Colin Ramshaw from the ICI New Science Group, who described their
studies on the application of centrifugal elds (so-called HiGee) in distillation
processes (11). A few months later the Annual Research Meeting, entitled
Process Intensication, was held at UMIST, Manchester (12). Interestingly, the
rst paper presented at that meeting concerned processing of gold ore using
intensive methodsa strange coincidence, indeed.
Both in the paper by Ramshaw and in the report from the UMIST conference,
first denitions (or rather descriptions) of process intensication can be found.
Ramshaw (11) describes PI as devising an exceedingly compact plant which
reduces both the main plant item and the installations costs, while according
to Heggs (12) PI is concerned with order-of-magnitude reductions in process
plant and equipment. In one of his subsequent papers, Ramshaw writes about typ-
ical equipment volume reduction by two or three orders of magnitude (13).
Until the early 1990s, process intensication was mainly a British discipline
and was focused primarily on four areas: the use of centrifugal forces, compact heat
transfer, intensive mixing, and combined technologies (14). It was also the Brits
who organized the rst international conference on PI (15). By that time, however,
process intensication had already become an international business, for many
research centers in different countries had entered the eld. In Holland, for instance,
Delft University of Technology, together with DSM, carried out research on
structured reactors (16). Another group in Delft investigated centrifugal adsorp-
tion technology (17). In France, Greth CEN institute in Grenoble carried out
extensive studies on compact heat exchange equipment (18). In Germany, research
on microtechnology ourished in the Institut fr Mikrotechnik Mainz (19), while
in China a special center at Beijing University was established to carry out R&D
activities in the area of high-gravity processing (20). In the United States a number
of research institutes started PI-related studies too, e.g., Pacic Northwest National
Laboratory in the eld of microchannel heat exchangers (21) and MIT in the eld
of microreactors (22). Also early on, a number of chemical companies got involved
in process intensication. This involvement resulted in the rst successful
commercial-scale applications, such as the methyl acetate process of Eastman
Chemical (23), the hydrogen peroxide distillation system of Sulzer (24), and the
hypochlorous acid process of Dow Chemical (25).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The end of the 20th century and the beginning of the 21st have seen a fast
growth in PI-related activities in both industry and academia. In the UK the Process
Intensication Network was launched, gathering a large number of industrial and
academic participants; a similar network has been established in the Netherlands.
Four international conferences and several smaller symposia on PI have been
organized so far. Process Intensication, traditionally tied up with the commodity
chemicals sector, has begun entering new areas, such as bioprocessing and fer-
mentation (2628) and, quite recently, ne chemistry (29). The denition of process
intensication has changed accordingly. It is no longer exclusively regarded as
drastically smaller equipment/plants (although equipment compactness remains
its most obvious feature). Process intensication, as it is widely understood now-
adays, comprises novel equipment, processing techniques, and process development
methods that, compared to conventional ones, offer substantial improvements in
(bio)chemical manufacturing and processing (30).
The question may arise why it took so long for PI to come into the picture.
One possible answer is the enormous expansion of the process industry in the
third quarter of the 20th century, expansion in market size but certainly also in
plant scale. There were very few incentives at that time for the very risky intro-
duction of new technologies. In the fourth quarter of the century, much effort was
spent on modeling, optimization, and control, resulting, among other things, in
the well-known onionskin methodologies of process development (e.g., Ref. 31).
Although very worthwhile at the time, these sequential, onionskin methodologies
(rst the reactor, then separation/purication, then heat integration, then process
control, safety, etc.) hindered the thinking in terms of integrated equipment. More
incentives were found in environmental engineering, also a topic of the second
half of the 20th century, that developed from the end-of-pipe solutions to prob-
lems to the integrated process solutions backsourcing the problems.
3. THE PHILOSOPHY AND OPPORTUNITIES
OF PROCESS INTENSIFICATION
The philosophy of process intensication has been traditionally characterized by
four words: smaller, cheaper, safer, slicker. And indeed, equipment size, land use
costs, and process safety are among the most important PI incentives. But process
intensication can (and should) also be placed in a broader contextthe context
of sustainable technological development. Several years ago DSM published a
picture symbolizing its own vision of process intensication (32), in which sky-
scraping distillation towers of the naphtha-cracking unit are replaced by a compact,
clean, and tidy indoor plant (see Figure 3). The importance of PI for sustainable
development and its role in the companys responsible business has been further
stressed in a recent publication by the companys CEO, Peter Elverding (33). Here,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
process intensication was the highest-rated activity of DSM within the known
Triple-P (protplanetpeople) triangle, as shown in Table 1.
From this general philosophy of process intensication follow concrete
opportunities that PI offers to chemical enterprises, as shown in Figure 4. These
opportunities exist primarily in four areas: costs, safety, time to market, and com-
pany image.
FIGURE 3 DSMs vision of process intensication.
TABLE 1 Process Intensication in the ProtPlanetPeople
Triangle of DSM
Triple P
Prot Planet People
Process intensication
Green routes
Recycling
Energy efciency
Source: Ref. 32.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 4 Main benets from process intensication.
3.1. Costs
Process intensication leads to substantially cheaper processes, particularly in
terms of:
Land costs, resulting from much higher production capacity and/or number
of products per unit of manufacturing area
Other investment costs, resulting from cheaper, compact equipment, reduced
piping, reduced civic works, integrated processing units, etc.
Costs of raw materials, due to higher yields/selectivities
Costs of utilities, in particular costs of energy, due to higher energy efciency
Costs of waste processing (less waste generated in process-intensive plants)
Figure 5 shows the estimated savings in some DSM technologies, after applying
the PI principles (grass-roots situation).
3.2. Safety
Process intensication drastically increases the safety of chemical processes. It
is obvious that smaller is safer. In Table 2 some of the more severe chemical
disasters of the past century are listed. The table shows clearly how disastrous
consequences may arise from the large inventories when something goes wrong.
And of course, one may not claim that process intensication would have prevented
all those tragedies. Yet a study done at AIChE showed that methyl isocyanate (MIC),
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the poisonous intermediate that was released at Bhopal, could be generated and
immediately converted to nal products in continuous reactors that contained a
total inventory of less than 10 kg of MIC (34)! But process intensication offers
not only smaller equipment but also much better possibilities for keeping processes
under control, for instance, via extremely efcient heat removal from exothermic
reactions (one speaks about heat transfer coefcients exceeding 20,000 W/m
2
K)
or via fully controlled gasliquid ow in structured catalysts that prevents liquid
maldistribution and hot-spot formation. Furthermore, intensication of the pro-
cessing plant often leads to elimination of one or more of its components, which
also has a direct advantageous effect on process safety (What you do not have
cannot leak).
3.3. Time to Market
Process intensication also offers substantial improvements to those sectors of
the chemical industry in which time to market plays a crucial role, e.g., the ne
chemical and pharmaceutical sectors. Ramshaw (35) discussed how process
intensication could shorten the time to market in case of a low-tonnage pharma-
ceutical process. The idea consists in developing a continuous lab-scale process
and using it directly as the commercial-scale process. One must not forget that
liquid ow of only 1 milliliter per second means, in continuous operation, circa
30 tons per year, which is quite a reasonable capacity for many pharmaceuticals.
FIGURE 5 Estimated savings in some DSM technologies, achieved by apply-
ing PI principles to process and plant design (grass-roots situation).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
TABLE 2 Some 20th Century Disasters in the Chemical Industry
Estimated
Place Date Chemicals amount Casualties
Oppau/ September 21, Ammonium sulfate, 4,500 tons exploded ca. 600 dead, 1500 injured
Ludwigshafen 1921 ammonium nitrate
Flixborough June 1, 1974 Cyclohexane 400-ton inventory, 28 dead, 89 injured
40-ton escaped
Beek November 7, Propylene (mainly) 10,000-m
3
inventory, 14 dead, 107 injured
1975 5.5 tons escaped
Seveso July 10, 1976 2,4,5 Trichlorophenol, 7-ton inventory, No direct casualties,
dioxin 3 tons escaped ca. 37,000 people
exposed
San Juan, November 19, LPG 10,000-m
3
inventory ca. 500 dead, 7000
Mexico City 1984 injured (mainly
outside the plant)
Bhopal December 3, Methyl isocyanate 41 tons released ca. 3,800 dead, 2720
1984 permanently disabled
Pasadena October 23, Ethylene, isobutane, 33 tons escaped 23 dead, 130300 injured
1989 hexene, hydrogen
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The advantages of such an approach over the conventional one, based on the
scale-up philosophy of stirred tank bigger stirred tank even bigger stirred
tank, always batch are twofold:
Process development takes place only once, with no scale-up via a pilot
plant to the industrial scale. The scale-up of a batch process in stirred
tanks is not straightforward, especially in the case of reactions with a
large heat effect or a strong viscosity effect, and therefore can be trouble-
some and time-consuming.
All the administrative (FDA) procedures involved in the legal approval of
the production technology of the drug take place only once: The lab-
scale technology is the commercial-scale technology.
In consequence, the start of commercial production can be greatly speeded up,
in some cases even by several years. Time to market will be shortened and the patent
lifetime of the drug will be much more effectively utilized (read: utilized longer).
3.4. Company Image
More and more chemical companies do recognize the fact that their image, their
reputation, plays a very important role in successful business. A proper image of
the company is necessary to ensure public support for its activities. A study done
in the United States showed that only the tobacco industry and the nuclear energy
sector had a worse reputation than the chemical industry. The situation in Europe
is probably not very much different. On the other hand, process intensication,
deeply anchored in the philosophy of sustainable development, in safe and envir-
onmentally friendly processing, presents perhaps the simplest, the most obvious
key to the improved image of the chemical industry.
4. TECHNOLOGICAL BREAKTHROUGHS
AND CREATION OF SHAREHOLDER VALUE
In the reality of the global markets of the 21st century, not only do chemical com-
panies compete with each other, they also have to compete with other sectors of
the economy by proving to their shareholders that the revenues they receive from
the chemical business are as good as or better than from other fast-growing sec-
tors, such as software and servicing. But the chemical process industry struggles
to create value for its shareholders. As John Goldhill of Arthur D. Little Inc.
wrote, the chemical industry has lagged other industries in creating value for
shareholders for at least the past 10 years (36). And indeed, when looking at
stock index developments in various types of enterprises in the period 19972002
(Figure 6), one notices that the value of chemical shares grew substantially slower
than in other sectors. The strategy of growth in the chemical process industry at
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the present time is based mainly on mergers, splits, takeovers, and modifying the
structure of the product portfolio. It is basically a strategy of growth via trade, not
via technological innovation. In most chemical companies nowadays, opportuni-
ties are sought in cost reductions via optimization of the primary business work
processes (e.g., operational excellence) and via opening up bottle necks in the
existing production facilities.
Unfortunately, neither of these activities can make a company very attrac-
tive to shareholders. In the optimization of work processes, a critical limit in cost
reductions will soon be reached, and competitors will also follow more or less the
same path, so the companys competitive advantage will only be temporary unless
a shakeout takes place. Opening up bottlenecks, squeezing out yet another few
percent from existing plants, is also not the way to convince investors that the
company is capable of delivering an adequate growth in earnings. One of the most
obvious solutions to that problem lies in innovations and technological break-
throughs, because only innovations and technological breakthroughs can ensure
a sustainable technological advantage, cost leadership, and growth potential.
Innovations and technological breakthroughs are what process intensication is
all about.
FIGURE 6 History of the Standard & Poor stock index in the chemical sector
and other selected sectors of the economy, 19972002. (From: www.
bloomberg.com.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
5. PROCESS INTENSIFICATION TOOLBOX
The toolbox for process intensication is schematically shown in Figure 7. It
includes process-intensifying equipment (PI hardware) and process-intensifying
methods (PI software). Obviously, in many cases overlap between these two
domains can be observed as new methods may require novel types of equipment
to be developed and, vice versa, novel apparatuses already developed sometimes
make use of new, unconventional processing methods. In Figure 7, examples of
both PI hardware and PI software are shown. Many of them will be discussed in
detail in other chapters of this book. Here, we give only a brief overview of the
more important PI items.
5.1. Process-Intensifying Equipment
As already mentioned, one classic example of technological breakthroughs in
process engineering was the invention and commercialization of static (motion-
less) mixers, examples of which are shown in Figure 8. Nowadays, static mixers
not only offer a more size- and energy-efcient method for mixing or contacting
uids. In the SMR static mixer reactor by Sulzer, mixing elements are made of
FIGURE 7 Process intensication toolbox.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
heat transfer tubes (Figure 9). Thanks to that, the SMR units can successfully be
applied in processes in which simultaneous mixing and intensive heat removal/
supply are necessary, e.g., in nitration, neutralization, and polymerization re-
actions.
For the cases when efcient mixing has to be coupled with a solid-catalyzed
reaction a whole family of open-crossow-structure catalysts has been devel-
oped. The best known of them are the so-called KATAPAK
s, commercialized by
Sulzer. One of them, KATAPAK-M
_
,
_
,
.
.
versus
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the light-phase or heavy-phase takeoff. The movement of the principal interface
is controlled by the back pressure of the light-phase takeoff, which is a function
of the rotor speed and phase density difference (24).
3.3. Residence Time
Liquid residence time in the packed rotor varies as a function of packing depth,
packing type, rotor speed, and liquid properties (26). Two basic approaches have
been applied to the measurement of liquid in the rotor. The rst measure is the
average residence time of the liquid within the rotor, and the second is the liquid
holdup on the packing. Due to the ow patterns described previously, not all of
the rotor packing is wetted and not all of the liquid resides on the packing sur-
face. As a result, average residence time and liquid holdup are distinct measures
of liquid ow, contrary to the experience with packed towers.
Tracer methods, both visual and electrical conductivity sensors, have been
applied to measure the residence time of the liquid in the rotor (15,26). Measured
liquid residence time ranges from about 0.2 seconds to about 1.8 seconds. Time
decreases as the rotor speed increases, as liquid ow rate increases, and as the
radial position increases. Gas ow rate and liquid viscosity (narrow test range)
have little impact on residence time (15,19,26).
Since liquid does not completely wet the packing and since lm thickness
varies with radial position, classical lm-ow theory does not explain liquid ow
behavior, nor does it predict liquid holdup (30). Electrical resistance measure-
ments have been used for liquid holdup, assuming liquid ows as rivulets in the
radial direction with little or no axial and transverse movement. These data can
then be empirically t to lm-ow, pore-ow, or droplet-ow models (14,19).
The real ow behavior is likely a complex combination of these different ow
models, that is, a function of the packing used, the operating parameters, and uid
properties. Incorporating calculations for wetted surface area with the lm-ow
model allows prediction of liquid holdup within 20% of experimental values (18).
Liquid holdup in liquidliquid extractors must be dened for both the
heavy and light phases. The light-phase outlet pressure is used to control the rel-
ative liquid holdup of the two phases. Higher light-phase outlet pressure increases
the light-phase holdup. This pressure has been correlated with the phase density
difference, rotor speed, and rotor dimensions (24). In addition, packing charac-
teristics of volumetric surface area and porosity inuence liquid holdup and
throughout capability (23).
3.4. Mass Transfer
Developing correlations to describe mass transfer in rotating packed beds has
proven to be a challenge. Penetration theory (31), lm-ow theory (32), and modi-
ed surface-renewal theory (12) are some examples of leveraging previous work
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
to the rotating packed bed. At issue is the need to include a multiplicity of variables
as well as to understand the hydrodynamics of gas/liquid contact within the rotor.
Each modeling approach compared experimental data to the models, with reason-
able t. However, these expressions have not yet been validated on multiple-RPB
designs and operating conditions. A key to developing a generalized model for
mass transfer performance is the proper understanding and treatment of the uid
ows within the rotor, as discussed previously in Section 3.1.
The combination of high surface area, high velocities, thin lms, and
intense mixing in the packing provides an environment for intensive mass trans-
fer, resulting in values for height of transfer unit (HTU) of 1.54 cm (26). Mass
transfer has been described using HTU, number of transfer units (NTU), mass
transfer coefcient (k
L
, k
G
), and volumetric mass transfer coefcient (k
L
a, k
G
a,
k
S
a). To accommodate the variation in packing surface wetting with radial distance,
an area transfer unit (ATU) has been proposed (33). Another proposed method of
evaluation uses a volume transfer unit (VTU) to account for the entire volume of
the packed rotor (34). Although the ATU and VTU methods may have merit in
evaluating RPB performance, these methods make comparison with other trans-
fer devices based on HTU more difcult.
The possible physical design parameters affecting mass transfer include
packing and packing supports. Atomization of the liquid as it impacts the spin-
ning rotor packing creates high-surface-area liquid drops, in addition to the lm
wetting of the high-surface-area packing. This atomization results in signicant
mass transfer apart from the packing surface. As a result, low-surface-area pack-
ings produce equivalent, if not better, volumetric mass transfer coefcients than
do high-surface-area packings (35,36). This implies that low-surface-area pack-
ing with high porosity can effectively replace high-surface-area packing, contrary
to the experience with packed towers. The result is lower-cost packing, reduced
pressure drop, and higher throughput. Packing supports at the inside diameter of
the rotor generally provide a positive effect on mass transfer (36). Due to the
atomization of liquid exiting the rotor, additional mass transfer occurs in the
space between the rotor and the housing (37).
Operational parameters of importance to mass transfer include rotor speed,
liquid rates, and gas/liquid ratios. Mass transfer increases proportionately to rotor
speed, decreases with increasing liquid ow, and increases with gas/liquid ratio
(17,26,36). Although most references present rotor speed as revolutions per
minute (rpm), expression as either tangential velocity (r) or multiples of gravity
(r
2
) provides a better basis for comparison among the different rotor designs and
for scale-up.
Gas-side mass transfer in rotating packed beds does not show the same
level of enhanced performance as liquid-side mass transfer. Average volumetric
gas mass transfer values for a wire screen packing increased with gas ow rate
but decreased with increased rotor speed. Compared to a packed tower, the RPB
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
mass transfer coefcient (18 s
1
) was similar when operated at similar super-
cial gas velocities (1 m/s). However, when gas velocities were increased
(412 m/s) in studies with parallel at plates as the rotor, the mass transfer coef-
ficient also increased, to a high of 45 s
1
(16). In a commercial-scale RPB, average
volumetric gas-side mass transfer coefcients of 4050 s
1
were achieved using
a wire screen packing and gas velocities of 45 m/s (9). The factors affecting gas-
side mass transfer are less understood than those of liquid-side mass transfer.
Liquidliquid mass transfer in centrifugal extraction contactors shows simi-
lar trends on performance as the gasliquid contactors. Mass transfer improves at
higher rotor speeds, higher solvent ratio, and higher phase density difference.
Since the light-phase outlet pressure controls the liquid holdup of both phases,
decreasing the light-phase outlet pressure decreases the light-phase holdup and
increases the number of transfer units (24). Packing characteristics of pore size,
porosity, and volumetric surface area also play a role in performance (23). Single
centrifugal extractors have achieved up to 10 theoretical stages of extraction (38),
but they could achieve up to 20 stages with suitable rotor design (11).
Liquidsolid mass transfer has also been studied, on a limited basis.
Application to systems with catalytic surfaces or electrodes would benet from
such studies. The theoretical equations have been proposed based on lm-ow
theory (32) and surface-renewal theory (39). Using an electrochemical cell with
rotating screen disks, liquidsolid mass transfer was shown to increase with rotor
speed and increased spacing between disks but to decrease with the addition of
more disks (39). Water ow over naphthalene pellets provided 46 times higher
volumetric mass transfer coefcients compared to gravity ow and similar super-
cial liquid velocities (17).
3.5. Pressure Drop
Gas pressure drop through the RPB rotor is an important consideration when
comparing the performance of the RPB with other mass transfer devices, such as
a packed tower. Numerous studies on pressure drop in RPB rotors employing a
variety of packings have yielded some surprising differences from conventional
packed towers. For example, lower pressure drop for wetted packing compared to
dry packing has been reported (26,40,41). Not all researchers observed this phe-
nomena, because pressure drop was found to be a function of packing type, rotor
design, gas rates, liquid rates, and rotor speed (41).
Pressure drop has been reported for a number of rotor internals, including
corrugated structured packing (28), foam metal (26,40,42), rectangular and ellip-
tical cylinder plastic grains randomly packed (41), wire screen (43), and glass
beads (17). In spite of the variation in porosity from 0.38 to 0.95 and in volumet-
ric surface area from 500 to 4000 m
2
/m
3
, all of these studies showed similarities
of increased pressure drop as rotor speed increased and gas rates increased.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
In addition to the differences in packing type and characteristics, these stud-
ies also had a variety of rotor and housing designs for the gas and liquid inlet and
outlet. All of them measured a gas pressure drop from the inlet gas piping or
housing to the outlet gas pipe. In an effort to develop models of the pressure drop,
most have attributed the pressure drop to centrifugal and frictional forces in the
rotor, using a lm-ow model (43). Pressure drop is proportional to the square of
rotor speed (26,42). Compared to conventional packed towers, the pressure drop
is lower per NTU (26) and about 15 times higher at ooding conditions (28).
To account for the differences in machine conguration and to better
explain the pressure-drop observations (e.g., lower pressure drop with onset of
liquid ow), a model based on conservation of mass and momentum, in particu-
lar gas angular momentum, was developed (40). This model divided the pressure
drop into four increments that included the gas inlet to the machine housing, the
rotor, the eye of the rotor, and the gas exit nozzle from the machine.
Although the models for pressure drop have a basis in theory, all are t
empirically to data generated from specic equipment. Application of these
models may not be relevant to machines of different congurations and packing
types (9).
In liquidliquid contactors, pressure drop is dened by the light phase. The
heavy phase enters at near atmospheric pressure and is accelerated by the rotor to
its discharge pressure. The pressure drop of the light phase is a function of phase
density difference, rotor speed, rotor diameter, and location of the principal phase
interface (24).
3.6. Heat Transfer
Most of the experimental work on heat transfer in centrifugal elds has been done
on spinning discs, which is the subject Chapter 3 in this book. A brief review of
the enhanced heat transfer rates is relevant here. Studies on a smooth, at spin-
ning disc show heat transfer coefcients as high as about 20 kW/m
2
K. The co-
efcient is highest at the inlet to the disc, due to disturbances as the liquid is
accelerated to the angular velocity of the disc. The heat transfer coefcient
increases with increased rotor speed but decreases with increased radial position.
Higher-viscosity uids decrease the heat transfer rate. Heat transfer is generally
higher than predicted from lm or penetration theory (44).
Modifying the surface of the disc allows enhancement of the heat transfer
by introducing liquid lm instabilities (waves). Best results come from the com-
bination of thin lms and large instabilities as revealed from the study of four sur-
face geometries: smooth, sprayed metal, and two types of concentric grooves. In
general, increased rotor speed gives higher heat transfer. However, with the
grooved disc, high speeds cause liquid separation from the disc, resulting in lower
heat transfer (45).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Heat transfer involving non-Newtonian uids has not been studied in rotat-
ing devices. Models have been developed for gravity-driven heat transfer for
power-law uids (46). These models may be useful as a starting point to evaluate
performance in higher-gravity elds.
Another method of introducing heat to uids in rotating devices involves
the generation of eddy currents by rotation through a stationary magnetic
field. This approach was successfully used in a polymer devolatilization
process (47).
3.7. Power
Estimating power consumption in rotating systems depends on several factors,
including acceleration of the liquid, windage effect of gas drag on the rotor, fric-
tion in the bearings and seals, and gas pressure drop (33,48). As would be expec-
ted from power consumption in such devices as centrifugal pumps, the largest
power component involves acceleration of the liquid to the angular velocity of
the rotor at the outer diameter. Gas pressure drop actually decreases power
consumption in the rotor. Frictional losses are dened by the design of the rotor,
bearings, and seals.
3.8. Rotor Internals
The rotor packing has an impact on all of the previously mentioned process fun-
damentals. Hydrodynamics, especially at the liquid inlet to the packing, is a func-
tion of packing porosity and volumetric surface area (12,13). These same packing
properties inuence pressure drop, residence time, and ooding velocity (26).
Liquid-side mass transfer performance is best with wire gauze as compared to
glass beads or parallel at plates (8). Gas-side mass transfer is better with paral-
lel at plates than in wire gauze (16). Flat plates provide the best medium for heat
transfer (34).
4. MECHANICAL DESIGN
Since the development of high-gravity elds requires rotating equipment, the
mechanical design is very important when considering operating performance,
cost of design and fabrication, ease of maintenance, and overall reliability.
Although most public reports on RPB studies describe the particular RPB design
used in the reported studies, very little information has been published on the
mechanical design principles. Original equipment manufacturers of rotating equip-
ment provide an effective resource for proper design and fabrication of RPBs. The
following discussion outlines some of the basic issues to be considered in the
machine design. Overriding all of the following discussion is the need to design a
stable rotor with minimal vibration under the desired operating conditions.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
4.1. Cantilevered Versus Centerhung Rotor
Once the rotor dimensions of inside diameter, outside diameter, and axial height
have been determined from the operating performance requirements, the rotor
orientation on the shaft must be determined. Two options are available, can-
tilevered, also called overhung, and centerhung. These relate to the position of the
rotor relative to the shaft and the support bearings. The cantilever design places
the rotor at the end of the shaft, while the centerhung design positions the rotor
in the middle of the shaft, with bearings on either side of the rotor. Often the
determining factor for selection is the ratio of axial height (AH) to outside rotor
diameter (OD). The conservative approach limits cantilever selection to AH/OD
0.5, though designs with ratios up to about 0.85 are possible. Numerous examples
of rotating equipment, such as pumps, compressors, and centrifuges, can be found
for each design conguration. Figure 5 illustrates the vertical-shaft cantilever
design; Figure 6 illustrates the horizontal-shaft cantilever design; and Figure 7
illustrates the horizontal-shaft centerhung design.
In addition to the rotor dimensions, other considerations for selection of
rotor shaft position include impact on operating performance, cost of manufacture,
maintenance, and number and type of seals. The operating performance is not
expected to deviate signicantly based on rotor position. The possible considera-
tions include rotor imbalance due to ooding of the housing and liquid distribution
on the rotor. In general the centerhung design is considered more stable, but it has
a slightly higher cost of manufacture due to the split case housing, is more dif-
cult to maintain, and requires two shaft seals instead of one. Standard equations for
fatigue and rigidity are used to determine shaft diameter for both orientations.
4.2. Horizontal Versus Vertical Shaft Orientation
The centerhung design is restricted to a horizontal shaft orientation. A vertical-
shaft cantilever design is expected to have slightly lower maintenance costs than
the horizontal-cantilever design. Both cantilever options should have similar
design and fabrication costs. Flooding of the housing due to insufcient liquid
drainage would be less of a problem with the vertical-shaft arrangement with
respect to rotor imbalance. Liquid distribution on the rotor can be inuenced by
gravity more on the vertical shaft, but the effect should be minimal. Reference 7
illustrates both the centerhung and cantilever horizontal-shaft arrangements and
discusses an application for use of the vertical-shaft cantilever design.
4.3. Seals
Two types of seals are needed to prevent uid leakage from the housing and to
ensure that gas passes through the rotor countercurrent to the liquid. Seals on the
shaft as it passes through the housing can be of a design appropriate for the uids
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 5 Pilot-scale RPB illustrating the vertical-shaft cantilever design with
direct motor drive. (Photo courtesy of The Dow Chemical Company.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
being handled. Mechanical seals, lip seals, and packing glands are some suitable
examples. As mentioned previously, a centerhung rotor requires two shaft seals,
whereas the cantilever rotor requires only one. To seal the rotor to prevent gas
bypassing, labyrinth seals and liquid ring seals are options. Figure 1 shows the
position of seals for a vertical-shaft cantilever design.
FIGURE 6 Pilot-scale RPB illustrating the horizontal-shaft cantilever design
with direct motor drive. (Photo courtesy of Higravitec Center of Beijing Uni-
versity of Chemical Technology.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
4.4. Power Train
Options for connecting the motor drive to the shaft depend on the shaft orienta-
tion. A vertical-shaft cantilever design would prefer a belt drive to reduce the cost
of manufacture of the support structure and to facilitate maintenance. A horizon-
tal shaft has the additional option of direct coupling. Variable speed can be
accomplished through a gearbox or preferably through variable frequency control
on the motor. In addition to the power requirements discussed previously, the
startup power to overcome the torque of the rotor must be considered. This start-
up power is related to the time required to reach the desired rotor speed.
4.5. Liquid Distribution
As discussed previously, proper liquid distribution on the rotor is critical to per-
formance, but it is also important to prevent rotor imbalance. Rotor imbalance
FIGURE 7 Commercial water deaeration RPB using the horizontal-shaft cen-
terhung design and direct motor drive. (Photo courtesy of Higravitec Center
of Beijing University of Chemical Technology.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
from liquid maldistribution is especially a problem with high-viscosity uids.
Liquid distributor pipes extending the axial length of the rotor, depending on
the pipe diameter and number, can be a source of additional gas pressure drop.
Gas ow around the distributor pipes can also be a source of vibration. In the case
of a vertical-shaft arrangement, the liquid head in the vertical distributor pipe
must be considered to ensure equal liquid distribution on the axial length of
the rotor.
The rotor can be used to assist liquid distribution either by attaching the dis-
tributor pipes to the rotor or by introducing the liquid onto the rotor and allowing
the centrifugal force to move the liquid to the packing. In the former option the
liquid must enter the RPB through the shaft, requiring machining of a channel in the
shaft and an additional seal. In the case of liquidliquid extraction, the shaft must
have at least one channel for introduction of one of the liquid phases (see Figure 2).
4.6. Rotor Packing
The selection of the type of rotor packing depends largely on the performance
requirements. However, there are some mechanical design considerations. Examples
of packing include woven wire screen, pellets randomly packed, foam metal, and
structured packing. The materials of construction must have physical properties suf-
cient to withstand the hydraulic forces created by the accelerating liquid. The pack-
ing must be dimensionally stable during operation to avoid rotor imbalance issues.
Some packing materials may require supports to keep them in place. Proper
design of the supports will consider porosity to prevent ooding, strength, impact
on uid distribution, and pressure drop.
4.7. Multiple Rotors
Several designs involving multiple rotors have been proposed. To accommodate
the need of additional transfer units in countercurrent gas/liquid contact, a verti-
cal shaft with at least two rotors and appropriate internals to conduct the gas from
the bottom to the top and liquid from top to bottom can be built (5). Another vari-
ation allows for heat transfer in addition to the mass transfer. By providing rotors
for condensation and for boiling and multiple packed rotors for gas/liquid con-
tacting, a self-contained distillation column on a single shaft is envisioned (6).
Obviously, these multiple-rotor devices are more complex from a mechanical
design and construction perspective. However, they offer some interesting possi-
bilities for reducing plant size by combining multiple unit operations and addi-
tional stages of separation in one piece of equipment.
5. APPLICATIONS
The operating and design principles given previously provide a basis for under-
standing the performance enhancement available to a wide variety of applications.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
These include standard mass transfer operations, such as absorption and strip-
ping, but also include reaction systems. The following section highlights some of
the applications for which data are available and suggests other opportunities for
exploitation of the intensied mass and heat transfer capabilities.
5.1. Absorption
Absorption of a component of a gas stream into a liquid is a common practice in
the chemical industry to affect cleanup of vent gases, conduct chemical reactions,
purify products, or to recover products from process streams. The enhanced mass
transfer capability of RPBs provides the opportunity to perform absorption pro-
cesses in smaller equipment, to lower inventories, to shorten startup and shutdown
times, and to lower pressure drop (48). Figure 8 provides a visual comparison of
the size of a conventional absorber tower next to three RPBs that handle the
equivalent gas and liquid ows (9).
An example of industrial relevance is the removal of sulfur dioxide (SO
2
)
from vent gases by absorption into water or a lime slurry (48). In the water
absorption process, both gas-lm and liquid-lm resistance to mass transfer
occurs. As a result the overall mass transfer rate is proportional to gas-ow rate
and acceleration but inversely proportional to liquid-ow rate. Due to the fast
reaction of SO
2
with lime, this system is only gas-lm diffusion limited. The
overall mass transfer rate is largely unaffected by gas- or liquid-ow rate and is
proportional to acceleration, but to a lesser extent than the water absorption
process. In both cases the overall mass transfer rate is reportedly much higher
than the corresponding conventional packed towers.
In another study of gas-side mass transferlimited absorption involving
SO
2
absorption into a sodium hydroxide solution using a wire screen packing, the
overall mass transfer coefcient was found to be lower than reported data for
packed towers (16). Replacing the wire screen packing with two parallel rotating
plates signicantly enhanced the mass transfer performance.
Absorption of hypochlorous acid into water, a liquid-side mass transfer
limited process, showed HTU values as low as 4 cm, with a strong dependence
on liquid-ow rate. Heat of absorption removal was identied as a potential issue
with absorption in rotating beds (9).
5.2. Stripping
Removal of volatile components from the liquid phase to a gas phase has been the
object of much study in RPB devices. One of the early successful applications
was oxygen removal from water for use in secondary oil eld recovery and boiler
water feed (7). The oil eld application demonstrated oxygen removal from 614
ppm to less than 50 ppb in both 50-T/h and 300-T/h RPBs using natural gas for
stripping. The packing had 92% porosity and 500-m
2
/m
3
volumetric surface area
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 8 Commercial use of RPB technology in HOCl process. (Photo cour-
tesy of The Dow Chemical Company.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
and was constructed of wire mesh. Comparison with conventional vacuum des-
orption in a packed tower combined with chemical reduction agents showed
lower cost and equipment size for the RPB approach. The proposed application
on oil platforms promises further advantages of weight reduction over conven-
tional process equipment.
The boiler feed water deaerator reduced oxygen content to less than 7 ppb
by the use of exhaust steam (low pressure). This system operated at lower tem-
perature (110C), used lower-pressure steam (0.05-MPa gauge), and achieved the
oxygen specication without the use of chemical reducing agents as compared to
conventional thermal desorption in a packed tower (7).
The preceding approaches to water deaeration used a gas continuous
process in the RPB. A liquid continuous RPB has been designed and tested for
this application as well (21). The liquid continuous process allows design of the
RPB for reduced power requirements, but it does require higher-pressure gas to
overcome the hydraulic head of the liquid. The schematic in Figure 2 shows the
liquid takeoff near the eye (inside diameter) of the rotor, thus recovering the
power needed to accelerate the liquid. In the case of oil platform water deaeration
using produced methane gas, boosting the pressure of the available gas would not
be necessary. As with the gas continuous process, mass transfer is enhanced by
increasing rotor speed and increasing gas-ow rate. Sampling at various radial
positions in the polyurethane foam packing revealed the possibility of liquid
back-mixing within the rotor that reduced the mass transfer efciency, i.e., fewer
transfer units than expected (21). Further work on the hydrodynamics of the gas
and liquid interaction may be warranted in order to realize the full potential of this
energy-saving approach for stripping (49).
A novel example of stripping in rotating packed beds is the stripping of
residual monomer and solvent from polymers (47). In polystyrene production,
conventional vacuum desorption achieves residuals reduction to about 500 ppm.
Steam-stripping technology is available to reduce residuals to about 200 ppm.
Compared to steam stripping, the RPB technology is expected to reduce capital
cost, energy costs, and equipment size and to eliminate the potential for side reac-
tions of steam with the polymer. A pilot-scale devolatilizer, called an Accelerator,
and a larger demonstration unit showed the viability of this approach. Data col-
lected at 510 mm Hg pressure followed the equilibrium curve for residual
styrene and solvent. This indicates that the mass transfer capability is more than
adequate to achieve equilibrium conditions in the short residence time in the
rotor. As a further effort to minimize process costs, the devolatilization rotating
packed bed was combined with a centrifugal pelletizer. Heating of the rotor and
polymer was accomplished by eddy currents generated by placing magnets on either
side of the rotor. Since the high viscosity of the polymer melt requires higher
g-force to achieve thin-lm ow over the packing compared to earlier gas/liquid
applications, the packing must have sufcient compressive strength to withstand
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the generated forces. A reticulated foam metal packing of high porosity (90%)
and high surface area (500 m
2
/m
3
) was used (47).
Air stripping of volatile organic compounds from groundwater shows the
possibility of using RPB technology for either continuous operation or intermittent
remedial operation. Since a wide variety of processes (membranes, air stripping,
biological activity, chemical oxidation, and carbon adsorption) are available to
remove volatile organics from water, the selection of RPBs will depend on
the performance requirements and the relative cost compared to the alternatives.
Tests on air stripping of jet fuel components from groundwater show the viability
of RPB use (33). Both a wire gauze packing and a reticulated foam metal
packing proved effective in removing compounds such as benzene, o-xylene,
toluene, 1,2,4-trimethylbenzene, and naphthalene. A demonstrated number of trans-
fer units as high as 12 gave corresponding height-of-transfer-unit values of 23 cm.
Another stripping application actually involves absorption and reaction as
well. Chlorine gas absorbs into sodium hydroxide aqueous solution, reacts to pro-
duce hypochlorous acid (HOCl), and is then stripped using excess chlorine gas.
The primary measure of performance of this operation is the recovery of stripped
HOCl. This study showed the importance of liquid distribution (type of spray
nozzle), gas/liquid ratio, and type of packing (wire gauze preferred over glass
beads or at plates). Above a minimal g-force, little performance improvement
was seen. Low-surface-area wire gauze packing (660 m
2
/m
3
) was just as effective
as high-surface-area (2800 m
2
/m
3
) packing (8). Scale-up to commercial operation
of this process showed a doubling of the HTU for this gas-side mass transfer
limited stripping. The actual pressure drop in the commercial scale RPB was half
the expected value. This same correlation, empirically based on centrifugal and
frictional factors of lm ow, effectively modeled the pilot RPB (9).
5.3. Distillation
Distillation combines absorption and stripping in one device. Rotating packed
beds perform distillation by use of external condensers and reboilers, as in con-
ventional towers (29), or by use of internal heat exchangers as part of the rotor (6).
Up to 20 theoretical plates were demonstrated in a rotor of 800-mm diameter (50).
Distillation was demonstrated on a 3-tons/h pilot plant separating an ethanol/
propanol mixture at total reux. The pilot plant consisted of two RPBs, one for
stripping and one for rectication, along with external reboiler and condenser,
respectively (51). Retrot of existing distillation towers with an RPB has been
proposed as a means to adding separation stages (52).
Another pilot distillation study employed only one RPB along with exter-
nal condenser and reboiler. The cyclohexane/n-heptane mixture was separated at
rates up to 9 tons/h at total reux. The system provided up to 6 transfer units
(NTU) of separation in a 21-cm packing depth. The primary variable affecting
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
separation was rotor speed. Two operating pressures and a range of gas loading
(reboiler duty) provided additional data for analysis (29,42).
5.4. Heat Transfer
Heat input or removal in rotating systems is best accomplished using plates to
separate the heat transfer uids from the process uids (45). Since spinning disc
technology is discussed in Chapter 3 of this book, this section will cover only the
application of heat transfer in conjunction with rotating packed beds and some of
the issues related to further development needs.
In the 1950s Hickman developed a centrifugal vapor compression evapora-
tor for seawater desalination (53). This device consisted of multiple spinning
discs. Seawater sprayed on one side of the disc evaporated, while the centrifugal
force removed the residue from the plate surface. The vapor was compressed and
returned to the opposite side of the plate, where condensation provided the heat
for evaporation and the desired freshwater for recovery. Overall heat transfer
coefcients of 18 kW/m
2
-K are about three times higher than those achieved in
steam turbine condensers.
A high-intensity heat pump, called Rotex, has been developed taking
advantage of the enhanced heat and mass transfer performance of rotating discs
(44). This single device carries out the processes of evaporation, condensation,
absorption, and heat transfer to a working uid.
The higher heat transfer coefcients experienced by Hickman led to the
concept of placing a peripheral reboiler and core condenser on either side of a
rotating packed bed (50). This concept would be useful for distillation applica-
tions that need reux and boilup. The internal exchangers as part of the rotor
would decrease the required heat transfer surface area but would involve add-
itional design and fabrication complexity.
Although heat exchangers on either end of a packed rotor are an option for
replacing external heat exchangers for distillation, the problem of heat transfer
within a porous packed bed remains. Heat input can be achieved by use of eddy
currents (47), microwaves, or sonic energy. Thus operations such as evaporation,
stripping, and endothermic reactions can be envisioned. Heat removal, however,
is more problematic. Exothermic reactions must be conducted adiabatically with-
in the rotor, unless a suitable means of extracting the heat of reaction can be
developed. One approach could be alternating packing and heat transfer plates.
This raises the complexity of design and fabrication but could provide the needed
cooling to approach isothermal operation. A simpler method of evaporative cool-
ing is possible if the evaporation is compatible with the chemical process.
5.5. Adsorption
Centrifugal adsorption technology (CAT) allows the use of very small adsorbent
particles (microns) to increase the mass transfer efciency. Application to ion
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
exchange, volatile organic removal from water, recovery of pharmaceutical pro-
teins, and production of ne chemicals are examples of potential commercial
interest. Process advantages include low inventory, low contact time, steady-state
operation, and relatively small equipment (54).
The CAT mode of operation involves introduction of the adsorbent near the
axis of the rotor, allowing the centrifugal force to move the particles radially out-
ward. Liquid introduced at the outer periphery of the rotor moves countercurrent
to the adsorbent and is removed at the axis of the rotor. Adsorbent slurry collects
at the periphery and is conducted to the rotor axis for discharge. Experiments
using activated carbon to adsorb n-butanol from water revealed that the degree of
back-mixing is the dominant factor in performance. Back-mixing is a function of
rotor speed, density difference between the phases, and the particle diameter (54).
The hydrodynamics of two-phase ow in CAT were compared to two-phase
ow under gravity using a large-diameter (1.3-mm) particle in water with a small
density difference and a small-diameter (81.8-micron) particle in water with a
large density difference. The throughput capacity of the CAT was higher than pre-
dicted from the homogeneous-ow model, though the model works well for the
gravity-ow column. Pressure drop estimates were used to predict void fractions
in the range of 0.70.8. Higher rotor speeds resulted in higher void fraction (55).
5.6. LiquidLiquid Extraction
The use of centrifugal elds for liquidliquid extraction was perhaps the rst
commercially successful application of rotating packed beds. Podbielniak modi-
ed a patented vaporliquid contactor (2), using a perforated spiral passageway
as the rotor packing, to solve problems with penicillin recovery in 1945 (1).
Penicillin broth forms stable emulsions that require centrifugal force to break.
Solvent extraction was effective only at low pH, which caused penicillin deg-
radation. Multiple stages were needed to affect the necessary concentration. In
addition, the fermentation liquor varied signicantly from batch to batch and plant
to plant. Conventional countercurrent solvent extraction, mixer-settlers, and mixer-
centrifuge combinations could not effectively solve these problems without prod-
uct loss. The centrifugal solvent extractor achieved 98% product recovery by taking
advantage of its low liquid holdup, short residence time, high centrifugal force,
and multistage countercurrent contacting.
Continuous glycerin washing of soap produced by saponication has been
demonstrated in a countercurrent centrifugal extractor (38). The device achieves
phase separation with as little as 0.02 specic gravity difference and accomplishes
up to 10 theoretical stages of extraction. Some of the advantages over prior opera-
tions reportedly include exibility in feed, low holdup, less waste due to more
efcient separation, simple operation, rapid startup, and small space requirements.
Rotors lled with ceramic foam instead of perforated cylinders have been
tested for liquid extraction of trace contaminants from water (23). The test solution
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
used a C
12
alkene to extract 1,2-dichloroethane from water. Flow patterns are sim-
ilar to the previous applications, with the heavy phase introduced at the inner
diameter of the rotor and the light phase at the outer diameter. Countercurrent
ow is achieved as the heavy phase moves outward, displacing the light phase
inward. The results indicate an optimum pore size for the ceramic foam, decreas-
ing height of transfer unit with increasing rotor speed, and increasing holdup with
increasing dispersed phase ow.
The ability of the centrifugal extractor to solve difcult liquidliquid separ-
ation problems, as illustrated in the previous examples, has allowed its use in a
wide range of extraction applications. The long history of use has given it a gen-
eral acceptance in chemical manufacturingan acceptance not shared by the
broader application of gasliquid interactions.
5.7. Crystallization
In the reactive precipitation process of reacting CO
2
with Ca(OH)
2
slurry to pro-
duce nanoparticles of CaCO
3
, the controlling steps of the process are absorption
of CO
2
and dissolution of solid Ca(OH)
2
. The degree of supersaturation depends
on the reaction rate and controls the nucleation rate and, therefore, the particle
size. The intense mass transfer and micromixing capability of the rotating packed
bed provides the environment to produce CaCO
3
particles of size 1530 nm with
a narrow size distribution. Reaction time reduces 4- to 10-fold, compared to
stirred-tank reactors. Rotor speed, gasliquid ratio, and initial calcium hydroxide
concentration inuence reaction rate. An increase in rotor speed reduces the aver-
age particle size. Addition of growth inhibitors also helps to control particle size
and size distribution (56).
High-gravity reactive precipitation (HGRP) has been extended to the pro-
duction of aluminum hydroxide and strontium carbonate (57). Aluminum hydroxide
fibrils precipitate from the reaction of sodium meta-aluminate (NaAlO
2
), water,
and carbon dioxide and are formed in diameters of 110 nm and lengths of
50300 nm. Rotor speed, gas- and liquid-ow rates, and initial reactant concen-
trations control particle size. Strontium carbonate particles of 40-nm mean dia-
meter and narrow size distribution have been produced from the liquidliquid
reaction of strontium nitrate and sodium carbonate.
Crystallization that occurs during evaporation can potentially be intensied
by use of vapor recompression and spinning discs. In this scenario, the evapor-
ated vapor is compressed and then condensed on the bottom of the discs to heat
the crystallizing uid (58). This approach may permit operation at higher tem-
peratures, lower surface area, and less time.
Recrystallization of an active pharmaceutical ingredient on a spinning disc,
employing a solvent/antisolvent approach to induce rapid precipitation, results in
the desired small particles (115 microns) and narrow particle size distribution (59).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
5.8. Reactions
A signicant number of chemical reactions of commercial interest have reaction
rates limited by heat or mass transfer rather than the intrinsic chemical kinetics.
Many of these processes could be intensied by application of the RPB or spin-
ning disc technology. Indeed, application of centrifugal elds to reacting systems
may represent its greatest potential. Improved yield performance may also be
possible (50). Spinning disc technology provides the advantage of heat transfer
capability. Thus, temperature control of exothermic reactions such as styrene
polymerization and intense mixing allow reduction in reaction time compared to
conventional batch reactors, especially in the latter stages of reaction, where vis-
cosity is higher (60,61).
Polycondensation reactions that are equilibrium controlled, such as poly-
esters, could benet from the thin lms generated in the RPB or spinning disc. In
these reactions, removal of the coproduct of polymerization, e.g., ethylene glycol,
is necessary in order to advance the polymerization, a task that becomes increas-
ingly difcult as the reaction proceeds. The thin lms and short residence time of
high-gravity devices aid the evaporation and may permit operation at higher tem-
peratures than conventional reactors (50).
As mentioned previously, RPB and spinning disc technology may provide
benets for reactions that are mass or heat transfer limited, i.e., for fast kinetic
reactions. Unfortunately, the true chemical kinetics are often unknown. A small-
scale RPB or spinning disc may prove to be a useful screening tool to determine
the intrinsic chemical kinetics. In one such study, six different reactions of inter-
est in the manufacture of pharmaceuticals were screened using a spinning disc
reactor (59). Three of the six reactions were found to be limited by liquidliquid
mixing. These include a phase-transfer-catalyzed Darzens reaction, a crystalliza-
tion, and a highly exothermic condensation reaction. In the Darzens reaction the
reactant inventory was reduced 99% and the impurity level decreased 93% as
compared to the conventional reactor. Crystallization achieved mean crystal size
of 3 microns, with a narrow size distribution. The highly exothermic reaction had
excellent temperature control.
A lab-scale RPB has also been used to investigate reactions that are mass
transfer constrained in conventional reactors. Testing a reaction that involves
release of a volatile organic as part of molecular weight buildup revealed overall
process reaction rates equivalent to conventional reactors in time frames more
than two orders of magnitude lower. Here the high surface area and surface
renewal capability of the RPB helped to overcome the transfer limitations across
the liquid boundary. Similar results were seen on other reaction processes that
were constrained by a liquidsurface interaction (62).
Reactions can be combined with other unit operations, as in the example of
reactive stripping in the production of hypochlorous acid (HOCl). An RPB was
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
used to absorb chlorine gas into an aqueous sodium hydroxide solution (caustic)
where reaction to HOCl occurs. Since HOCl is unstable in the presence of the
coproduct sodium chloride, stripping of the HOCl into the gas phase is necessary
to recover a stable product. The reaction of chlorine with caustic is essentially
instantaneous: therefore the process reaction rate is liquid-side mass transfer con-
trolled. Stripping of HOCl, on the other hand, is believed to be gas-side mass
transfer controlled. The intense mass transfer capability of the RPB allowed 10%
higher yields while using less than half the stripping gas as compared to conven-
tional spray tower operation. This study showed low-surface-area, high-porosity
wire screen packing to perform better than glass beads or parallel at plates.
Packing support design and liquid distributor type inuenced performance.
Operating parameters of importance included rotor speed and the gasliquid ratio
(8). Scale-up issues and performance of the commercial HOCl operation (9) are
discussed in Section 6.
Fermentation reactions are often limited by oxygen transfer rates. The
enhanced mass transfer achieved in centrifugal elds applied to bioreactions should
be expected to increase productivity. A centrifugal eld bioreactor (CFBR) demon-
strated higher productivity in the overproduction of lipase with Staphylococcus
carnosus as compared to conventional fermenters (22). Both batch and semibatch
fermentation in the CFBR showed no inuence on the biological activity of
growth or exoprotein synthesis. Lipase productivity rates were proportional to
oxygen transfer rates, which were 10 times higher than in shaken cultures. The
CFBR process involved feed of air and liquid to the outer diameter of the rotor,
with takeoff at the center. Air was dispersed in the liquid by either a sieve drum
or a multilayer-sintered screen. The inward radial movement of the gas helped to
suspend the bacteria in the culture against the centrifugal force. An external cir-
culation loop for the liquid allowed heat exchange and product analysis. Since
many fermentation reactions are characterized by foaming, the CFBR was
equipped with a foam breakera stator with needles positioned at the inside
diameter of the rotor.
5.9. Other Applications
Centrifugal elds in an electrochemical cell facilitate the removal of gas bubbles
from the electrodes, thus reducing the voltage requirement. A rotating chlorine cell
showed a drop in voltage from 3.17 V to about 2.8 V at 3-kA/m
2
current density
when accelerated to 200 g (50). Demonstration of a rotating air cathode provided
greater voltage drop at higher current density as compared to a stationary cell (50).
Dedusting or demisting in rotating devices provides opportunity to remove
small particles at very high throughput. A mop-fan built with exible bers in
a conventional fan housing effectively removes 50% of two-micron particles
of slaked lime dust in conjunction with water spray on the rotor. Inline rotary
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
demisters employing reticulated metal foam are used for oil separation from air
on turbines (50).
6. SCALE-UP AND COMMERCIAL USE
Although considerable studies on the use of centrifugal elds in chemical pro-
cessing have been reported for lab- and pilot-scale operations, little information
is public on scale-up criteria for either performance parameters or equipment
design. Three examples of commercial use of centrifugal elds are available for
review. These include liquidliquid extraction, water deaeration, and reactive
stripping for hypochlorous acid production.
Commercial application of centrifugal elds encounters considerable
resistance from both the technical and business communities due to both real and
perceived risks. The real risks involve reliable mechanical design of rotating
equipment, which includes seals, bearings, and rotor stability. Perceived risks
on process performance may derive from a lack of understanding of the process
fundamentals and how performance may change with the scale of operation.
Overcoming the tendency to use what we know and understand represents a
challenge that goes beyond the effort at technology development.
Convincing the technical community to accept the risk of rotating equip-
ment for chemical processing may be easier on applications with clear perform-
ance advantages over conventional process equipment. A good example is the
liquidliquid solvent extraction of penicillin (1), in which the low residence time
and ability to handle emulsions and solids allowed 98% product recovery. The
10% higher yields and 50% reduction in stripping gas for the HOCl reactive strip-
ping process provides another example of performance advantage (8).
In addition to the lower operating costs associated with enhanced perform-
ance, the business community is interested in lower capital investment and assur-
ance that the process will reliably perform as designed in terms of product
capacity, on-stream time, and product quality. The smaller size of the centrifugal
equipment may satisfy the capital investment question. This was the primary
driver for implementation of water deaeration in China (7). Lower capital is also
a driver for the polymer devolatilization application (47). The question of reliable
performance is best addressed through convincing the technical community and
leveraging the considerable industry experience with design and manufacture of
rotating equipment, such as pumps, compressors, and centrifuges.
6.1. Scale-Up Criteria
A number of parameters can be considered for scale-up of rotating packed beds,
including rotor packing, liquid distribution, ooding, pressure drop, rotor speed,
HTU, NTU, temperature, and pressure. Since the same packing material (same
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
porosity and volumetric surface area) is used on scale-up as in the pilot equip-
ment, HTU is expected to scale directly. Results from water deaeration (7) and
HOCl production (9) indicate this may be true for liquid-side mass transfer
controlled operations but not for gas-side mass transfercontrolled operations.
Flooding of the rotor in gas continuous operations would be expected at the
same gas velocities as in the pilot RPB. Flooding normally occurs at the inside
diameter of the rotor due to the lower cross-sectional area and higher velocities.
However, a check of the porosity of the outer packing support may be necessary
to ensure that no ooding occurs. If scale-up of rotor speed is based on constant
rotor tangential velocity instead of constant g-force, then the gas velocity at ood-
ing will be lower with larger-diameter rotors. Throughput capability and back-
pressure control of the light-phase takeoff (24) control ooding in liquidliquid
or gas-dispersed systems.
Using a pressure drop model based only on centrifugal acceleration and
frictional drag, the HOCl scale-up overpredicted the pressure drop of the com-
mercial RPB by a factor of 2 (9). A more rigorous approach to pressure drop cal-
culation that takes into account the conservation of angular momentum and the
inlet and outlet zones of the rotor and housing (40) should provide more pre-
dictable scale-up performance.
Rotor speed has an impact on mass transfer performance, ooding, and
pressure drop. Rotor speed on scale-up can be determined based on maintaining
constant tangential velocity (r) or constant acceleration (r
2
). Rotor speed will
be higher for constant-acceleration scale-up. Impact on both process performance
and equipment design must be understood in making this determination. Scale-up
based on constant acceleration is conservative for mass transfer and ooding per-
formance, while constant tangential velocity is conservative for pressure drop.
Liquid distribution may be an important parameter, as demonstrated in the
HOCl process, where different liquid distributors provided signicantly different
results (8). The initial contact of the liquid with the rotor inuences the mass
transfer performance of the RPB in gas continuous operations (15). Although the
use of a packing support at the inside diameter of the rotor would be expected to
impact this initial liquid contact with the rotor, experiments did not show any
reduced mass transfer performance (36).
As mentioned earlier, the same rotor internals used in pilot tests should be
used upon scale-up. The rotor dimensions of inner diameter and axial height
are determined by maintaining a constant supercial gas velocity at the rotor eye.
The radial packing depth, and thus the outer diameter, is based on the number of
transfer units required. Adjustments in packing depth and packing type may be
necessary to achieve the desired liquid holdup or residence time, e.g., for chemi-
cal reaction (26).
As with any chemical operation, the physical properties of the uids, such
as density, viscosity, and heat capacity, must be known. If chemical reaction is
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
involved, then the intrinsic kinetics must be understood. Of particular relevance
is the inuence of mass transfer rates on overall reaction rates.
6.2. Scale-Up Design
Once the rotor dimensions have been determined along with the operating condi-
tions, attention shifts to the mechanical design of the RPB. The major concern
with rotating equipment is maintaining stable operation, i.e., limiting vibration.
Excessive vibration results in premature seal and bearing failure, poor process
performance, metal fatigue, and increased maintenance costs and downtime.
Proper mechanical design principles determine the option of cantilevered or
centerhung rotor, the shaft diameter, the type and position of bearings, and seal
design. The drive train, whether belt driven or direct coupled, is determined by
the power requirements and the shaft orientation. The housing must be sufcient
to contain the temperature and pressure of the operation and to provide adequate
inlet and outlet nozzles for the process uids.
6.3. Commercial Examples
Two commercial examples of rotating packed-bed operation are water deaeration
for the Chinese oil elds (7) and HOCl reactive stripping in the United States (9).
These two cases illustrate nicely the range of process conditions and design
features available for successful scale-up. Water deaeration (Figure 7) uses a
direct-coupled drive on a horizontal-shaft centerhung rotor to process a low gas-
to-liquid operation (3: 1 vol/vol). The HOCl process (Figure 9) employs a belt-
driven, vertical-shaft cantilever rotor to contact a high gas-to-liquid ratio.
The water deaeration process employed a staged scale-up program. From
the lab operations, a 50 tons/hour (T/h) pilot RPB was built and tested in the oil
eld. Using natural gas for stripping at a gas/liquid ratio of over 2, the desired
oxygen content in the exit liquid of less than 50 ppb was demonstrated. This suc-
cessful demonstration led to the installation of a full-scale commercial RPB to
process 300 T/h. This unit has rotor dimensions of 600-mm ID, 1000-mm OD, and
700-mm AH. The wire screen packing has high porosity (92%) and low surface area
(500 m
2
/m
3
). The rotor spins at a modest 750 rpm. Performance matched that of the
lab and pilot units, achieving a typical 30-ppb oxygen content. Two 250-T/h units
have been designed for installation on an oil platform to process seawater, provid-
ing advantages in size and weight as compared to conventional technology (7).
Figure 9 shows the commercial-scale RPB for the reactive stripping process
for HOCl production. Figure 8 provides a visual impression of the process intensi-
cation that occurs using RPBs. The three RPBs shown in the lower left of the
picture process the same volume of gas and liquid as the tall absorber tower to the
right. The scale-up factor from the pilot unit of over 400: 1 yielded a rotor of
slightly less than 2 m in diameter. Performance of product yield from raw materials
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
met or exceeded that of the pilot unit. Pressure drop half of that expected implies
the need for better predictive correlations. Due to the higher gas-handling capa-
bility and the conservative scale-up design, much higher capacities are anticipated
as compared to the design. The liquid-side mass transfer performance as meas-
ured by chlorate formation showed performance equivalent to or better than that
of the pilot RPB. However, the gas-side mass transfer, as represented by HOCl
stripping, showed a doubling of the HTU to about 8 cm. The mechanical relia-
bility after two years of operation indicates no issues due to RPB operation. The
RPB is very easy to start up and shut down (9).
These two successful commercial applications of rotating packed beds
prove that scale-up from pilot-scale equipment can achieve the desired process
performance in commercial-scale operations. In addition, the mechanical reli-
ability of the rotating equipment is in line with the experience with other rotating
FIGURE 9 Commercial RPB for HOCl production using the vertical-shaft
cantilever design with belt drive. (Photo courtesy of The Dow Chemical
Company.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
devices. Thus, the risk concerns of performance and reliability can be managed
acceptably. Both the technical and business communities can have condence
that future applications will meet expectations of process performance and on-
stream time.
7. FUTURE
Extension of the use of centrifugal elds into chemical processing, beyond the
physical movement of uids, has shown limited niche application in the past, in
spite of considerable research activity. Specialty application of centrifugal elds
to liquidliquid extraction has enjoyed success for more than 50 years. Advant-
ages stem from operation at low density differences, breaking of emulsions,
short contact times, and higher efciencies as compared to other liquidliquid
extractors.
The commercial use of rotating equipment for the broader eld of gas
liquid operations has only a ve-year history. Numerous examples of possibilities
in the areas of absorption, adsorption, stripping, distillation, reactions, crystalliza-
tion, and other operations have been referenced. The chief objections to the use of
centrifugal elds have been associated with the risks of scale-up and the operation
of rotating equipment. The two commercial applications of water deaeration and
HOCl reactive stripping demonstrate the ability to reliably scale up processes
involving a wide range of gasliquid loadings. Process performance in both cases
met or exceeded design criteria, with good operating reliability.
Further application will likely require signicant cost or performance
advantages over more conventional process technology. Considerable commer-
cial experience will be needed before centrifugal elds will enjoy common
acceptance among both technical and business interests in the chemical industry.
To gain that status, projects must be selected carefully to ensure that advantages
are realized over alternative technologies.
The most likely opportunities for exploitation will come from mass transfer
limited reactions and the combination of unit operations in one device. Examples
of reactions mentioned earlier include polymerization, condensation reactions,
crystallization, and heterogeneous catalysis. Combined unit operations are illus-
trated by reactive distillation, polymer devolatilization with pelletization, and the
use of heat exchangers (reboilers and condensers) with distillation.
In addition to research on process applications, research to dene the fun-
damental performance characterizations is needed. A number of empirical corre-
lations have been developed for pressure drop, residence time, power, ooding,
etc. More generalized theoretical expressions for these parameters that accurate-
ly predict performance on a wide range of rotor designs and sizes would be very
benecial to condently scale-up the technology.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
REFERENCES
1. Podbielniak WJ, Kaiser HR, Ziegenhorn GJ. Centrifugal solvent extraction. Chem
Eng Prog Symp Ser 1970; 66(100):4350.
2. Podbielniak WJ. U.S. Patent 2,044,996, 1935; U.S. Patent 2,172,222, 1939; U.S.
Patent 2,281,796, 1942.
3. Pilo CW, Dahlbeck SW. U.S. Patent 2,941,872, June 21, 1960.
4. Podbielniak WJ. U.S. Patent 3,233,880, Feb. 8, 1966.
5. Todd DB. U.S. Patent 3,486,743, Dec. 30, 1969.
6. Ramshaw C, Mallinson RH. U.S. Patent 4,283,255, Aug. 11, 1981.
7. Zheng C, Guo K, Song Y, Zhou X, Ai D. Industrial practice of Higravitec in water
deaeration. In: Semel J, ed. 2nd International Conference on Process Intensication
in Practice. London: BHR Group, 1997:273287.
8. Trent D, Tirtowidjojo D, Quarderer G. Reactive stripping in a rotating packed bed for
the production of hypochlorous acid. In: Green A, ed. 3rd International Conference on
Process Intensication for the Chemical Industry. London: BHR Group, 1999:217231.
9. Trent D, Tirtowidjojo D. Commercial operation of a rotating packed bed (RPB) and
other applications of RPB technology. In: Gough M, ed. 4th International Conference
on Process Intensication in Practice. London: BHR Group, 2001:1119.
10. Peel J, Howarth CR, Ramshaw C. Process intensication: Higee seawater deaeration.
Trans IChemE 1998; 76(Part A):585592.
11. Barson N, Beyer GH. Characteristics of a Podbielniak centrifugal extractor. Chem
Eng Prog 1953; 49(5):243252.
12. Ding X, Hu X, Ding Y, Wu Y, Li D. A model for the mass transfer coefcient in rotat-
ing packed bed. Chem Eng Comm 2000; 178:249256.
13. Burns JR, Ramshaw C. Process intensication: visual study of liquid maldistribution
in rotating packed beds. Chem Engr Sci 51 1996; (8):13471352.
14. Basic A, Dudukovic MP. Hydrodynamics and mass transfer in rotating packed beds.
In: Heat and Mass Transfer in Porous Media Conference Proceedings, 1992:
651662.
15. Guo K, Guo F, Feng Y, Chen J, Zheng C, Gardner NC. Synchronous visual and RTD
study on liquid ow in rotating packed-bed contactor. Chem Engr Sci 2000; 55:
16991706.
16. Sandilya P, Rao DP, Sharma A, Biswas G. Gas-phase mass transfer in a centrifugal
contactor. Ind Eng Chem Res 2001; 40:384392.
17. Munjal S, Dudukovic MP, Ramachandran P. Mass transfer in rotating packed beds
II. Experimental results and comparison with theory and gravity ow. Chem Engr Sci
1989; 44(10):22572268.
18. Lin CC, Chen YS, Liu HS. Prediction of liquid holdup in countercurrent-ow rotat-
ing packed bed. Trans IChemE 2000; 78(Part A):397403.
19. Burns JR, Jamil JN, Ramshaw C. Process intensication: operating characteristics of
rotating packed bedsdetermination of liquid hold-up for a high-voidage structured
packing. Chem Engr Sci 2000; 55:24012415.
20. Ramshaw C. U.S. Patent 4,715,869. Dec. 29, 1987.
21. Peel J, Howarth CR, Ramshaw C. Process intensication: Higee seawater deaeration.
Trans IChemE 1998; 76(Part A):585593.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
22. Voit H, Gotz F, Mersmann AB. Overproduction of lipase with Staphylococcus
carnosus (pLipPS1) under modied gravity in a centrifugal eld bioreactor. Chem
Eng Technol 1989; 12:364373.
23. Lee JGM, Howarth CR, Ramshaw CR. Trace efuent removal from large owrate
aqueous phase using a packed rotary extractor. In: Proceedings of Value Adding
Solvent Extraction (Pap ISEC 96), Melbourne, 1996:11851190.
24. Jacobsen FM, Beyer GH. Operating characteristics of a centrifugal extractor. AIChE J
1956; 2(3):283289.
25. Sherwood TK, Shipley GH, Holloway FAL. Flooding velocities in packed columns.
Ind Eng Chem 1938; 30:768.
26. Keyvani M, Gardner NC. Operating characteristics of rotating beds. Chem Engr Prog
1989; 85(9):4852.
27. Singh SP, Wilson JH, Counce RM, Villiers-Fisher JF, Jennings HL, Lucero AJ, Reed
GD, Ashworth RA, Elliott MG. Removal of volatile organic compounds from ground-
water using a rotary air stripper. Ind Eng Chem Res 1992; 31:574580.
28. Lockett MJ. Flooding of rotating structured packing and its application to conven-
tional packed columns. Trans IChemE 1995; 73(Part A):379384.
29. Kelleher T, Fair JR. Distillation studies in a high-gravity contactor. Ind Eng Chem
Res 1996; 35(12):46464655.
30. Basic A, Dudukovic MP. Liquid holdup in rotating packed beds: examination of the
lm ow assumption. AIChE J 1995; 41(2):301316.
31. Tung H-H, Mah RSH. Modeling liquid mass transfer in Higee separation process.
Chem Eng Commun 1985; 39:147153.
32. Munjal S, Dudukovic MP, Ramachandran P. Mass transfer in rotating packed beds
I. Development of gasliquid and liquidsolid mass-transfer correlations. Chem Eng
Sci 1989; 44(10):22452256.
33. Singh SP. Air Stripping of Volatile Organic Compounds from Groundwater: An
Evaluation of a Centrifugal VaporLiquid Contactor. Ph.D. dissertation, The Univer-
sity of Tennessee, Knoxville, 1989.
34. Rumford F, Rae IJ. Performance characteristics of a centrifugal gas absorber. Trans
Instn Chem Engrs 1956; 34:195203.
35. Zhu J, Feng Y, Zheng C, Gardner N. Modeling of mass transfer in rotating packed
beds. Proceedings of First International Workshop on High-Gravity Engineering and
Technology, Beijing University of Chemical Technology, Beijing, 1996.
36. Guo F, Zhao Y, Cui J, Guo K, Chen J, Zheng C. Effect of inner packing support on
liquid controlled mass transfer process in rotating packed beds. In: Gough M, ed. 4th
International Conference on Process Intensication in Practice. London: BHR
Group, 2001:107113.
37. Hassan-Beck HM, Ramshaw C. Process intensication: mass transfer for countercurrent
rotating bed. Proceedings of First International Workshop on High Gravity Engineering
and Technology, Beijing University of Chemical Technology, Beijing, Elsevier, 1996.
38. Podbielniak WJ, Ziegenhorn GJ, Kaiser HR. Continuous soap washing and nishing,
using multistage, countercurrent, centrifugal contactors. J Am Oil Chem Soc 1957;
34:103106.
39. Sedahmed GH, Al-Abd MZ, El-Taweel YA, Darwish MA. Liquidsolid mass trans-
fer behavior of rotating screen discs. Chem Eng J 2000; 76:247252.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
40. Zheng C, Guo K, Feng Y, Yang C, Gardner NC. Pressure drop of centripetal gas ow
through rotating beds. Ind Eng Chem Res 2000; 39:829834.
41. Liu H-S, Lin C-C, Wu S-C, Hsu H-W. Characteristics of a rotating packed bed. Ind
Eng Chem Res 1996; 35:35903596.
42. Kelleher T, Fair JR. Distillation studies in a high-gravity contactor. Separations
Research Program, University of Texas, Austin, 1993.
43. Kumar MP, Rao DP. Studies on a high-gravity gasliquid contactor. Ind Eng Chem
Res 1990; 29:920924.
44. Aoune A, Ramshaw C. Process intensication: heat and mass transfer characteristics
of liquid lms on rotating discs. Int J Heat Mass Transfer 1999; 42:25432556.
45. Jachuck RJJ, Ramshaw C. Process intensication: heat transfer characteristics of
tailored rotating surfaces. Heat Recovery Systems CHP 1994; 14(5):475491.
46. Shang D-Y, Anderson HI. Heat transfer in gravity-driven lm ow of power-law
uids. Int J Heat Mass Transfer 1999; 42:20852099.
47. Cummings CJ, Quarderer G, Tirtowidjojo D. Polymer devolatilization and pelletiza-
tion in a rotating packed bed. In: Green A, ed. 3rd International Conference on Process
Intensication for the Chemical Industry. London: BHR Group, 1999:147158.
48. Gardner N, Keyvani M, Coskundeniz A. Flue gas desulfurization by rotating beds.
U.S. Department of Energy, DOE#DE-FG22-87PC 79924, 1993.
49. Al-Shaban K, Balasundaram V, Howarth CR, Ramshaw C, Peel JRA. The hydro-
dynamic and mass transfer characteristics of a large centrifugal water deoxygenator.
In: Proceedings of Energy Efciency Process Technology, Process Intensication
Conference, Athens, 1993:475484.
50. Ramshaw C. The opportunities for exploiting centrifugal elds. Heat Recovery
Systems CHP 1993; 13(6):493513.
51. Ramshaw C. Higee distillationan example of process intensication. Chem Eng
1983; 389:1314.
52. Fowler R. Higeea status report. Chem Eng 1989; 456:3537.
53. Hickman K. U.S. Bureau of Saline Water R&D Progress Report No. 12, Nov. 1956.
54. Bisschops MA, van der Wielen L, Luyben K. Centrifugal adsorption technology for
the removal of volatile organic compounds from water. In: Semel J, ed. 2nd Inter-
national Conference on Process Intensication in Practice. London: BHR Group,
1997:299307.
55. Bisschops MAT, Luyben K, van der Wielen L. Hydrodynamics of countercurrent
two-phase ow in a centrifugal eld. AIChE J 2001; 47(6):12631276.
56. Chen J, Wang Y, Jia Z, Zheng C. Synthesis of nanoparticles of CaCO
3
in a novel re-
actor. In: Semel J, ed. 2nd International Conference on Process Intensication in
Practice. London: BHR Group, 1997:157164.
57. Chen J-F, Wang Y-H, Guo F, Wang X-M, Zheng C. Synthesis of nanoparticles with
novel technology: high-gravity reactive precipitation. Ind Eng Chem Res 2000; 39:
948954.
58. Ramshaw C. Process intensicationincentives and opportunities. In: Doraiswamy LK,
Mashelkar RA, eds. Frontiers in Chemical Reaction Engineering. Vol 1. New York:
Wiley, 1984:685697.
59. Oxley P, Brechtelsbauer C, Ricard F, Lewis N, Ramshaw C. Evaluation of spinning
disk reactor technology for the manufacture of pharmaceuticals. Ind Eng Chem Res
2000; 39:21752182.
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60. Boodhoo KVK, Jachuck RJ, Ramshaw C. Spinning disc reactor for the intensica-
tion of styrene polymerization. In: Semel J, ed. 2nd International Conference on
Process Intensication in Practice. London: BHR Group, 1997:125133.
61. Boodhoo KVK, Jachuck RJ, Ramshaw C. Process intensication: spinning disc poly-
merizer for the manufacture of polystyrene. In: Ramshaw C, ed. 1st International
Conference on Process Intensication for the Chemical Industry. London: BHR Group,
1995:175180.
62. Winnington TL, Drgemller P. Speeding up slow processes. 4th International
Conference on Process Intensication, Brugge, Belgium, 2001.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
3
The Spinning Disc Reactor
C. Ramshaw
University of Newcastle upon Tyne, Newcastle upon Tyne,
England
1. INTRODUCTION
When considering the options for intensifying reactions that involve multiple
uids, it is helpful to identify the shortcomings of the conventional equipment
that is currently in use. In this context, perhaps the most frequently used item is
the stirred vessel tted with a cooling jacket, shown in Figure 1. A turbine impeller
generates a circulation comprising two toroidal vortices, and the turbine torque is
normally prevented from driving a free vortex by the use of wall bafes, as
shown. If a gasliquid reaction is involved, then the gas is usually injected directly
below the impeller via a suitable sparging arrangement. The popularity of the
stirred vessel is due to its perceived simplicity and adaptability, coupled with the
fact that it is supercially straightforward to scale-up from the laboratory beaker
that was used when the process was being developed. Unfortunately, it suffers
from several serious problems, as indicated later.
In the normal case of a geometrically similar scale-up, it can be readily
shown that the surface area per unit volume varies inversely with the vessel dia-
meter. Thus larger vessels are more difcult to cool, since the heat generated by
a reaction in a potential runaway situation is proportional to the vessel volume,
whereas the surface area available to dissipate a given heat output is decreased.
Vigorous reactions may require the reactor to be detuned by operating with
more dilute feedstock in order to reduce the full-scale reaction intensity. This
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
could inuence the reaction temperature trajectory and compromise the yield and
selectivity.
A further unfortunate characteristic of the stirred vessel is that its mixing
capability is also a strong function of its size. Scale-up usually proceeds on the
basis of a constant impeller tip speed, and since the mean circulation speed in the
vortices is broadly proportional to the tip speed chosen, the circulation time is
proportional to the vessel diameter. Thus the turnover time of the vessel contents
increases at the larger scale and the macro mixing performance deteriorates.
These fundamental shortcomings of the stirred vessel have generated a con-
siderable degree of uncertainty when ne chemical or pharmaceutical processes
are being developed for full-scale operation. This has led the relevant regulating
authorities, e.g., the U.S. Food and Drug Administration, to insist on a process
validation at laboratory, pilot, and full scale. Since each validation entails signi-
cant administration and delay, the procedure can hold up the implementation of
commercial production by several years. Because a new metabolically active
molecule will be patented as soon as possible and certainly before clinical trials
and process development, this delay signicantly erodes the time available under
patent cover to recoup a companys R&D expenditure and make a prot from a
potential blockbuster drug.
1.1. The Desktop Continuous Process
The predominant culture that prevails for the production of ne chemicals/drugs,
with an output of up to (say) 500 tons per year, is to operate batchwise. As already
noted, this stems from the fact that the process is almost always developed from
a batch-operated beaker or ask. However, it is worth observing that an output of
500 tons/year of active substance corresponds to a continuous process ow rate
of around only 70 mL/second. This allows various items of intensied equipment
FIGURE 1 Stirred vessel showing circulation pattern.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
to be assembled and operated continuously literally on a desktop to meet the
production demand. The decision to switch from batch to continuous processing
immediately confers an intensication benet because the peak batch process
loads (e.g., heat output, liquid removal, etc.) are distributed in time, so equipment
size can be reduced. Thus with a new process, the laboratory scale becomes the
full scale when allowed to run continuously and the scale-up delays described
earlier are largely avoided. This strategy is generating considerable industrial
interest as the commercial pressure to bring new molecules to market rapidly con-
tinues to increase.
A further factor that favors continuous desktop manufacture is its poten-
tial impact on the overall business process of making and marketing ne chem-
icals. Thus it goes without saying that with very short process residence times, the
operation can be much more responsive so that grade changes can be effected in
seconds rather than hours. This facilitates just-in-time manufacture, which can
lead to dramatic reductions in the capital costs associated with the multiple grades
of stock that may be needed rapidly to satisfy demanding customers.
1.2. Exploitation of Centrifugal Fields
Approximately two-thirds of the unit operations performed in process engineer-
ing involve multiphase contact (e.g., distillation, gas/liquid reaction, boiling). In
the absence of an imposed acceleration eld, the system uid dynamics are dom-
inated by surface forces so that the interfacial area developed is relatively small,
and, with no buoyancy force, there can be no countercurrent interfacial motion.
When these conditions prevail, the intensity of the operation is very low, with lit-
tle if any process performance (e.g., reaction, separation, heat transfer) being
exhibited. This scenario leads naturally to the suggestion that a high-acceleration
eld would stimulate the generation of smaller bubbles, higher ooding veloci-
ties, and more intense shear stresses.
This Higee strategy has been championed over many years because of its
profound and benecial impact upon many important multiphase operations:
Absorption
Distillation
Boiling
Condensation
Liquid extraction
Particle disengagement
Heat pumps
Etc.
One particular embodiment of this approach is the rotating packed bed,
which was originally conceived as the Higee equivalent of a packed column (1),
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
shown schematically in Figure 2. The equivalent stage height within the toroidal
packing is about 1.5 cm for a gas lmlimited system, compared with about
60 cm in a conventional packed column. Equivalent ooding velocities may
be estimated from the Sherwood plot and can be very high, even for packing with
a specic surface area exceeding 1000 m
1
. Since the Higee duty was origi-
nally envisioned as being purely orientated to mass transfer, no specic heat
transfer capability was provided. However, the spinning disc reactor (SDR) may
be regarded as an alternative to the Higee rotor. It can act as a mass transfer/
contacting device (possibly with multiple discs) or as a particularly intense
gasliquid reactor (when tted with heating/cooling provision). Its attraction lies
in the high heat and mass transfer rates that can be stimulated between the disc
and the thin liquid lm generated on its surface, and between the lm and the
adjacent gas. The performance and applications of the SDR are considered in
detail later.
As might be expected, the enhanced acceleration eld is established on a
permanent basis within a rotor that receives and discharges the working uid. The
alternative approach, which relies upon a permanent vortex eld, i.e., a cyclone,
FIGURE 2 The Higee contactor (continuous gas phase).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
will not be considered here, primarily because the uid residence time within a
vortex cannot be easily controlled independent of the desired acceleration. At this
juncture it is helpful to consider the basic physics of motion in a rotating system.
1.3. Free Motion of a Particle Around an Axis
Consider the free (frictionless) motion of a particle P of mass m rotating around
a xed axis O on a smooth surface, as shown in Figure 3. The particle is con-
strained to move in a circular trajectory by a light string that exerts an inward ten-
sion T and generates a corresponding acceleration. This can be estimated as
follows: In time t, P moves along an arc that subtends an angle to the axis.
The angular velocity of P is given by ddt and its speed is v r, where
r is the length of the string. During the time t the change of velocity of P is
v v sin () and as 0, v is directed along the radius toward O.
The acceleration is
Hence,
accelerationr
2
and the string tension needed to maintain this is
Tm
2
r
dv
dt
v d
dt
v
sin ( )
as 0
FIGURE 3 The free motion of a particle around an axis.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
If the string is broken, then the acceleration ceases and the particle leaves its cir-
cular trajectory and continues along a tangent at a velocity v.
If the string is slowly shortened then:
1. The particle moves toward Oin a spiral trajectory involving many turns.
2. Work must be done in order to overcome the string tension T.
For the proposed frictionless system, this work input results in an increase
in the particles kinetic energy. Conversely, if the string were lengthened, the par-
ticles velocity would decrease. Figure 4 shows the spiral trajectory of the parti-
cle and the corresponding velocity diagram. The radial and tangential velocity
components are drdt, v, respectively, giving a resultant V
R
that is a tangent to the
spiral trajectory.
Noting that drdt << v, the angle between v and V
R
is , where
tan(drdt )v. As the particle moves inward towards O, the component of T
along the spiral trajectory is responsible for increasing its speed.
Hence, with an inward tension deemed to be negative we have:
or
(1)
This conrms that v increases for an inward spiral trajectory (i.e., when
drdt is negative). From Eq. (1) we have
and integration from v
1
r
1
to v
2
r
2
gives
dv
v
dr
r
dv
dt
dr
dt
v
r
m
dv
dt
T m
v
r
dr
dt v
sin ( )
2
1
0 as
FIGURE 4 Spiral trajectory as a particle moves toward the center of rotation.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
i.e.,
(2)
This is an important result because it shows that in a frictionless or free situation,
angular momentum is conserved.
The same conclusion can be reached from energy considerations, noting
that the work done by the string tension as r is reduced is equal to the gain in par-
ticle kinetic energy, i.e.,
Hence
leading again to Eq. (2).
The practical consequence of Eq. (2) for rotational uid ow can be quite
dramatic, as demonstrated by the high wind speeds that may be generated near
the center of free vortex owse.g., tornadoes and typhoons.
1.4. Flow Over a Rotating Surface
If we now consider the behavior of a liquid lm on a rotating disc, the motion is
no longer free, because the lm is inuenced by the disc via the shear force
generated at the solid/liquid interface. Liquid supplied to the inner region of the
disc is rst brought up to the discs rotational velocity by the tangential shear
force and then moves radially outward, to be discharged from the disc periphery.
In a stationary frame of reference, the liquid trajectory is therefore a spiral with
arms separated by a radial distance given by
In a rotating frame of reference (i.e., that of an observer anchored to the disc),
the trajectory is nearly radial. Since this reference frame is most relevant when
we consider the disc/uid interaction, it is helpful to evaluate the ow on this
basis.
We shall assume that frictionless ow occurs through a closed radial chan-
nel that is xed to the rotating disc. Thus as the uid moves outward, the only
2
dr
dt
v
r
dr dv
T dr m
v
r
dr d m
v
mv dv
2 2
2
_
,
v r v r
2 2 1 1
ln ln
v
v
r
r
2
1
1
2
_
,
F
m r
dM
dt
dr
dt
1
2
dM d r r r dr ( ) 2
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
it traveled over a spinning glass disc. Care was taken to supply the liquid from a
central axisymmetric distributor in a particularly uniform manner. After calibration,
the local lm thickness was inferred from the density of the photographic image
at that point.
Even when great care was taken to ensure that the liquid feed was intro-
duced to the disc in an axisymmetric manner with the minimum disturbance, the
smooth inner lm always broke down into an array of spiral ripples, as shown in
Figures 5 and 6. These spiral structures then broke down further until the wave
pattern became utterly chaotic, provided that the disc was big enough. It is known
that liquid lm ow over a surface is intrinsically unstable, and the phenomenon
has been studied by several workers (37). It appears to be qualitatively equiva-
lent to the breakdown of a smoke plume rising from a lighted cigarette, where a
chaotic zone is generated about 20 cm above the source. The behavior can also be
observed when a liquid lm ows over a stationary surface such as a windowpane
or a dam spillway.
Woods concluded that two types of wave existed: nearly two-dimensional
(2D) and three-dimensional (3D). The amplitude of the two-dimensional spiral
waves grew rapidly, and therefore a theory based on the assumption of small ampli-
tude is not valid across the whole disc. A transition from 2D to 3D waves occurred
once their amplitude reached about three to four times the local lm mean thick-
ness. Higher liquid ow rates stimulated a more rapid breakup of the wavelets.
Only about 1% increase in liquid surface area was ascribed to the presence of
waves. Thus any improvement in mass/heat transfer performance generated by
the waves is due to the additional shear they induce. It will be appreciated that
even in the absence of ripples, highly sheared thin liquid lms, such as those that
can be readily generated on a spinning surface, provide an ideal uid dynamic
environment for the rapid transmission of heat, matter, and momentum. This is
due to the short diffusion path length involved for transfer between the adjacent
gas phase to the liquid lm and thence to the disc surface. These characteristics
of a spinning disc (or more generally a rotating surface of revolution) make it
ideal for performing any intrinsically rapid physical or chemical transformation
in a liquid, even if it is viscous. Typical examples include polymerization, pre-
cipitations, and rapid exothermic organic reactions. Some of these are described
in more detail later.
2.1. The Nusselt-Flow Model
While the uid dynamics of the actual lm-ow process across the disc is daunt-
ingly complex, a very approximate interim ow model may be based upon
Nusselts treatment of the ow of a condensate lm. This assumes that the ow is
stable (i.e., ripple free), that there is no circumferential slip at the disc/liquid sur-
face, and that there is no shear at the gas/liquid interface. The treatment is based
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 5 Liquid lm behavior on a rotating disc, with Q19 cm
3
/s and
(a) 100, (b) 200, (c) 300, (d) 400, (e) 500, (f) 600 rpm.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 5 (cont.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 5 (cont.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 6 Local liquid lm behavior on a rotating disc, with (a) Q19 cm
3
/s,
100 rpm; (b) Q19 cm
3
/s, 200 rpm; (c) Q13 cm
3
/s, 400 rpm;
(d) Q19 cm
3
/s, 500 rpm; (e) Q19 cm
3
/s, 600 rpm; (f) Q19 cm
3
/s,
600 rpm.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 6 (cont.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 6 (cont.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
on the schematic representation given in Figure 7. Part b represents the local lm
at a radius r. The shear stress on the annular plane at a distance y from the disc
provides the radial acceleration for the uid lying between y y and y s. Thus a
force balance on the lm lying between r r and r r dr, with zero shear
stress at the gasliquid interface, gives
(5)
The boundary conditions are:
1. u 0 at y 0 since there is no uid slip at the disc/liquid interface.
2. dudy 0 at y s since there is no shear stress at the gas/liquid
interface.
2
r s y
du
dy
( )
FIGURE 7 (a) Sketch of a liquid lm on a rotating disc. (b) Detail of a liquid
lm on a rotating disc.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Hence
(6)
The average lm velocity is given by
The maximum lm velocity (at y s) is
(7)
Referring to Figure 7a, the liquid is supplied to the disc at a radius r
i
and a
mass ow rate M. It is deemed to instantaneously acquire and maintain the disc
angular velocity as it moves over the disc to be discharged at its periphery. At a
radius r the mass ow rate is given by
(8)
Eliminating U
av
from Eqs. (7) and (8) gives
(9)
Inserting Eq. (9) into Eq. (8) gives
(10)
Hence the average time required for the liquid to travel from r
i
to r
o
is
(11)
If we consider a typical example of water owing over a disc under the fol-
lowing conditions:
M
3 10 10 10
2 3 3
kg/s N-s/m kg/m
2 3
t
dr
U M
r r
o
o
i
R
R
i
0 3
4
12
2
2 2
1 3
4 3 4 3
_
,
( )
/
/ /
M w
r
2 2
2
1 3
1 3
12
_
,
/
/
U
w r M
r w
av
2
2 2 2
2 3
3
3
2
_
,
/
s
M
w
r
3
2
2 2
1 3
2 3
_
,
/
/
M U s r
av
2
U
w rs
U
max
.
2 2
2
1 5
av
U
s
u dy
w rs
s
av
1
3
0
2 2
u
r
sy
y
2 2
2
_
,
10
5
6 10
9
4
m s
s
m
2
/
k
D
t
L
e
_
,
1 2 /
Fo
Dt
s
e
2
r r
i
o
5 10 0 25 100
2
m m s (955 rpm)
1
.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Thus Fo 0.014.
Equation (7) shows that the lm surface velocity is given by
Hence from Eq. (11),
(14) t
M
r r
e
32
9
3
4
2
2 2
1 3
4 3
1
4 3
_
,
( )
/
/ /
U U
M
r
max
.
/
/
1 5
9
32
2 2
2
1 3
1 3
av
_
,
FIGURE 8 Concentration distribution at various times in a slab x for
zero initial concentration and surface concentration C
0
.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Inserting this into Eq. (13) gives
(15)
However, it must be noted that as the lm ows over the disc, the lm thick-
ness progressively decreases, provided the liquid fully wets the disc. As this
occurs, the concentration proles normal to the disc plane are compressed, there-
by causing a proportionate enhancement of the solute diffusion rate beyond that
predicted by penetration theory. Thus the local value of k
L
can be corrected to
account approximately for the steepened concentration gradients by multiplying
by a factor s
1
s, where s
1
is the lm thickness at a radius r
1
as given by Eq. (9).
The corrected local value of k
L
is then
(16)
At the point of lm formation, where r r
1
, Eq. (16) shows that k
L
.
However, the average value of k
L
over the disc surface is given by
(17)
This requires numerical integration. As pointed out at the outset, these estimates
of the mass transfer performance are likely to be conservative as the disturbance
of the lm by ripples has been neglected. This will reduce the exposure time sig-
nicantly, particularly with inviscid liquids.
2.1.2. Heat Transfer
The Nusselt model was originally developed to correlate the performance of
vapor condensers. In this case, the latent heat of condensation is discharged at
the gasliquid interface and subsequently conducted through the draining con-
densate lm, the conduction path length being the local lm thickness. When a
liquid lm is heated or cooled on a spinning disc, the conduction path length is
less (about 50% of the thickness) because all of the sensible heat does not have
to be conducted through the entire lm. Since the thermal diffusivity of most
liquids is typically of the order of 10
7
m
2
/s, compared with a mass diffusivity of
around 10
9
m
2
/s, the Fourier numbers involved in the heat transfer version of
Figure 8 are approximately 100 times their mass transfer equivalent. This implies
that the heat transfer process involves the whole liquid lm rather than merely
k
r r
k r dr
L L
r
r
av
1
2
2
2
1
2
1
2
( )
k
D M r
r
r r
L
_
,
_
,
_
,
( )
1 2 2 2
2
1 6
1
2 3
4 3
1
4 3
1 2
2
3
1
/
/ /
/ /
/
k
D M
r r
L
_
,
_
,
( )
1 2 2 2
2
1 6
4 3
1
4 3
1 2
2
3
1
/
/
/ /
/
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
a thin layer near the disc surface. The Higbie model for heat transfer is therefore
inappropriate.
For the larger Fourier numbers involved in the heat transfer it is reasonable
to represent the lm temperature prole approximately by a quadratic expression:
(18)
A, B, and C are constants determined by these boundary conditions:
It can be shown that
(19)
and
(20)
Since the lm temperature gradient perpendicular to the disc will be much
greater than that in the radial direction, the local heat ux (Q) into the lm will
be controlled by the value of dTdy at the disc surface. Hence
Thus the effective lm coefcient is
(21)
For our earlier example with water on a 0.5-m-diameter disc, Eq. (21)
implies that the heat transfer lm coefcient at the periphery is 43 kW/m
2
k, with
the predicted lm thickness of 28 microns. For this estimate to be realistic it is
essential that the lm wet the disc and not break up into rivulets. This depends
upon a force balance at an incipient dry-out point, as indicated in Figure 9. At
the lm stagnation point the lm momentum is potentially destroyed by the action
of the component of the surface forces parallel to the disc. Thus for an average lm
velocity U
av
we must satisfy the following condition for rivulet maintenance:
T U s ( cos ) 1
2
av
h
Q
T T
k
s
w s
2
Q k
dT
dy
k
s
T T
y
w s
_
,
0
2
( )
dT
dy
T T
s
y
s
w s
2
1
( )
_
,
T T T T
y
s
T T
y
s
w w s w s
2
2
2
( ) ( )
1 0
2
3 0
.
.
.
T T y
T T y s
dT dy y s
w
s
at
at
at
T A By Cy
2
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
where T is the surface tension per unit length, is the contact angle, is the liq-
uid density, and s is the local lm thickness.
Coherent lms are less likely as they become thinner and their velocity
decreases. An inspection of Eqs. (9) and (10) reveals that U
2
av
s is proportional to
2/3
M
5/3
. Hence the tendency to form rivulets is less at higher disc speeds and liq-
uid ow rates and increases with large T and small .
2.1.3. Film-Flow Instability
The existence of the wave structure within the lm is of major practical interest, as
was highlighted by some elegant experimental work conducted by Brauner
and Maron (7). They monitored the instantaneous local lm thickness of a
liquid owing down a stationary inclined plane using a capacitance technique.
FIGURE 9 Schematic showing liquid lm dry-out on a rotating disc.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Simultaneously the local mass transfer coefcient was measured between the disc
and the liquid, using the limiting electrolytic current method. Their plots are repro-
duced in Figure 10. It was clear that the passage of a ripple was associated with a
signicant enhancement of the mass transfer coefcient, as a consequence of the
ow eld associated with ripple propagation. An analogous phenomenon may be
observed when sand particles are disturbed by wavelets in shallow seaside pools.
While the phenomenon has considerable theoretical interest, its immediate practi-
cal implication is very important because it suggests that the disc heat and mass
transfer performance could be enhanced still further by appropriately engineering
the disc surface prole. Some experimental results are discussed next.
FIGURE 10 Simultaneous time traces of local instantaneous lm thickness
and transfer rate.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2.2. Heat/Mass Transfer Performance
An early application of the SDR to heat transfer duty was developed by Hickman
(10), who was interested in the desalination of brackish water using a vapour
compression evaporator. A sketch of his initial arrangement is shown in Figure 11,
where brackish water owing on one side of a rotating disc assembly was evapo-
rated by condensing steam on the other. The very high overall heat transfer coef-
cients that could be achieved (up to 45 kW/m
2
K) ensured that the pressure ratio
demanded from the vapor compressor was minimal, thereby establishing very
efcient operation. In a further development of the idea (11), a series of disc
assemblies was mounted on one vertical shaft that was enclosed within a tower,
as shown in Figure 12. It is signicant that Hickman did not report any problems
associated with the deposition of crystal scale, even though his experimental runs
lasted for several hundreds of hours. Radial rather than spiral stains were, how-
ever, exhibited, which suggested that the inuence of the Coriolis acceleration
was minimal. Since the temperature difference between the condensate and the
evaporating brackish water was only 12C, it is presumed that the equivalent
supersaturation was insufcient to cause signicant crystal nucleation.
The ability of the spinning disc to operate with very small driving tempera-
ture and concentration differences can improve the thermodynamic efciency of
the overall process system. This is clearly the case with the Hickman vapor com-
pression evaporator, and it is also exemplied in the applications described next.
In general, the power needed to rotate the spinning disc assembly is a small frac-
tion of that saved by virtue of the establishment of an intensied uid dynamic
environment.
2.2.1. The Rotating Electrolytic Cell
A laboratory-scale rotating chlor-alkali membrane cell was constructed and tested
some years ago in ICI. The electrodes comprised closely spaced catalyzed discs that
were separated by a Naon membrane. The anolyte and catholyte concentrations
corresponded to those in the brine and sodium hydroxide solutions used in the
standard (FM21) industrial version of the membrane cell. As can be seen from
Figure 13 (taken from Ref. 12), while the industrial cell voltage at a current density
of 3 kA/m
2
was 3.17 V, that of the rotating unit was a function of the applied accel-
eration, falling to about 2.75 V at 100 g. At a higher current density, the benets
of enhanced acceleration were even more marked. It will be recognized that
the enhanced buoyancy forces generated by the high acceleration can eliminate
the polarization effects associated with bubbles that adhere to the electrodes/
membranes or remain in the electrolytes. In principle a compact rotor comprising
a bipolar cell assembly of closely spaced discs is capable of an exceptionally high
chlorine production rate while operating at exceedingly competitive voltage.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 11 Schematic of the single-element Hickman still.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 12 (a) Schematic of the multiple-disc Hickman still. (b) Full-scale
Hickman still.
2.2.2. The Rotex Absorption Heat Pump
The main factor that has been responsible for the slow adoption of absorption heat
pumps for heating and air conditioning duties has been their high capital cost
compared with that of vapor compression equivalents. This is due largely to the
cycle complexity, as shown in Figure 14, which displays the four principal cycle
elements, all of which involve vaporliquid systems:
1. Condenser
2. Evaporator
3. Generator/boiler
4. Absorber
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 12 (cont.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The only single-phase item involved is the solution heat exchanger, which
is intensied by the use of laminar ow in a matrix of ne channels. A sketch of
the single-effect Rotex (13) design is shown in Figure 15, where it can be seen
that a hermetically sealed rotating disc assembly fullls the four functions listed.
The working uid consists of a water solution of either mixed alkali metal
hydroxides or lithium bromide.
The evaporator receives low-grade heat from the circulating ambient air and
vaporizes the refrigerant at low pressure, the vapor being promptly absorbed at
the absorber disc immediately opposite. Working uid from the absorber sump,
now rich in refrigerant, is returned to the generator via a solution pump and a
solution heat exchanger. The latter consists of a matrix of closely spaced metal
foil, which, as discussed earlier, gives very efcient heat transfer in a small vol-
ume. The heat of condensation and absorption is removed from the condenser/
absorber disc assembly by circulating water that enters and leaves via a mechan-
ical seal. The working uid is pumped around the cycle by a pitot tube assembly,
with the tubes dipping into a peripheral liquid trough. Since the Rotex machine
operates with a horizontal axis, the pitot tube arm is counterweighted to resist the
frictional torque exerted by the trough.
Information recently released (14) shows that the double effect air condi-
tioning version of Rotex has achieved a coefcient of performance of 1.0 at a tem-
perature lift of 35C using lithium bromide solution. This unit is about to enter
eld trials. Its high performance is entirely due to the intensity of the heat and
mass transfer environment generated on the liquid lm owing over the discs.
It is also worth noting that Alfa Laval has developed a process evaporator
for fruit juice and milk concentration using a nested stack of cones. Figure 16
FIGURE 13 Voltage characteristics of a rotating chlorine cell.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
shows the arrangement, in which steam is caused to condense outside the cones
while the process uid is concentrated on the lm owing on the inside surface.
In this context it may be observed that the disc and the cone are specic exam-
ples of the general case of a rotating surface of revolution. The acceleration caus-
ing the outward movement of the liquid lm is the resolved component of
2
r
along the surface in question.
Koerfer (15) performed an interesting study with a series of perforated and
smooth rotating discs 600 mm in diameter at speeds up to 600 rpm. The mass
transfer performance was measured using the oxygen/water system, with the
results shown in Figure 17. Very good performance was recorded with the perfor-
ated discs, and this was attributed partly to the short exposure time of the lm as
it negotiated each perforation and partly to the extra lm area created.
Interestingly, the lm behavior was much more predictable when it owed
over the disc surface containing the raised lips arising from the punching oper-
ation. Film ow on the alternate side tended to leak through the disc, particu-
larly at lower liquid ows, presumably due to the Coanda effect as liquid
negotiated the rounded edge of the holes.
As part of a general development to use spinning discs in an intensied
absorption heat pump, Aoune and Ramshaw (16) measured both the local and
average heat transfer performance on smooth rotating surfaces. The disc surface
FIGURE 14 Single-effect absorption heat pump cycle.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
temperature was estimated by extrapolating the values given by the digitized out-
put from thermocouples embedded at depths of 1 mm and 9 mm in a brass disc.
The local lm temperature was measured by a thermistor contained in a stylus
that could be traversed over the disc surface.
Using water, the heat transfer coefcient on the 50-cm-diameter disc regu-
larly exhibited a minimum value at a radius of about 17 cm. On the other hand,
with the use of a water/60% monopropylene glycol mixture, no minimum was
observed and the absolute performance was much poorer than that obtained with
water. This behavior is attributed to the tangential uid slip generated as the feed
liquid is brought up to the rotors angular velocity. This slip appears to be more
marked with low-viscosity liquids, which seems intuitively reasonable.
FIGURE 15 (a) Rotex design concept. (b) Rotex prototype.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Mass transfer studies were then performed, based upon the aeration of liquid
that had been previously stripped. The local liquid oxygen concentration was estab-
lished by carefully abstracting a lm sample via a quill that could be traversed over
the disc. An Orbisphere oxygen analyzer was used. Rather poor agreement was
obtained between the experimental results for water (k
L
410 m/s 10
4
) and
the Higbie predictions (approx 1 m/s 10
4
) based upon total exposure time of
liquid on the disc. Clearly, liquid mixing within the lm generates exposure times
that are much shorter than the liquid residence time on the disc.
Another study, by Jachuck and Ramshaw (17), explored the inuence of
surface prole upon the heat transfer performance of a spinning disc. Using a
smooth disc as a benchmark it was shown that disc surfaces disrupted with metal
powder or grooves gave a signicantly improved performancepresumably due
to the better lm mixing. The best performance at modest disc speeds was
obtained with undercut grooves (Figure 18), which were originally conceived
as a technique for improving the circumferential distribution of any radial
rivulets. At higher disc speeds, the lm radial velocity was such that liquid was
projected off the disc, thereby compromising the heat transfer process.
FIGURE 15 (cont.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 16 Alfa Laval concentrator.
2.3. Reactor Applications
2.3.1. Strategic Considerations
At the most basic level, the SDR is an extremely effective gasliquid contacting
device. This makes it ideal for performing many intensied heat or mass transfer
operations and, as will be discussed later, it may be deployed as an evaporator or
an aerator/desorber. However, its principal application in the process industry is
likely to be as a very high-performance reactor. Since the reactor is the heart of
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 17 Mass transfer performance of a rotating disc (O
2
/H
2
O system).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
any process, the SDR can radically improve the economics and efciency of
many key processes, both in the commodity and in the ne chemical area.
In order to exert full control over the progress of a chemical reaction or phys-
ical transformation, the uid dynamic environment must be sufciently intense so
as to ensure that the mixing and heat transfer rates are faster than the intrinsic
chemical kinetics. This concept is shown diagrammatically in Figure 19, which
illustrates the progress of a reaction represented simply as ABC, with the
reactants A, B traveling in plug ow along a tubular reactor. When the interdiffu-
sion of A, B is slow compared with the reaction rate, then C is produced near the
original plane of AB separation. This represents a total loss of control on two
counts:
1. The AB stoichiometric ratio varies wildly across the reactor diameter.
Therefore the selectivity for the desired product C is likely to be com-
promised because a more realistic reaction scheme will usually include
many side reactions.
FIGURE 18 Types of disc grooves tested.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2. Most of the reaction to C occurs in the immediate neighborhood of the
plane of AB separation. Thus only a small fraction of the available
reactor volume is utilized and an opportunity for intensication is lost.
On the other hand, when mixing is fast, the AB ratio is uniform and con-
trol over the product spectrum can be maintained. All the reactor space is used to
maximum effect. Since the intrinsic kinetics are allowed free rein, the reactor
is able to operate at the maximum intensity permitted by the specic chemical
system.
While it should be self-evident that a rational reactor design demands a
knowledge of both the uid dynamic environment and the detailed process kinet-
ics, the latter are rarely available. In many instances this leads to the severe limi-
tation of many important reactions by an inadequate uid dynamic intensity.
Some of these are known to be fast, e.g., liquid-phase nitrations, while others are
(incorrectly) assumed to be slow, e.g., most polymerizations. In these circum-
stances the pragmatic approach is to use a high-intensity reactor for each system
and then to assess the impact upon the spacetime productivity. Obviously, an
intrinsically slow system is resistant to further acceleration and this will rapidly
become evident. One signicant qualication of this contention involves the very
FIGURE 19 The inuence of mixing and reaction rates on reactor behavior.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
short residence time in the SDR compared with its conventional counterparts. In
certain reactions the process temperature is restricted to one that avoids product
breakdown in the time available. Since the residence time in the SDR when per-
forming a polymerization reaction is up to 10 seconds rather than the several
hours involved in a conventional stirred vessel, we must re-examine the processs
temperature trajectory. A higher operating temperature may well be acceptable
because the undesired breakdown components may not have time to be generated.
However, the higher temperature will reduce the liquid viscosity and accelerate
the reaction. The lower viscosity will reduce the residence time still further.
Therefore the SDR can exploit a process operating envelope that is much larger
than what is accessible to conventional technology.
With regard to the processing of viscous liquids, by far the most important
application relates to the manufacture of polymers. The key processes are:
1. Condensation reactions
2. Radical reactions
3. Devolatilization
The progress of a condensation reaction is controlled by an equilibrium
with a volatile product, which, if continuously removed, drives the reaction for-
ward. Unfortunately, as polymerization proceeds, the liquid viscosity increases,
rendering the removal of the volatile component much more difcult. The batch
stirred vessel, which is conventionally used for polymer manufacture, has a limi-
ted ability to remove a volatile component from the increasingly viscous polymer
melt. On the other hand, the SDR can maintain effective mass transfer and, as will
be shown in Section 2.3.2, can achieve in one pass (taking several seconds) the
same increment in polymerization as would conventionally require tens of min-
utes. The SDR with one or more discs on the same shaft is therefore capable of
performing polycondensation extremely rapidly. The short residence time also
facilitates rapid changes of product grade with minimum wastage.
The rate of a polymerization that proceeds via a series of radical reactions is
controlled by the micromixing environment within the polymer melt. Once again
the stirred vessel is a poor means to achieve the high desired intensity, whereas the
SDR has an impressive capability in this respect. It is well known that UV radia-
tion is a very effective means of radical generation, and this technique has been
proposed in the past for stimulating certain radical polymerizations. However, the
radiation extinction distance in a polymer melt is only a few millimeters, so a poly-
merization reactor comprising a stirred vessel having a diameter of several meters
is not a rational option. On the other hand, the thin polymer lms that can be cre-
ated and maintained on the SDR allow all of the polymer to receive a continuous,
uniformly high radiation dose and thereby maintain a very high reaction intensity,
as described later for the manufacture of butyl acrylate.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The industrial manufacture of polymers is rarely taken to completion, and
this requires unreacted monomer to be removed from the productwhen its vis-
cosity is highest. This devolatilization procedure is notoriously difcult because
it usually involves the vacuum stripping of a stirred vessels contents for many
hours. Just as the SDR promotes the removal of the volatile component of a con-
densation reaction, it is also effective in dramatically accelerating the
devolatilization process.
2.3.2. Polymerization
Polystyrene. The manufacture of polystyrene from various grades of prepoly-
mer has been performed (18,19) on a 36-cm brass SDR using the arrangement
shown in Figure 20. A series of concentric grooves was machined in the disc sur-
face in order to improve liquid mixing within the lm. The reaction operates via
free radicals, which were initiated in this case using benzoyl peroxide. In the rst
instance a series of batch runs was performed in a conventional laboratory-scale
stirred vessel in order to produce a calibration curve (Figure 21) of conversion
FIGURE 20 Schematic of an SDR styrene polymerizer.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
versus time. This vessel was then used to produce about 200 mL of prepolymer
at a range of conversions that was supplied to the inner spinning disc surface over
a period of about 30 seconds. The SDR was heated from below by a stationary
radiant ring, and the polymer produced was collected in a cooled annular trough
surrounding the disc. The styrene was diluted with about 16%
w
/
w
toluene in order
to reduce the viscosity.
Figure 21 also shows the increment in polymer conversion in one pass over
the disc as a function of the initial conversion in the preliminary batch. It can be
seen that the equivalent batch time that can be ascribed to one pass on the disc
increases (up to 58 minutes) as the initial conversion increases to 63%. This
implies that the benets of the SDR become more marked as the polymer visco-
sity increases. It is envisaged that the process can be scaled up either by using a
larger disc or by mounting several discs on one shaft. The latter approach (i.e.,
several discs in series) does, however, involve the problem of transferring poly-
mer from the peripheral collection trough to the center of the next disc. An alter-
native may be to operate discs on one shaft in parallel. For the experiments just
described, the feed rate was roughly 510 mL/s, which is equivalent to an output
of up to 250 tons/year on a continuous basis, though at this early stage this should
not be considered the ultimate limitation.
FIGURE 21 Free-radical polymerization of styrene.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The fundamental reasons for the high performance of the SDR are still a
matter for debate. The signicance of micromixing and the consequent improved
probability of radical interaction has already been mentioned. However, another
factor is expected to be the divergent character of the ow on the disc. This may
be expected to align the polymer molecules and thereby encourage the juxtapos-
ition of the reactive groups.
Polycondensation. The reaction between maleic anhydride and ethylene
glycol has been studied as an example of polycondensation (19). Since the reac-
tion proceeds on an equilibrium basis, in order to drive it to completion the water
produced must be eliminated from the increasingly viscous polymer melt. The
grooved brass 36-cm disc described earlier for the polystyrene experiments was
used at a temperature of 200C and a disc speed of 1000 rpm. As before, the
experimental procedure involved the establishment of a benchmark batch cali-
bration against which the subsequent disc runs could be compared. A typical acid
number plot versus batch time is presented in Figure 22. As the acid number
decreases, the conversion to polymer increases. The water of reaction was removed
from the polymer lm by maintaining a large nitrogen purge to the vapor space.
This technique, rather than the application of a vacuum, was the preferred method
for reducing the water vapor partial pressure.
It can be seen that the increment in polymerization following one pass in
the SDR corresponds to many minutes of reaction in the small batch reactor used
as a reference. This is particularly encouraging because the mass transfer intensity
in the laboratory stirred reactor is likely to be much greater than its industrial-scale
FIGURE 22 Time savings in the SDR for polyestirication.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
equivalent, and it therefore provides a demanding benchmark for the spinning
disc performance.
2.3.3. Fine Chemical Manufacture
The intense heat and mass transfer environment that can be established within the
liquid lm owing over the disc allows high selectivities and conversions to be
achieved when fast liquid-phase reactions are performed. Very encouraging results
were achieved in an industrial study of a phase-transfer-catalyzed (p-t-c) Darzens
reaction to produce a drug intermediate (20). In comparison with the currently used
batch processes, the ptc reaction on the SDR had a 99.9% reduced reaction time, a
99% reduced inventory, and a 93% reduced impurity level. A more recent study has
involved a 20-cm-diameter SDR with a catalytically activated surface to perform
the rearrangement of -pinene oxide to campholenic aldehyde (21), which is an
important intermediate used in the fragrance industry. The comparative perform-
ance of the batch reactor and the SDR is shown in Table 1. For equivalent conver-
sion and selectivity, the unoptimized SDR gave a much higher throughput than the
equivalent batch reactor and avoided the need to separate a catalyst slurry from the
product. Figure 23 shows the variation of selectivity as a function of disc speed and
feed ow rate; Figure 24 gives the conversion levels achieved. While conversion
falls from 100% at the higher ows and speeds, presumably due to the reduced liq-
uid residence time on the disc, the selectivity increases. Thus it might be
expected that a larger disc (or a sequence of small discs) could combine high con-
version and high selectivity. The batch reactor performance is summarized in
Figure 25, where it can be seen that 100% conversion requires 5 minutes (1 sec-
ond on the disc) and a maximum selectivity of 65% is reached.
2.3.4. Precipitation/Crystallization
The operation of crystallizers and precipitators is critically dependent upon the
supersaturation environment prevailing within the crystal magma because this
inuences both the nucleation of new particles and the growth of those that
TABLE 1 Comparison of the Best SDR Runs with Batch Results for
Conversion of -Pinene Oxide to Campholenic Aldehyde
Batch process SDR (continuous)
Process time (s) 300 1
Processed feed 1.2 kg/h 209 kg/h
Conversion (%) 100 100
Selectivity (%) 64 62
Note Catalyst separated from No loss of
the product mixture catalyst
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 23 Selectivity towards campholenic aldehyde at 85C at various feed rates.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 24 Conversion of -pinene oxide at 85C and various disc speeds.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 25 Batch reaction: conversion and selectivity towards campholenic aldehyde.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
already exist. In general, the growth rate has a rst-order dependence on super-
saturation for diffusion-limited systems and 1.5- to second-order where the surface
integration resistance is signicant (22). On the other hand, the nucleation rate,
whether primary or secondary, has a higher-order dependence on supersaturation,
typically in the range 29 (23), with the lower values being obtained mainly with
low-molecular-weight solutes. Hence it will be recognized that high supersatur-
ation can be readily achieved on SDRs. This feature makes them attractive for
producing very small or nanosized particles, which are currently of intense indus-
trial interest.
Supersaturation can be generated in several ways. Perhaps the simplest
technique is merely to cool a solution saturated at a higher temperature.
Alternatively, supersaturation can be created by removing the solvent or adding
an antisolvent for systems where the solubility is only a weak function of tem-
perature. Finally, supersaturation can be created by reactionbetween either two
liquids or a liquid and a gas. In all these cases the intense environment created
within an initially crystal-free liquid lm moving in plug ow over the disc can
generate very high supersaturation and consequently small and fairly uniform
crystals. This characteristic of the SDR may be attractive in several industries
(e.g., pharmaceuticals and coatings), where the product quality is intimately relat-
ed to the neness of the crystals and the tightness of the size distribution. The
concept has recently been tested (24) in a spinning cone precipitator (Figure 26),
which shares most of the characteristics of a spinning disc except that the cen-
trifugal acceleration vector is not aligned to the cone surface. Barium sulfate was
generated by mixing equimolar solutions of BaCl
2
and Na
2
SO
4
in a central reser-
voir. A thin liquid/slurry lm owed to the cone rim, from where it was collected
and subsequently analyzed in a Malvern Mastersizer. Equivalent batch experi-
ments were performed, for the purpose of comparison, in a 50-mL agitated
beaker. At a supersaturation of 500, dened as
the cone produced crystals at 6000 rpm that had a Sauter mean diameter of
3.2 microns, compared to 6.85 microns from the batch runs. However, at a
supersaturation of 5000, the batch yielded a Sauter mean diameter of 0.75 microns,
compared with 0.180.32 microns from the disc. The particle size distributions
reproduced in Figure 27 highlight the cone behavior at 8000 rpm more starkly,
with a decided shift to 0.11 microns, compared with 110 microns in the batch.
Thus it can be seen that for many systems, spinning precipitators hold out
the prospect of generating the crystal size distributions that have considerable
industrial interest. This view is further reinforced by some earlier work by
SmithKline Beecham (20), which crystallized an unnamed product (API) on a
Molar concentration of Na SO or BaCl
Molar solubility of BaSO
2 4 2
4
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
15-cm spinning disc. Figure 28, reproduced from their work, compares the prod-
uct size distribution from the SDR with that of the standard industrial material.
Crystallization was induced by adding an antisolvent, and it can be seen that a
very signicant impact could be made on the normal product size distribution,
which was smaller and narrower on the disc. The stainless steel disc was subject
to crystal scaling after a few runs. However, a thin layer of PTFE suppressed this
without signicantly impairing the discs heat transfer performance.
2.4. Comparative Spinning Disc Reactor Costs
It should be borne in mind that the SDR is most effectively exploited when it is run
on a continuous basis. The industrial units constructed to date have had disc diam-
eters up to 30 cm and have been capable of processing around 30 g/s of feedstock.
This corresponds to a continuous annual output of (e.g., polymer) 1000 tons/year.
For a typical pharmaceutical product, a 15-cm disc could process about 7 g/s,
equivalent to an annual output of 200 tons. With conventional stirred-vessel tech-
nology, a roughly equivalent unit to the 30-cm SDR is a 2000-L batch reactor
FIGURE 26 Spinning cone reactor layout.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
fabricated in 316 stainless steel, complete with computer control and a service
unit delivering a disc temperature in the range 20C150C. The cost of such a
reactor is estimated to be 250,000 with a range of 200400K.
Comparative SDR costs have been supplied by the most experienced manu-
facturers (Triton Chemical Systems Ltd), which has been collaborating closely
with Newcastle University during the last 5 years of SDR development.
2.4.1. Spinning Disc Reactor Layout/Specication
The SDR system is available as a desktop or a oor-standing unit. The latter
is easier to use at pressure and is more versatile for use with ancillaries such as
feed units. The desktop system is restricted to the core system shown within the
circle in Figure 29, which is a schematic representation of the oor standing
arrangement. Experience has shown that SDR design and manufacturing details
are very important in ensuring that the unit operates satisfactorily over its full per-
formance range. Thus care must be taken with respect to the feed arrangements
to ensure that instantaneous stoichiometric ratios are held constant and that feed
liquids are mixed exceedingly rapidly on the disc. A sophisticated feed system is
provided to ensure that the delivery of two liquid feeds is accurate. If this level of
complexity is not required, then there may be a signicant cost saving. As shown
in Figure 29, feed liquids are supplied by means of two ram injectors accurately
driven by precision step motors. Product is drained from the disc casing into a
FIGURE 27 BaSO
4
size distribution for a supersaturation of 5000.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
lower receiving vessel, which can be isolated during SDR operation. This allows
product removal without interfering with the progress of the reaction.
Specications for all systems include:
a. Constructed with 316L stainless steel contact parts for the reactor
(other materials are available).
b. Constructed with a vessel to take 3-atm pressure or vacuum (other pres-
sures available). Vessel has twin-wall construction to allow heating or
cooling of the jacket.
c. Supplied complete with:
i. Temperature measurements at the disc.
ii. Electronics and interfaces for:
1. Up to 8 measurements of temperature.
2. Up to 8 measurements of pressure etc.
iii. An advanced computer control and data-logging system.
The main variables on a specic spinning disc reactor are:
d. The material of construction.
e. The range of ambient conditions under which the reaction take place
(temperature and pressure).
f. The range of disc speeds available.
g. The degree of instrumentation required.
FIGURE 28 Recrystallization of an API: comparison of size distributions.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2.4.2. Prices
These prices are for the spinning disc reactor as just dened in points a to c, includ-
ing advanced control and data-logging software with computer and at screen. The
following ancillaries are usually necessary for the system, and these may exist, or
Triton can recommend units or can supply them integrated into the system.
a. Feed systems
b. Heat transfer uid system(s) for the disc/vessel/feeders
c. Reaction atmosphere control systems, e.g., pressure/vacuum/gas feed
Example prices are given in Table 2. As can be seen from the table, the cost
of the SDR system is signicantly less than that for a stirred vessel with a simi-
lar productive capacity. However, cost considerations are likely to be much less
signicant than the competitive edge that SDR technology is likely to bring in
terms of improved selectivity and product quality.
FIGURE 29 Schematic of the SDR manufactured by Triton.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
3. CONCLUSION
It will be apparent from the examples cited that centrifugal elds in general, and
rotating surfaces in particular, can exert a profound inuence upon process
engineering. Our experience at Newcastle University has repeatedly demonstrated
that the greatest gains are achieved when the SDR is presented with the most
severe process conditions. While our original target was simply to reduce equip-
ment size and installed cost, it rapidly became apparent that reduced size alone
would be insufciently persuasive for the acceptance and adoption of SDR tech-
nology. However, it has now been demonstrated that in addition to yielding
TABLE 2 Spinning Disc Reactor Costs
M/C type Description Price
Type K-01 Small benchtop system, speeds from 100 to
2000 rpm, suitable for disc temperature to 100C
15-cm disc 40,000
30-cm disc 60,000
Type P-01 Free-standing system, speeds from 200 to
4000 rpm, suitable for disc temperatures to 100C
15-cm disc 75,000
30-cm disc 90,000
70-cm disc 120,000
Options Price
For either system, typical options are:
a. Heat/cool system, to provide cooling at the walls to 17,500
20C and heating/cooling at the disc for 5C to 120C
b. Injector system, 2000-mL capacity, with twin walls to allow 5,000
heating cooling; feed rates from 0.07 to 7mL/s;
fast down, with index and control system
c. Stirrers for the injectors 1,000
d. Cooled deector ring system 1,400
e. Receivers, for operation up to 10 bar
1 L 980
2 L 1,400
4 L 1,960
f. Additional instrumentation
Measurement of heat transfer uid ow rate 1,400
Measurement of temperature difference across disc 400
Added temperature measurements (per channel) 100
Added pressure measurement (per channel) 400
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
a better product (i.e., tighter size/molecular weight distributions, improved purity,
etc.), the SDR can transform the whole business process.
As with any radical step, the main obstacle to its implementation is the nor-
mal human resistance to change. In order to overcome this it is vital that chemists
who are developing new processes be as fully conversant with SDRs as with their
beakers and asks. There is therefore a latent market for miniature versions of this
equipment throughout the worlds industrial and teaching laboratories. Once the
cultural block is overcome and company decisionmakers fully appreciate the
breadth of impact in prospect, then the process industry will be fully prepared to
meet the challenges of the new century.
REFERENCES
1. Mallinson R, Ramshaw C. European Patent No. 2568B, 1969.
2. Woods WP. The hydrodynamics of thin liquid lms owing over a rotating disc.
Ph.D. dissertation, Newcastle University, Newcastle, U.K., 1995.
3. Thomas S, Faghri A, Hankey W. Experimental analysis and ow visualization of a
thin liquid on a stationary and rotating disc. Trans AsmeJ Fluids Eng 1991; 113
(March):7380.
4. Wasden FK, Dukler AE. A numerical study of mass transfer in free-falling wavy
lms. AIChE 1990; 36(9):13791390.
5. Oron A, Davies SH, Bankoff SG. Long-scale evolution of thin liquid lms. Rev
Modern Physics 1997; 69(3):931980.
6. Brauner N, Maron DM, Dukler AE. Modeling of wavy ow in inclined thin lms in
the presence of interfacial shear. Chem Eng Sci 1985; 40(6):923937.
7. Brauner N, Maron DM. Characteristics of inclined thin lms, waviness and the asso-
ciated mass transfer. Int J Heat Mass Trans 1982; 25(1):99110.
8. Carslaw HS, Jaeger JC. Conduction of Heat in Solids. 2d ed. Oxford University
Press, Oxford, 1959:101.
9. Higbie R. The rate of absorption of pure gas into a still liquid during short periods of
exposure. Trans Am Inst Chem Eng 1935; 31:365.
10. Saline Water Conversion Report for 1959. U.S. Dept. of Interior Ofce of Saline
Water, 1959:40.
11. Saline Water Conversion Report for 1957. U.S. Dept. of Interior Ofce of Saline
Water, 1957:7.
12. Ramshaw C. The opportunities for exploiting centrifugal elds. Heat Recovery
Systems CHP 1993; 13(6):493513.
13. Ramshaw C, Winnington TL. An intensied absorption heat pump. Proc Inst Refrig
1988; 85:2639.
14. Gilchrist K, Lorton R, Green RJ. Process intensication applied to aqueous Li
Brotating absorption chiller with dry heat rejection. 7th UK National Conference
on Heat Transfer, Nottingham, U.K., Sept. 1012, 2001.
15. Koerfer M. Hydrodynamics and mass transfer of thin liquid lms owing on rotat-
ing perforated discs. Departmental Report, Chemical Engineering Department,
Newcastle University, Newcastle, UK, 1986.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
16. Aoune A, Ramshaw C. Process intensication: heat and mass transfer characteristics
of liquid lms on rotating discs. Int J Heat Mass Trans 1999; 42:25432556.
17. Jachuck RJJ, Ramshaw C. Process intensication: heat transfer characteristics of
tailored rotating surfaces. Heat Recovery Systems CHP 1994; 14(5):475491.
18. Boodhoo KVK, Jachuck RJJ, Ramshaw C. Process intensication: spinning disc poly-
merizer for the manufacture of polystyrene. In: Ramshaw C, ed. 1st International
Conference on Process Intensication in the Chemical Industry, Antwerp, Dec. 1995.
19. Boodhoo KVK, Jachuck RJJ, Ramshaw C. Spinning disc reactor for the intensica-
tion of styrene polymerisation. In: Semel J, ed. 2nd International Conference on
Process Intensication in Practice, Antwerp, Oct. 1997.
20. Oxley P et al. Evaluation of spinning disc reactor technology for the manufacture of
pharmaceuticals. IEC Res 2000; 39(7):21752182.
21. Vicevic M, Jachuck RJ, Scott K. Process intensication for green chemistry:
rearrangement of -pinene oxide using a catalyzed spinning disc reactor. 4th Inter-
national Conference on Process Intensication for the Chemical Industry, Brugge,
Belgium, Sept. 10, 2001.
22. Mullins JW, ed. Crystallization. 2d ed. Butterworths, London, 1972:162.
23. Mullins JW, ed. Crystallization. 2d ed. Butterworths, London, 1972:162.
24. Hetherington P, Scalley MJ, Jachuck RJ. Process intensication: continuous produc-
tion of barium sulphate using a spinning cone precipitator. 4th International Confer-
ence on Process Intensication for the Chemical Industry, Brugge, Belgium, Sept. 10,
2001.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
4
Compact Multifunctional Heat Exchangers:
A Pathway to Process Intensication
B. Thonon and P. Tochon
Greth, CEAGrenoble, Grenoble, France
1. INTRODUCTION
In the rst part of this paper, the different technologies of compact heat exchangers
are presented and their range of application is given. The second part presents the
state of the art for heat transfer and uid ow characteristics for single-phase,
evaporation, condensation, and heat and mass transfer. The last part presents
applications of compact multifunctional heat exchangers.
As proposed by Shah and Mueller (1), heat exchangers may be character-
ized by the compactness factor, in m
2
/m
3
, and it is generally admitted that values
greater than 700 m
2
/m
3
characterize compact heat exchangers. Often, compact
heat exchangers also refer to nontubular heat exchangers, even if shell-and-tube
heat exchangers can have high compactness factors. For the heat exchanger con-
sidered, the hydraulic diameter ranges from less than 1 mm to 10 mm. There are
mainly two types of compact heat exchangers: the plate type (primary surface
heat exchanger) and the platen type (secondary surface heat exchanger). These
two types of heat exchangers are described and new technologies are presented.
In the process industry, there are only four basic operations: reaction, sep-
aration, mixing, and heat transfer. The traditional unit operation is to perform each
task in one or more pieces of equipment sequentially, for example, heat transfer in
heat exchangers and reaction in reactors. Combining two or more tasks in one piece
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
of equipment is implemented only for control or enhancement purposes; one exam-
ple is cooling in a jacketed stirred-tank reactor. But this is not an intensied process,
because it requires a batch operation, which has poor efciency, and the reaction
cannot be controlled effectively. Examples of multifunctional heat exchangers are:
Multistream heat exchanger (heat transfer between more than two uids)
Reactor heat exchanger (reaction and heat transfer)
Reux condenser (heat transfer and separation)
This chapter presents the state of the art in compact heat exchanger technol-
ogy and provides heat transfer and mass transfer characteristics of these devices
and their use in the process industry.
Heat transfer is commonly required in the process industry for heating, cool-
ing, vaporizing, or condensing. In most cases, only two streams (one hot and one
cold) are in thermal contact within the heat exchanger. The most commonly used
heat exchanger is the shell-and-tube heat exchanger, which has poor heat transfer
performance and requires a signicant volume and ground area. Compact heat
exchangers and enhancement technologies allow reducing the heat exchanger
volume, to increase its effectiveness and to reduce capital and operating costs.
Compact heat exchanger technologies are sufciently advanced, but their
use and acceptance in the process industry are not yet widespread. Reasons are
the lack of awareness of their benets and the absence of reliable design methods
and investigations under actual operating conditions. Compact heat exchangers
include plate heat exchangers as well as platen heat exchangers, which are
characterized by hydraulic diameters between 1 and 10 mm. But recent develop-
ments in manufacturing techniques, such as printed circuit heat exchangers and
diffusion-bonded and superplastic-formed heat exchangers, allow reaching hydraulic
diameters below 1 mm. These heat exchangers offer compactness greater than
1000 m
2
/m
3
and are suitable for industrial processes.
Rapid advances in range of design and operational reliability have made
compact heat exchangers attractive for many applications in various industries.
Their high performance has already made their use widespread in the automotive,
aerospace, air conditioning, refrigeration, and electrical equipment industries for
single-phase and phase-change duties. In the automotive industry, plate-type heat
exchangers are used as heaters, evaporators, and condensers (2), and since the
1970s, the volume/heat capacity ratio has been divided by a factor of 2 (Figures 1
and 2). This improvement has been achieved because of a radical change in heat
exchanger technology and by the adoption of mass production systems integrat-
ing innovative technologies.
Compact heat exchangers produced individually are generally more expensive
than a conventional shell-and-tube unit, and their payback time will be longer.
But taking space, weight, and convenience into account compact heat exchangers
can be used cost effectively in a wider range of applications than the niches cur-
rently being used in the process industry (3).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2. COMPACT HEAT EXCHANGER TECHNOLOGY
2.1. Classication of Compact Heat Exchangers
Heat exchangers can be classied in many different ways, such as according to
transfer processes, number of uids, surface compactness, ow arrangements,
heat transfer mechanisms, type of uids (gasgas, gasliquid, liquidliquid, gas
two-phase, liquidtwo-phase, etc.), and industry. Heat exchangers can also be
classied according to the construction type and process function (Figure 3). Refer
FIGURE 1 Progress in evaporator technology. (From Ref. 2.)
FIGURE 2 Progress in condenser technology. (From Ref. 2.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
to Shah and Mueller (1) for further details. In the follo1wing sections, only non-
tubular heat exchangers will be described.
2.2. Plate Heat Exchangers
Plate heat exchangers (PHEs) were formerly used for milk pasteurization and
gradually became the standard choice for heat treatment in the liquid-food indus-
try. Actually, pasteurization must be considered a biological reaction, because the
native composition of the liquid is denatured during the heat transfer process. In
practice this denaturation leads to fouling. The facility of dismantling plate heat
exchangers is one of the main reasons for their extensive use in the food industry.
Furthermore, because the heat transfer coefcients are high, the uid path length
will be shorter and relatively well dened. Due to the lack of large dead areas in the
channels, the corresponding residence time distribution is short and homogeneous.
Eventually, with the development of larger plates, their use began to grow
quickly in the chemical, petrochemical, district heating, and power industries, but
essentially for single-phase duties. The concept of phase change in PHEs originated
in the 1970s for ocean thermal-energy conversion (OTEC) applications; the work-
ing uids were Freon R22 or ammonia (4). These rst studies on evaporation and
condensation have been used for the development of PHEs in the refrigeration
FIGURE 3 Classication of heat exchangers.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
industry (510). Now PHEs have come to be used more often in the process
industry (1112), but their use is still not widespread.
In terms of technology, PHEs are made from corrugated plates (Figure 4)
that are pressed together. The plate size ranges from 0.02 m
2
to over 3 m
2
with con-
ventional pressing technology (Figure 5), but can reach up to 15 m
2
for explosion-
formed plates (Figure 6). The hydraulic diameter lies between 2 and 10 mm for
most common plates, but free passages and wide gap plates exist for viscous uid
applications. Typically, the number of plates is between 10 and 100, which gives
550 channels per uid. Furthermore, the use of high-quality metal and manu-
facturing techniques makes lead plate heat exchangers less prone to corrosion
failure than shell-and-tube units (13).
To ensure tightness, three technologies are available: gaskets, semiwelded
or totally welded, and brazing. The gasketed PHE is the most common type, with
the gasket material selected as a function of the application (temperature, uid
nature, etc.). Temperatures up to 200C and pressure up to 25 bars can be
achieved by such heat exchangers. For applications where gaskets are undesirable
(high pressure and temperature or very corrosive uids), semiwelded or totally
welded heat exchangers are available (Figure 7). The last variant is the brazed-
plate heat exchanger. The plate pattern is similar to conventional gasketed units,
but tightness is obtained by brazing the pack of plates. For common applications
copper brazing is used, but for ammonia units nickel brazing is possible. This
technology leads to inexpensive units, but the plate size is generally limited to
less than 0.1 m
2
. The drawback is that the heat exchanger cannot be opened, and
fouling will limit the range of application.
FIGURE 4 Plate heat exchanger. (Courtesy of Alfa-Laval Vicarb.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2.3. Spiral Heat Exchangers
The spiral heat exchanger consists of two metal sheets that are welded together and
then rolled to obtain spiral passages. The passages can be either smooth or corru-
gated; in some cases, studs or spacers are introduced between the metal sheets.
These devices have two functions: (1) to adjust the spacing and (2) to induce tur-
bulence and increase heat transfer. The general ow conguration can be crossow
(single or multipass) or counterow, depending on the conguration of the inlet and
outlet distribution boxes. The heat transfer surface ranges from 0.05 m
2
for refrig-
eration applications (Figure 8) to 500 m
2
for industrial processes (Figure 9). Spiral
heat exchangers are often used for phase-change applications, because the geome-
try of the hot and cold stream channels can be adapted to the process specications.
Recent developments in manufacturing technologies (laser welding) have
allowed the manufacture of cost-effective recuperators based on the spiral con-
cept (Figure 10) or the folded-plate recuperator (1415).
FIGURE 5 Corrugated plates. (Courtesy of Alfa-Laval Vicarb.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2.4. Plate-and-Shell Heat Exchangers
The basic principle of these heat exchangers is to insert a bundle of plates in a
shell (Figure 11). On the plate side, the uid ows inside corrugated or embossed
channels (more often in two passes). On the shell side, the ow is similar to shell-
and-tube heat exchangers, and bafes can be inserted. This technology can be
used for revamping an application, because the shell can be kept identical to that
for a bundle of tubes. These heat exchangers are often used in the process indus-
try as boilers (boiling on the shell side) because high pressures can be reached very
easily on the shell side. Furthermore, a large gap on the shell side allows the use
of dirty services, because cleaning is possible via removal of the bundle of plates.
2.5. PlateFin Heat Exchangers
Aluminium platen heat exchangers (PFHEs) were initially developed in
the 1940s to provide the aerospace industry compact, light, and highly efcient
heat exchangers for gas/gas applications. Because the mechanical characteristics
of aluminum are increased at low temperatures, this technology has been used
since 1950 for the liquefaction of natural gases. Nowadays, aluminum plate
n heat exchangers are extensively used in applications such as air separation,
hydrocarbon separation, and industrial and natural gas liquefaction (16). The
platen heat exchanger offers process integration possibilities (12 simultaneous
FIGURE 6 Explosion-formed plate. (Courtesy of Packinox.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 7 Various welded plate heat exchangers.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
different streams and more in one single heat exchanger) and high efciency under
close temperature approach (12C) in a large variety of geometric congurations.
The brazed platen exchanger consists of stacked corrugated sheets (ns)
separated by at plates, forming passages that are closed by bars, with openings
for the uid inlet and outlet (Figures 12 and 13).
FIGURE 8 Spiral heat exchanger for the refrigeration industry. (Courtesy of
Spirec.)
FIGURE 9 Spiral heat exchanger for the process industry. (Courtesy of Kapp.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
In its simplest form, a heat exchanger may consist of two passages, with the
cooling uid in one passage and the warming uid in the other. The ow direc-
tion of each of the uids relative to one another may be countercurrent, cocurrent,
or crossow.
The ns and the parting sheets are assembled by fusion of a brazing alloy
to the surface of the parting sheets. The brazing operation happens in a vacuum
furnace in which the brazing alloy is heated to its point of fusion. All parts in
FIGURE 10 Laser welding of a spiral recuperator. (Courtesy of ACTE.)
FIGURE 11 Shell plate heat exchangers. (Courtesy of ACM and Barriquand.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
contact are bonded by capillary action (Figure 14). Once the brazing alloy has
solidied, the assembly becomes one single block. All passages for ow distri-
bution and heat transfer of the streams are contained in the internal geometry of
the block. Inlet and outlet headers with nozzles for the streams are tted, by weld-
ing, around the openings of the brazed passages. These nozzles are used for con-
necting the heat exchanger to existing plant pipework.
Numerous n corrugations have been developed, each with its own special
characteristics (Figure 15). Straight ns and straight perforated ns act like par-
allel tubes with a rectangular cross section. Convective heat exchange occurs due
to the friction of the uid in contact with the surface of the n. The channels of
serrated ns are discontinuous, and the walls of the ns are offset. For air ows,
FIGURE 12 Components of a brazed aluminum platen heat exchanger.
(From Ref. 12.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
louver ns are extensively used; for process applications (single- and two-phase),
continuous or offset strip ns are used.
For higher-temperature applications or when aluminum is not acceptable,
stainless steel (temperatures up to 700C) or copper materials can be used. For
very high temperatures (gas turbine heat recovery; T 1200C), a ceramic
platen heat exchanger has also been developed (17) (Figure 16).
For high-pressure applications in the hydrocarbon and chemical processing
industries, a titanium compact heat exchanger has been developed by Rolls-
Laval. This heat exchanger consists of diffusion-bonded channels that are created
by superplastic forming of titanium plates (18). This heat exchanger can handle
high pressure and corrosive uids and is suitable for marine applications.
2.6. Flat Tube-and-Fin Heat Exchangers
The concept of at tube and ns in heat exchangers has been developed in the
automobile industry for engine cooling and air conditioning (1921). In such
applications one of the two uids is air and the other is either water or a refriger-
ant. The nonequilibrium of the heat capacities of the two uids leads to the adop-
tion of different enhancement technologies for both uids. Generally on the air
side the surface is nned (plain or louver ns), and on the other side the uid
ows in small-diameter channels (Figures 17 and 18). The technology is based on
FIGURE 13 Platen heat exchangers. (Courtesy of Nordon Cryognie.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
assembling aluminum elements, by either mechanical expansion or brazing. For
conventional applications, the pressure can be up to 20 bars. Recently, heat
exchangers with operating pressures up 140 bar have been manufactured (22) for
car air conditioning systems, using carbon dioxide as refrigerant.
2.7. Microchannel Heat Exchangers
Microchannel heat exchangers are compact heat exchangers where the channel
size is around or lower than 1 mm. Such heat exchangers have been developed for
severe environments, such as offshore platforms (23). New applications are also
arising for high-temperature nuclear reactors (24). To manufacture such small
channels, several technologies are available (25): chemical etching, micro-
machining, electrodischarge machining, etc.
The most common one is the printed circuit heat exchanger developed by
the Heatric Company. The channels are manufactured by chemically etching into
FIGURE 14 Stainless steel brazed platen heat exchanger. (Courtesy of
Nordon.)
FIGURE 15 Different n geometries.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
a at plate. The plates are stacked together and diffusion bonded. These heat
exchangers can support pressures up to 5001000 bar and temperatures up to
900C (not simultaneously with high pressure). The typical size of the channels
is 1.0 2.0 mm, and the plate size can be up to 1.2 0.6 m (Figure 19). The
processing technique is as exible as for platen heat exchangers, and crossow
FIGURE 17 Condenser. (Courtesy of Livernois.)
FIGURE 16 Ceramic recuperator. (Courtesy of Cramiques et Composites.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
and counterow congurations are employed. The main limitation of the
microchannel heat exchanger is the pressure drop, which is roughly inversely pro-
portional to the channel diameter. For high-pressure applications, the pressure
drop is not a constraint; but for other elds of application it will be the main bar-
rier to the use of such heat exchangers.
More recently, Chart-Marston has developed the Marbon heat exchanger (26).
This heat exchanger is made of stainless steel plates stacked and bonded together
(Figure 20). Several congurations are possible: (1) shell and tube, and (2) platen.
The use of such a heat exchanger as a chemical reactor is under consideration,
and the thermal and hydraulic characterization has been undertaken as European-
funded project (27).
Very compact heat exchangers are also used for cooling electronic devices
or microreactors (Figure 21). In these heat exchangers the channel size ranges from
50 m to 1 mm. Single phase and boiling are encountered in such applications
(28). Applications in the chemical processing industries are also foreseen (29).
These units can be very small in size and the heat duty per unit volume is very
high, up to15 kW/cm
3
.
2.8. Matrix Heat Exchangers
Perforated, or matrix, heat exchangers are highly compact and consist of a stack
of perforated plates made of high-thermal-conductivity material, such as copper
or aluminum, alternating with spacers of low thermal conductivity, such as plas-
tic or stainless steel. The pack of alternate low- and high-thermal-conductivity
FIGURE 18 Extruded aluminum minitube.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
plates are bonded together to form leakproof passageways between the streams
(Figure 22). The main bonding technique adopted is diffusion bonding; more
information can be found in Ref. 30.
Such heat exchangers have been developed for cryogenic and low-
temperature applications (31) and for fuels cells (32). They are suitable for a large
range of operating conditions, but there is very little information on their thermal
and hydraulic behavior. Furthermore, as the heat is transferred by conduction in
the plate, the temperature distribution is not homogeneous.
2.9. Selection of Heat Exchanger Technology
The selection of the technology of compact heat exchangers depends on the oper-
ating conditions, such as pressure, ow rates, and temperature, as well as on other
parameters, such as fouling, corrosion, compactness, weight, maintenance, and
reliability. Table 1 summarizes the major limits for the different types of compact
heat exchangers.
FIGURE 19 Printed circuit heat exchanger. (Courtesy of Heatric.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
3. SINGLE-PHASE FLOW
3.1. Flow Pattern
For corrugated heat exchangers, the ow is almost three-dimensional, and the
velocity eld is difcult to measure. Flow visualization (3334), realized in a
high-scale channel, clearly shows a recirculation area downstream of the corru-
gation edges (Figure 23). These areas are large at low Reynolds number (left of
picture). But the transition to turbulent ow (Figure 24), which occurs at
Re 200, reduces the size of these areas. Local information (3538) on the heat
FIGURE 20 Marbond heat exchanger. (Courtesy of Marston.)
FIGURE 21 Microchannel heat exchangers.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
transfer and velocity elds indicates that the heat transfer coefcients are linked
to the ow pattern and to the mixing intensity in the channel; variations of 50%
were measured. Furthermore, the size of the recirculation areas could be limited
by a proper design or by choosing appropriate operating conditions. The work of
Amblard (39) and Hugonnot (34) has shown that choosing the appropriate corru-
gation angle, and with the Reynolds number above a critical value, a quasiplug
ow can be obtained. This indicates that corrugated heat exchangers could be suit-
able for chemical reactions. The angle of corrugation has some inuence on the
global ow pattern. If we consider the entire channel as a two-dimensional medium,
the ow behavior can be studied. At this scale the ow can be considered homogen-
eous if there is the same ow rate through the channel width. Thonon et al. (37)
have shown that for low aspect ratio and low corrugation angle ( 30), there is
ow inhomogeneity, up to 15% of the ow rate distribution. But at high corruga-
tion angle or for higher aspect ratio (Ar 2), the ow is almost homogeneous.
In platen heat exchangers, the ow structure depends on the n geometry.
Continuous ns can be assimilated to rectangular channels and the ow is almost
identical to pipe ows. For offset strip ns or louvered ns, there is a high degree
of mixing (40), and the ow becomes turbulent even at low Reynolds number
(Figure 25).
3.2. Heat Transfer and Pressure Drop
For corrugated heat exchangers, extensive information is available in the literature
(3742); these studies have shown that the major geometric parameter is the
FIGURE 22 Matrix heat exchanger.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
corrugation angle. The enhancement of heat transfer, compared to a smooth chan-
nel, is up to six times greater. But at the same time, the pressure drop can be
increased by a factor of 100. Other geometric parameters are also inuential, and
manufacturers are continuously improving the plates design.
For platen heat exchangers in single-phase ow, the heat transfer coef-
cients are related to the developed heat transfer surface, and the area ratio must
be taken into account. As related to the projected surface, the overall heat transfer
coefcient is very high. Heat transfer and pressure drop can be estimated from
correlations (4344), but these correlations give only an estimate of the perform-
ance, because local modication of the n geometry will affect heat transfer and
pressure drop.
For microchannel heat exchangers there is a large discrepancy between
various experimental reports (45). Recent studies (46) have shown that down to
TABLE 1 Operating Conditions of Compact Heat Exchangers
Maximal Maximal
pressure temperature Number of
Technology (bars) (C) streams Fouling
Aluminum platen 80120 70200 10 No
heat exchanger
Stainless steel platen 80 650 2 No
heat exchanger
Ceramic platen heat 4 1300 2 No
exchanger
Diffusion-bonded 5001000 8001000 2 No
heat exchanger
Spiral heat exchangers 30 400 2 Yes
Matrix heat exchangers 1000 800 2 No
Flat tube-and-n 200 200 2 No
heat exchanger
Brazed-plate heat 30 200 2 No
exchanger
Welded-plate heat 3040 300400 2 Yes/no
exchanger
Plate-and-shell heat 3040 300400 2 Yes/no
exchanger
Gasketed-plate heat 2025 160200 2 Yes
exchanger
Graphite-plate heat 7 180 2 Yes
exchanger
Plastic-plate heat 5 200250 2 Yes/no
exchanger
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
0.5 mm, there is no signicant deviation, compared to large tube correlations, but
the size of the channels has to be accurately measured. More work is still needed
to fully understand heat transfer and uid ow in submicronic channels.
3.3. Fouling
The design of heat exchangers under foulant conditions results in oversizing, thus
substantially raising the cost of plants. Fouling is also responsible for process
inefciencies, due to increased thermal resistance. In water-cooling applications,
particulate and precipitation fouling are frequently responsible for the decrease in
heat transfer performance. Hence, the thermal and hydraulic performances need
to be well understood if the heat exchange capability of practical equipment
needs to be accurately predicted.
FIGURE 23 Flow structure in a corrugated channel: laminar ow (Re 150).
FIGURE 24 Flow structure in a corrugated channel: turbulent ow (Re 5000).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Plate heat exchangers are frequently used in industrial processes because
they are more compact and have higher thermal performance than conventional
shell-and-tube heat exchangers, and it is generally admitted that plate heat exchan-
gers are less prone to fouling than conventional shell-and-tube heat exchangers
due to the higher level of the shear stress. Measured fouling resistances (4750)
clearly indicate that fouling resistance values are about 10 times lower in corru-
gated channels than on a plain surface and that the geometry (Figures 26 and 27)
and the uid velocity (Figure 28) are the major inuential parameters. For instance,
it has been shown that the fouling resistance is almost inversely proportional to
square of the uid velocity. This implies that the uid velocity has to be con-
trolled properly while operating plate heat exchangers.
FIGURE 25 Flow structure in platen heat exchangers.
FIGURE 26 View of the deposit (30 corrugation angle at a velocity of 0.5 m/s).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
While sizing plate heat exchangers, the great sensitivity of fouling to the
uid velocity and channel geometry precludes the use of a single value for the
fouling resistance. If the TEMA fouling resistance values are applied to plate heat
exchangers, excess heat transfer surface will be required, which can lead to poor
efciency. It is often recommended that the fouling margin not exceed 25% of the
FIGURE 27 View of the deposit (60 corrugation angle at a velocity of 0.5 m/s).
FIGURE 28 Void fraction in a corrugated heat exchanger.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
extra heat transfer surface. Furthermore, the inverse velocity dependence of the
fouling resistance needs to be taken into account at the design stage. If the extra
surface required for fouling is provided by adding plates, a maximum heat duty
is reached; but adding more plates will nally reduce the heat duty. In design pro-
cedures, this needs to be taken into account. In the case of severe particulate foul-
ing conditions, 60 corrugation angle plates should be selected rather than lower
corrugation angles, and a minimum uid velocity of 0.3 m/s is suggested.
4. PHASE-CHANGE HEAT TRANSFER
4.1. Two-Phase Flow Characteristics
During vaporization or condensation, thermal and hydraulic performances depend
essentially on the two-phase ow structure. Furthermore, as very often in indus-
trial processes, the heat exchanger operates in thermosyphon or under natural circu-
lation; knowledge of the pressure drop and liquid holdup is of major importance.
But there is very little information on two-phase ow characteristics in compact
geometries.
Carey (51) has studied pressure drop and void fraction in different types of
compact heat exchangers and has outlined the differences with plain tube geom-
etries. Kreissig and Muller-Steinhagen (52) and Margat et al. (53) have shown
that the principles of the methods developed for plain tubes can be used but need to
be adapted. The main results of these studies are that the liquid holdup is signi-
cantly affected by the mass ow rate (Figure 28); the liquid holdup is underesti-
mated by conventional correlation; the two-phase ow multiplier can be estimated
from a Chisholm-type correlation.
Winkelmann et al. (54) have studied airwater ows in a corrugated heat
exchanger. Flow visualization and two-phase pressure drop measurements have
been performed. The ow visualizations have shown that the ow pattern is complex
and that a wavy or a lm ow occurs in most cases (Figure 29). The two-phase
pressure drop depends on the total ow rate and vapor quality, and Chisholm-type
correlation is proposed. More work is required to characterize the ow structure
in compact heat exchangers and to develop predictive methods for the frictional
pressure drop and the mean void fraction.
4.2. Vaporization
Vaporization is the most common unit operation to be found in the process indus-
try; the use of compact heat exchangers as evaporators began 40 years ago for the
concentration of sugar or salt solutions. Nowadays, compact heat exchangers are
used in several industrial processes, and this is particularly true for platen heat
exchangers, which are closely integrated in distillation and separation processes
of natural and industrial gases. In most cases, evaporation takes place in an upward
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
ow and the uid enters subcooled. The heat exchanger operates either in natural
or forced circulation. In the refrigeration industry, the heat exchangers are often
located directly after the expansion valve, so a two-phase mixture is fed at the
bottom of the heat exchanger. The main problem with such a conguration is to
obtain a homogeneous phase distribution among the channels. Some manufactur-
ers insert a distribution device in the inlet port, and it has been shown that a sig-
nicant improvement in thermal performance can be achieved. For large compact
heat exchangers operating under two-phase ow at the inlet, each phase of the
mixtures is fed independently in the channel in order to ensure an effective phase
distribution.
The design of compact heat exchangers for vaporization duties requires
knowledge of the heat transfer coefcients, and it is generally admitted that the
basic mechanisms occurring during ow boiling are similar to those encountered
in plain tubes (5557), but no general predictive method is available. For plate
heat exchangers, most of the data published have been obtained with pure refriger-
ants, and the operating conditions are rather different than those encountered in
the process industry. The general trend of these studies is that the heat transfer
coefcients are signicantly higher than those obtained in conventional plain
tubes, but the pressure drop is also increased. Concerning boiling of mixtures, com-
pact heat exchangers provide high single-phase heat transfer coefcients; hence
the vapor phase will be well mixed, and no major degradation of the heat trans-
fer coefcient should be observed.
Concerning platen heat exchangers, the design of such units is much more
complicated because up to 12 different uids can ow in the heat exchangers.
FIGURE 29 Two-phase ow visualization in plate heat exchangers.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
For distillation and separation processes, the uids encountered are mixtures, and
specic pinch methods have been developed (5859); a temperature approach of
less than one degree can be obtained. To optimize the number of layers per uid
and the type of ns, the heat transfer coefcients need to be accurately predicted
in the different boiling zones (subcooled, nucleate, convective, dryout, etc.).
Therefore, tests were performed with cryogenic uids, hydrocarbons (6061), and
refrigerants (62) in order to measure the heat transfer coefcients under actual ow
and geometric conditions. Tests with cryogenic uids are required because the
behavior of such uids is signicantly different than that of organic uids.
Microchannel heat exchangers are used for boiling applications, but there is
a lack of data for process uids. Studies using water or refrigerant at low pressures
have outlined differences in the ow pattern and in the heat transfer coefcients
(6364). This comes from the fact that the bubble diameter is limited by the chan-
nel size. For low and intermediate vapor qualities, the heat transfer coefcients are
increased as compared to plain tubes of larger diameters. But for higher vapor qual-
ities, partial dryout may occur and will reduce heat transfer. Because microchannel
heat exchangers might operate under large temperature differences, estimation of
the critical heat ux is important; but most of the correlations were obtained for at
plates and single tubes, so their extension to microchannels is doubtful (65).
To select and apply a boiling method to compact heat exchangers, several
facts must be taken into account. The method must be based on the fundamental
mechanisms occurring, because purely empirical and curve-t methods cannot be
generalized. The basic assumptions for developing such a method is that both
nucleate boiling and convective boiling occur and that the dominant mechanism
depends on geometric and operating conditions (Figures 30 and 31). The effect of
FIGURE 30 Vaporization in a platen heat exchanger.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
geometry must be taken into account in the convective area, and that of the oper-
ating conditions in the nucleate regime. It is assumed that nucleate boiling corre-
lations, established for plain tubes, are sufciently accurate and general to be
applied for compact heat exchangers. In the convective regime, the heat transfer
coefcient is reported to the single-phase liquid heat transfer coefcient, and an
enhancement factor is introduced to take into account the liquidgas interactions.
The main questions are to evaluate the single-phase heat transfer coefcient of the
given geometry, especially at low Reynolds numbers, and to characterize the
enhancement factor. The fundamental problem is to learn whether enhancement
factors developed for plain tubes can be applied successfully to compact geom-
etries. Work is being carried out in several R&D organizations, and knowledge on
boiling in compact geometries should be improved in the near future.
4.3. Condensation
Condensation occurs in many industrial processes, but rarely with pure uids.
The uids encountered are mixtures, and noncondensable gases are often present;
this makes the condensation process very complex.
In compact geometries the heat transfer coefcient depends on the two-phase
flow pattern (5167). For low condensation rates, the heat transfer is gravity
controlled, and the heat transfer coefcient depends on the liquid lm thickness.
For higher condensation rates, the heat transfer coefcient depends on the vapor
shear effect, and for small passages the liquidvapor interaction leads to high heat
transfer coefcients.
FIGURE 31 Vaporization in plate heat exchanger.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
In the case of mixtures or in the presence of a noncondensable gas, the con-
densing vapor must diffuse through the gas to the phase interface. For this to hap-
pen a partial pressure gradient toward the phase interface is necessary. The partial
pressure of the vapor falls from a constant value at a rather large distance from the
phase interface to a lower value at the interface. Correspondingly, the accompany-
ing saturation temperature also falls toward the interface. Therefore, during con-
densation, the condensing vapor arrives by diffusion at the condensate surface, and
it is the thermal resistance in the vapor that limits the process. Hence in order to
improve the heat transfer, one must reduce the thermal resistance on the vapor
side. Several factors can enhance the condensation process by reducing the vapor-
side resistance. During condensation of mixtures or of vapors that contain non-
condensables, the heat transfer on the vapor side can be improved by raising the
vapor velocity. It has been shown that the heat transfer coefcient can be improved
by approximately 30% by increasing the vapor velocity. The use of a nely undu-
lated surface can also achieve signicant augmentations in heat transfer during
condensation. It has been shown that corrugation can promote turbulent equili-
brium between the phases and thus contribute to the increase in heat transfer.
Compact heat exchangers are characterized by small hydraulic diameters
(110 mm), and there is no reliable design method to estimate heat transfer coef-
cients during condensation in such small passages. In the available literature,
condensation of mixtures and of vapor in the presence of noncondensables has
been studied, but essentially for conventional geometries (plain tubes), and only
few results have been published with uids representative of actual process condi-
tions (hydrocarbons). A 2002 study (68) has shown that in laminar regime there
was a signicant mixture effect (decrease in the heat transfer coefcient), but in
turbulent regime the mixtures behave as pure uids (Figure 32). This outlines the
high degree of mixing encountered in such heat exchangers, which is not surpris-
ing, since the geometric pattern of the plates is similar to modern column packing.
5. HEAT TRANSFER AND MASS TRANSFER
5.1. Macromixing
Macro- and micromixing are two major issues for compact multifunctional heat
exchangers. Macromixing is closely linked to the ow pattern and has often been
studied using ow visualization techniques. An effective macromixing will give
high transfer rates and homogeneous ow distribution in the channel. The typical
scale of macrostructures ranges from half of the channel height to one-tenth of the
channel height. Micromixing is associated with much smaller scales and will
affect the reaction rate.
In this section, we will focus on two technologies able to produce both heat
transfer and mixing: the corrugated heat exchanger and the platen heat exchanger.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
These heat exchangers have a exible design and high heat transfer performance
and might be suitable for combined heat transfer and mass transfer services. The
thermal-hydraulic performances of the two technologies were presented in previ-
ous sections. Flow visualization has often been used for analyzing ow structures,
but it only gives access to qualitative information or time-average measurements.
Using advanced numerical methods allows simulating single-phase ow in com-
plex geometries, such as those encountered in compact heat exchangers. The
determination of the mixing ability for water at a Reynolds number equal to 2000
is managed under the aspects of the computational uid dynamics (CFD) method.
An extensive review of turbulence models useful for compact heat exchanger
simulation is available in the literature (70). The most appropriate model for each
selected geometry will be discussed next.
For corrugated heat exchangers, the ow is almost three-dimensional.
Analyzing the stream function inside the 60 heat exchanger (Figure 33), we can
see that ow is mainly in the direction of the ow inlet, which is a characteristic
of subchannel ow. However, a small part of the uid is deviated by the channels:
furrow ow. So for this angle, quasiplug ow can be obtained, which is in
FIGURE 32 Mixture effect during condensation.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
accord with the work of Amblard (39) and Hugonnot (34). The ow can be con-
sidered homogeneous since there is the same ow rate through the channel width.
This indicates that high teta corrugated plate heat exchangers could be suitable
for chemical reactions where macromixing is needed. Analyzing the stream func-
tion inside the 30-angle heat exchanger (Figure 34), we can see that the ow fea-
ture is equally in the direction of the ow inlet (subchannel ow) and inside the
furrow (furrow ow). This result is in good agreement with Gaiser (35).
For a two-dimensional wavy channel, a numerical analysis performed at
GRETh (69) has shown that the mixing efciency of corrugated channels is excel-
lent because one corrugation is nearly sufcient to have perfect mixing (Figure 35).
For nned passages, all the described phenomena (Figure 36) are in good
accord with the regime predicted by the literature (70). Indeed, the ow hits the
front edge of the rectangular obstacle and separates immediately. The shear layer
reattaches to the wall and splits in two parts: one part ows upstream, creating a
recirculating and high-shear area; the other is convected downward by the mean
ow. With time, the shear layer becomes unstable near the reattachment point,
and it oscillates; it generates a vortex production inside the bubble and a
growth of the recirculating area. Due to impinging shear layer instabilities, the
FIGURE 33 Stream function inside the 60-angle plate heat exchanger.
FIGURE 34 Stream function inside the 30-angle plate heat exchanger.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 35 Numerical analysis of the mixing efciency in a corrugated channel.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
long bubble is broken, and an eddy is liberated and convected toward the trailing
edge. At the same time, the bubble length decreases. This vortex shedding occurs
on both faces of the obstacle, and a Von Karman street is formed in the wake of
the n.
In platen heat exchangers, the ow structure depends on the n geometry.
For offset strip ns, there is a high degree of mixing (25), and the ow becomes
turbulent even at low Reynolds numbers (Figure 37). Indeed, after six rows of ns
(e.g., about 20 mm), the ow is homogeneous, so the macromixing in the platen
heat exchanger is very efcient.
5.2. Micromixing
Micromixing technologies have only recently been applied to the design of
miniaturized devices for chemical applications, so called microreactors. The main
components of such microreactors are mixers and heat exchangers.
FIGURE 36 Closeup of the ow pattern inside the offset strip n geometry.
FIGURE 37 Evolution of a passive scalar inside the offset strip n geometry.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Two ranges of applications can be distinguished:
The laminar regime for highly viscous uids (such as glue), slow reactions,
and long residence time
The turbulent regime for classical gas- or liquid-phase reactions, fast reac-
tions, and low residence time
The present work will only focus on the turbulent regime, which is charac-
terized by eddies with a wide range of length and time scales. The largest eddies
are typically comparable in size to the characteristic length of the mean ow. The
smallest scales are responsible for the dissipation of turbulent kinetic energy,
which is related to the turbulent uctuation of the velocity. The higher the uctu-
ation, the smaller the scales in the ow and the better the micromixing efciency.
So for highly turbulent ows (high velocity or large hydraulic diameter), the
micromixing will be very efcient, without any inventive turbulent generators.
However, for compact heat exchangers where the hydraulic diameter is not large
(a few millimeters) and the velocity not very high (maximum 1 m/s), enhance-
ment techniques are needed in order to lower the turbulent-transition limit.
The mixing efciency is determined by both the value of the pressure drops
and the turbulent energy dissipation, (m
2
/s
3
):
where is given by
and L is the total length of the passage, is the voidage of the passage, p is the
pressure drop through the passage, and is the density of the uid. The higher the
mixing efciency, the better is the micromixing.
For corrugated heat exchangers, using the numerical simulation for both
60 and 30, we can evaluate directly from the computation and from classi-
cal correlation (57) (Table 2). The lower the angle, the lower the mixing ef-
ciency. Indeed, while lowering the angle, the ow pattern moves from subchannel
ow (helicoidal motion) to furrow ow (duct ow), which reduces the mixing.
The mixing efciency is very low (below 10%), so corrugated heat exchangers,
which are able to produce high heat ux, e.g., high macromixing, are not able to
produce micromixing.
For platen heat exchangers, using the numerical simulation for the OSF
geometry, we can evaluate directly from the computation and from classical
correlation (8) (Table 2). The OSF geometry is able to produce both macro- and
microturbulent scales. For the Reynolds number considered, the fully turbulent
pu
L
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
regime is not achieved (one must increase the velocity or the plate width by a fac-
tor of 2), but this geometry is efcient for heat transfer and mixing. It could be a
good concept in the area of temperature-controlled reactions.
5.3. Two-Phase Flow Heat Transfer and Mass Transfer
Numerous industrial operations involve a heat transfer between a liquid phase and
a gaseous phase, with an important mass transfer effect, either as desorption-
evaporation or as absorption-condensation. Here are some examples: reconcen-
tration, by evaporation, of solvents, toxic industrial efuents; production, by
absorption, of industrial aqueous acid solutions; reversible or irreversible chemical
reactions (oxidation, hydrogenation, sulfonation); purication of permanent gases
(air, smoke) by scrubbing of soluble vapors; desorbers and absorbers for heat pumps,
where these two operations occur simultaneously.
In these multifunctional processes, heat transfer and mass transfer are two
combined and simultaneous functions, and the objective is to substantially improve
these functions in order to save energy, to increase the process efciency, and to
reduce the size and cost of industrial plants. Corrugated pads are often used in the
dehumidication process or in chemical heat pumps, but a higher efciency could
be reached by using diabatic units, where the wall could exchange heat with the
liquid lm.
6. APPLICATIONS
6.1. Feed/Efuent Heat Exchangers
Feed/efuent heat exchangers are used in many industrial processes to warm up
the uid before the reactor and to cool it down after treatment at high tempera-
ture. The conventional design of such heat exchangers is based on shell-and-tube
units. But to increase the thermal effectiveness of the heat exchangers, the
required heat length becomes very important, and high pressure drop will occur.
TABLE 2 Micromixing Performance for Plate Heat
Exchangers (PHE) and Offset Strip Fin (OSF) Heat Exchangers
PHE
30 angle 60 angle OSF
Turbulent intensity (%) 6.2 11.0 10
(m
2
/s
3
) 0.43 2.01 17.1
(W/kg) 13.1 51.0 24.1
(%) 3.2 5.7 71
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The alternative to conventional shell-and-tube units is to use plate-type heat
exchangers (71). The advantages of PHEs are a high thermal effectiveness for a
low pressure drop, compactness, and a low propensity to fouling (72). In the ren-
ing industry, large PHEs are used in hydroteater (HDT and HDS); the aim of
these treatments is to reduce the naphtha contaminants (sulfur, hydrogen, arsenic,
lead, etc.).
With the use of such units, two main problems arise: two-phase ow distri-
bution and fouling. At the inlet of the efuent, the ow is a two-phase mixture
(gas oil hydrogen) with vapor qualities up to 20%. To ensure a homogeneous
flow distribution, the two phases are fed independently at the inlet of each channel
(up to 200 channels in parallel). These devices allow reaching high thermal effec-
tiveness and a low-temperature approach. Concerning fouling, because these heat
exchangers are totally welded and cannot easily be cleaned, tests have been per-
formed under laboratory conditions and on site to measure the fouling resistance.
Full-scale tests, realized at the Belgium Rening Corp in Antwerp (Figure 38), have
shown that after two years the thermal performance remained constant. A more
precise study was also performed using the Alcor fouling apparatus. A PHE and
shell-and-tube unit were connected in parallel; under similar operating condi-
tions, the PHE exhibited no fouling while the shell-and-tube heat exchanger
reached fouling resistance values up to 3 10
4
m
2
K/W.
Work is still required to optimize the design of such PHEs because the heat
transfer mechanisms are complex. On the feed side, a complex mixture is vapor-
ized; on the efuent side, the mixture is condensed with the presence of noncon-
densable gases.
6.2. Process Evaporators
Concentration of liquid by evaporation is widely used in industry, and a large
variety of techniques have been adopted. Two cases are considered: (1) the efu-
ent is desolved in water (salt solution, for example); (2) the efuent and the water
act as a mixture (wateracid solutions, for example). In the rst case, the con-
centration process is very efcient and high concentration can be obtained. In
specic cases, crystallization of the efuent can be achieved. Most of the techno-
logical developments have been obtained on the projects dealing with desalina-
tion of seawater or the sugar industry. For mixtures, the liquid efuent to be
concentrated is partially evaporated in a heat exchanger; at the outlet, the vapor
phase is richer with more volatile compounds and the liquid phase is richer with
less volatile compounds. The evaporator acts as a rst stage of distillation. The
effectiveness of the evaporation process depends essentially on the mixture-phase
equilibrium. In most of the cases, the heating uid is steam. As a consequence,
the channel geometry must me adapted on each side of the heat exchanger to
achieve optimal performance. Furthermore, as in most cases, the evaporating uid
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
has high fouling capacities, so the evaporating side must be cleanable and the
dead zone should be avoided.
Different types of evaporators are used in concentration processes: (1) ash
evaporation through a discharge valve, (2) horizontal tubular or plate reboilers
(submerged or falling lm), (3) vertical tubular or plate evaporators (climbing or
falling lm), (4) specic evaporators (direct contact, scraped surface, etc.). Compact
heat exchangers are mostly used as vertical evaporators with either falling lm
(Morgenroth et al. (73)) or climbing lm (Brotherton (12), Patel and Thomson (11)).
A special high-capacity compact falling-lm evaporator has been developed for
sugar plants. The use of falling-lm evaporators allows one to reach higher heat
transfer coefcients than with climbing-lm evaporators, especially for low tem-
perature differences. Compared to conventional systems, the overall heat transfer
performance can be up to two to ve times higher, as a function of the uid
FIGURE 38 Process ow sheet. (Courtesy of Packinox.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
viscosity. Plate heat exchangers are also used as evaporator in sugar plants, with
a similar level of enhancement. All the tests realized (lab scale, pilot and indus-
trial units) have shown that plate heat exchangers, even with small hydraulic
diameters, are not more sensitive to fouling than plain tubes. Other applications
in concentration processes of such compact heat exchangers should be developed,
especially in the area of mixture concentration.
6.3. Integrated Heat Exchangers in Separation Processes
Distillation and separation processes for purifying products requires up to 40% of
the overall energy demand in chemical processes (Trambouze (74)), and great
efforts have been made by engineers to reduce this energy consumption. The inte-
gration of the reboiler and the condenser in distillation columns has already been
studied, but the entire potential of integrated heat exchangers has not been achieved
(Lyon et al. (75)). As an example, plate heat exchangers have been installed in an
isopropanol dehydration plant as reboilers and condensers, and they have been
found to be very effective from the viewpoint of heat transfer.
Condensers and evaporators used in distillation processes are generally
based on the horizontal shell-and-tube design, and this conventional design leads
to large units, which have generally low energy efciency. The integration is not
optimal, and the heat exchanger is still a part of the unit. Introducing compact heat
exchangers in place of shell-and-tube units will permit greater compactness and
lower energy consumption. Because the heat exchanger operates purely in coun-
tercurrent, heat is available at a higher temperature than with horizontal shells. For
long-term developments, diabatic distillation and separation units must be studied.
Reux condensers are often used in the top of a distillation column, as a
rst stage to separating the lighter and heavier components. Because the liquid
ow and gas ow are countercurrent, a critical gas ow rate exists above which
ooding occurs. Although considerable work in the literature has been devoted to
free-falling lms (mostly in pipes), the issue of ooding in countercurrent gas/
liquid ow has not been settled yet. Furthermore, the literature concerning ood-
ing in narrow passages is extremely poor. Thus, for the case of compact con-
densers, there is no reliable tool for engineering-type predictions of ooding.
From the viewpoint of heat transfer, reux ows are more complex to study than
downward ows. Heat and mass transfer occur simultaneously between the
phases, and heat transfer is present between the liquid phase and the walls.
Literature provides neither experimental data nor a reliable prediction method for
these special system conditions. Studies about condensation inside channels have
been carried out only for concurrent downward ow of pure vapors in tubes with
large diameters. At present the design parameters for reux condensation can
only be estimated by the classical annular-ow model presented in heat transfer
handbooks. However, this model is not applicable under the given conditions, and
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
it is known from practical applications that the real condensation rate in compact
heat exchangers deviates drastically from predictions according to the classical
model. Modeling reux condensation (dephlegmation) in a compact platen heat
exchanger has been carried out (Urban et al. (76)), and the critical aspect raised
is the distribution of the liquid lm on the ns and the importance of the ow-
distribution device. An integrated heat exchanger distillation column has been
developed by Nakaiwa et al. (77), and a plate technology has been adopted. The
analysis outlines the energy savings that can be obtained as well as the higher
compactness.
Aluminum platen heat exchangers are often used as condensers in distil-
lation and separation processes, but they require nonfouling and noncorrosive
uids. In the chemical industry, stainless steel or welded-plate heat exchangers
have been used as top condensers of distillation columns, because they can be
either directly installed inside the column or closely integrated outside (Figure 39),
FIGURE 39 Overhead reux condensers.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
thereby avoiding extra piping and a pump for the condensate. In these compact
heat exchangers, condensation can take place in downward or reux ows. For
reux condensation, ooding may occur at high gas-ow rates, and the design of
nontubular heat exchangers is essentially based on correlations and methods
developed for plain tubes or larger hydraulic diameters. Studies on reux ows in
noncircular and small-hydraulic-diameter channels are required for a better design
of such apparatus.
Looking more closely at the basic structure of compact heat exchangers, it
can be noticed that the geometry is quite similar to the packing for distillation
columns. Because the wetting area is signicantly higher than for plain tubes and
higher mixing occurs in liquid lms, an additional rectication effect may occur
during reux condensation. This phenomenon needs to be evaluated because it
may reduce the height of the distillation column.
6.4. Reactor Heat Exchangers
The development of integrated chemical reactor heat exchangers requires sizing
tools for aiding the design and operation of the process. The thermal performance
of these heat exchangers is of prime importance for a global analysis of energy
efciency. Furthermore, a local analysis of ow and heat transfer conditions is also
required for a better characterization in terms of chemical reactors (mixing inten-
sity and residence time distribution).
At bHr Group (Phillips et al. (78)), tests performed on fast exothermic reac-
tions have shown that energy savings up to 40% could be achieved and that the
amount of by-product was signicantly reduced. Extension of this work to com-
mercial compact heat exchangers is currently being considered; the rst results
indicate that chemical heat exchangers (CHEs) could be suitable as continuous
chemical reactors.
Catalytic plate reactors already exist, but their range of application is
extremely limited (Jachuck and Ramshaw (79)). The basic idea is to bring into
contact the heat source (catalytic reaction) and the heat sink (cooling medium).
The catalyst is coated as a thin layer on one side of the plate, and on the other side
ows the coolant uid. For dehydrogenation applications, a plate-type catalytic
reactor has been developed (Arakawa et al. (80)); the benets are its higher ex-
ibility, via the control of the process temperature, and its higher productivity, via
the reduction in by-product formation. An alternative solution is to pack small
balls of catalyst between two plates. Plate catalytic reactors can operate under
high heat uxes and probably allow innovative reaction schemes (reaction with
pure oxygen or under pressure).
At ECN, an example of coupling reactions has been studied for reforming
of methanol. Combustion and reforming of methanol are done in two catalytic
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
compartments of the reactors. The catalyst has been coated on the internal
surfaces of a stainless steel platen heat exchanger. A monolith structure is used
for each reacting channel, and a model has been developed to calculate the heat
transferred between the channels. This heat exchanger reactor has been developed
for integration in a fuel cell plant.
The design of a heat exchanger reactor has to match several objectives:
The residence time must be sufcient to ensure a complete reaction within
the heat exchanger.
The uid temperature must be controlled, which implies high heat transfer
coefcients.
If the feed and the reactant are not premixed and well dispersed, a sufcient
turbulent intensity must be generated by the channel geometry.
The pressure drop must be acceptable.
The chemical process gives the enthalpy of reaction, the ow rate, the reaction
time, and the required reaction temperature. The rst step in the sizing procedure
is to calculate the required number of channels for the heat exchanger. Then the
pass arrangement is selected in order to achieve the highest possible Reynolds
number within an acceptable pressure drop. For example, if the total number of
channels is xed by the residence time: channels in series will induce high veloc-
ities and high pressure drop; channels in parallel will induce low velocities and
low pressure drop. The second step is to estimate the heat transfer coefcient and
to check that the heat ux can effectively be controlled by the secondary uid (the
lower heat transfer coefcient should be on the reaction side).
The use of compact heat exchangers, where the channel characteristic
dimension is between 1 and 10 mm, allow high heat transfer and mass transfer
coefcients, even for low Reynolds numbers. The limitation will come from the
mixing intensity, which may not be sufcient to ensure droplet breakdown and to
avoid droplet coalescence, which will directly affect the reaction. Preliminary
studies have shown that corrugated heat exchangers and OSF platen heat
exchangers are in turbulent ow even at low Reynolds numbers (Re 300) and
that they should be suitable for chemical reactions. Investigation of the uid ow
is of prime interest for such applications, and advanced numerical methods pro-
vide local and instantaneous values that can be used to characterize the chemical
reaction. These advanced CFD methods may also be used to develop specic
compact heat exchangers for chemical reactions as well as mixing devices.
Microchannels are also envisioned as a structure for heat exchanger reac-
tors. If the channel dimensions range between 100 and 500 m, the area per unit
volume is very high and allows catalytic reactions within the heat exchanger. An
example of such a heat exchanger reactor is given by Rebrov et al. (81). Several
studies are ongoing for applications in ne chemicals, reaction screening, and
micro hydrogen reformers (29).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
7. CONCLUSIONS
In this chapter, the different types of compact heat exchangers have been reviewed
and their applications described. Single-phase ow applications are now common
in the process industry; due to their high thermal effectiveness, compact heat
exchangers are real alternatives to conventional shell-and-tube units.
For multiphase applications, the use of compact heat exchangers is still not
widespread, but in some industries these heat exchangers are widely used. In par-
ticularly, in the refrigeration industry, plate heat exchangers are often used as boil-
ers and condensers. A great opportunity to transfer knowledge and technology can
be applied to compact heat exchangers. On the one hand, within the new environ-
mental requirements, mixtures will replace the conventional refrigerants (pure u-
ids), and the refrigeration industry is not used to dealing with mixtures. Transfer of
knowledge from the process industry, which is used to dealing with mixtures, could
help the refrigeration industry. On the other hand, because the refrigeration indus-
try already uses compact heat exchangers, the transfer of technology to the process
industry will be fruitful. New applications for compact heat exchanger should also
arise in environmental systems (Shah et al. [82]). Heat exchangers can also be con-
sidered an active component in the process and not only a utility. For instance, heat
exchanger reactors (Phillips et al. [27]) or diabatic distillation columns (Nakaiwa
et al. [77]) may be designed using compact heat exchanger technology.
Process intensication (PI) is described as a key for future development in
process plants (Green [83]), and because the cost of energy is now decreasing in
Europe, the search for compactness in equipment is the goal to be achieved. There-
fore, adopting compact heat exchangers is probably the most effective way to
intensify a process. To support and develop intensive technologies, there is a need
for basic studies on heat transfer and mass transfer in compact geometries (R&D
projects) and also targeted actions on specic applications (demonstration projects).
As outlined at the Compact Heat Exchangers for the Process Industry conference
(Shah [8486]), the development of new products must be realized in collabora-
tion with the process industry, and the reliability of compact heat equipment is the
rst goal to achieve. Furthermore, manufacturers must propose manufacturing
standards and design methodologies. Finally, the high potential of compact heat
exchangers clearly matches the objectives of process intensication, and a much
wider use should emerge within 510 years.
REFERENCES
1. Shah RK, Mueller AC. Heat exchange. In: Ullmanns Encyclopedia of Industrial
Chemistry, Unit Operations II. Vol. B3. Weinheim, Germany: VCH, 1988:Chapter 2.
2. Ohara T. The latest heat exchanger technology for vehicles. In: Shah RK et al., eds.
Compact Heat Exchangers and Enhancement Technology for the Process Industry.
Begell House, 1999:916.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
3. Rom L. Heat exchangers: is it time for a change? Chem Eng 1996; (Feb):7073.
4. Panchal CB, Rabas TJ. Thermal performance of advanced heat exchangers for
ammonia refrigeration systems. Heat Transfer Eng 1993; 14(4):4257.
5. Kumar H. The design of plate heat exchangers for refrigerants. Proceedings of the
Institute of Refrigeration, 199192, 1992:5.15.5.
6. Syed A. The use of plate heat exchangers as evaporators and condensers in process
refrigeration. In: Foumeny EA, Heggs, PJ, eds. Heat Exchange Engineering. Ellis
Horwood Series in Chemical Engineering. Vol. 1: Design of Heat Exchangers,
London, 1992: Chap. 10.
7. Navarro JM, Bailly A. Compact brazed plate heat exchanger. In: Recent Develop-
ments in Heat Exchanger Technology. Paris: Elsevier, 1994, pp 276283.
8. Sterner D, Sunden B. Performance of some plate and frame heat exchangers as evap-
orators in refrigeration systems. Proceedings of the 5th UK Heat Transfer Confer-
ence, IMechE, 1997.
9. Pelletier O, Palm B. Condensation and boiling of hydrocarbons in small plate heat
exchangers. Nordiske kle-ogvarmepumpedager, Reykjavik Iceland, June 1922,
1997.
10. Palm B, Thonon B. Thermal and hydraulic performances of compact heat exchang-
ers for refrigeration systems. In: Compact Heat Exchangers and Enhancement Tech-
nology for the Process Industry. Begell House, 1999:455462.
11. Patel N, Thompson. Plate heat exchangers for process evaporation and condensation.
In: Foumeny EA, Heggs PJ, eds. Heat Exchange Engineering. Ellis Horwood Series
in Chemical Engineering. Vol. 2. Compact Heat Exchangers: Technique of Size
Reduction, 1992, Chap. 20.
12. Brotherton F. Evaporation in plate heat exchangers. Heat Recovery Systems CHP
1994; 14(5):555561.
13. Turisini et al. Prevent corrosion failures in plate heat exchangers. Chem Eng Prog
1997; (Sept):4450.
14. Bacquet N. The spiral heat exchanger: concept and manufacturing technique. In:
Shah et al., eds. Compact Heat Exchangers and Enhancement Technology for the
Process Industry. Begell House, 2001:265267.
15. McDonald C. Low-cost compact primary surface recuperator concept for microtur-
bines. Appl Thermal Eng 2000; 20:471497.
16. Alpema. The standards of the brazed aluminium platen heat exchanger. Houston:
Association Alpema, 1994.
17. Ferrato M, Thonon B. A compact ceramic platen heat exchanger for gas turbine
heat recovery. In: Shah RK, ed. Compact Heat Exchangers for the Process Industry.
Begell House, 1997.
18. Adderley CI, Fowler JO. High-performance titanium platen exchanger using a
novel manufacturing process. In: Design and Operation of Heat Exchangers. Springer
Verlag, 1992.
19. Cowell T, Achaichia N. Compact heat exchangers in the automobile industry. In: Shah
RK, ed. Compact Heat Exchangers for the Process Industry. Begell House, 1997:
1128.
20. Trauger P, Hughes GG. Construction and Performance Characteristics of the PFE
Evaporator. SAE paper No. 930155, 1993.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
21. Webb RL. Advances in air-cooled heat exchanger technology. In: Proceedings of the
Heat Exchangers for Sustainable Development Conference, paper IL.6, Lisbon, June
1998:677692.
22. Pettersen J, Hafner A, Skaugen G, Rekstad H. Development of compact heat exchang-
ers for CO
2
air conditioning systems. Int J Refrigeration 1998; 21(3):180193.
23. Johnston N. Development and applications of printed circuit heat exchangers. Com-
pact Heat Exchangers for the Process Industry Conference, Snowbird, UT, June 1997.
24. Takeda T, Kunitomi K, Horie T, Iwata K. Feasibility of the applicability of a diffusion-
welded compact intermediate heat exchanger to next-generation high-temperature
gas-cooled reactors. Nucl Eng Design, 1997; 168:1121.
25. Tonkovich AL et al. Microchannel heat exchanger for chemical reactors. AICHE
Symposium Series 1996; 92(310):119125.
26. Watton B, Symonds K, Symonds S. Heat exchanger. International Patent, WO
97/21064, June 1997.
27. BHR PI 3 Phillips C. Development of a novel compact chemical reactor heat
exchanger. In: Proceedings of the 3rd International Conference on Process
Intensication, BHR-Group publication, No. 38, 1999, pp 7188.
28. Mehendale S, Jacoby A, Shah R. Heat exchangers at micro- and meso-scale. In: Shah
RK et al., eds. Compact Heat Exchangers and Enhancement Technologies for the
Process Industry. Begell House, 1999:5574.
29. Schubert K et al. Microstructure devices for application in thermal and chemical
process engineering. Microscale Thermophys Eng 2001; 5:1739.
30. Krishnan J et al. Manufacture of a matrix heat exchanger by diffusion bonding.
J Material Processing Tech 1997; 66:8597.
31. Navarro JM, Bailly A. Compact brazed-plate heat exchanger. In: Recent Develop-
ments in Heat Exchanger Technology., Paris: Elsevier, 1994.
32. Ahuja V, Green R. Application of matrix heat exchangers to thermomechanical
energy recovery from liquid hydrogen. Cryogenics 1998; 38(9):857867.
33. Focke WW, Knibbe PG. Flow visualization in parallel ducts with corrugated walls.
J Fluid Mech 1986; 165:7377.
34. Hugonnot P. Etude locale et performances thermohydrauliques faibles nombres de
Reynolds dun canal plan corrugu: application aux changeurs plaques. Thesis,
University of Nancy I, June 1989.
35. Gaiser G, Kottke EV. Effect of corrugation parameters on local and integral heat
transfer in plate heat exchangers and regenerators. In: Proceedings of the 9th Heat
Mass Transfer Conference, Jerusalem, Vol. 5. New York: Hemisphere Publishing,
1990:8590.
36. Breiziat D, Devienne R, Lebouch M. Local ow structure for non-Newtonian uids
in a periodically corrugated wall channel. J Enhanced Heat Transfer 1995; 2(12):
7177.
37. Thonon B, Vidil R, Marvillet C. Recent research and developments in plate heat
exchangers. J Enhanced Heat Transfer 1995; 2(12):149155.
38. Stasiek J, Collins MW, Ciofalo M. Investigation of ow and heat transfer in corru-
gated passages. I. Experimental results. Int J Heat Mass Transfer 1996; 39(1):149164.
39. Amblard A. Comportement hydraulique et thermique dun canal plan corrug: appli-
cation aux echangeurs de chaleur ; plaques. Thesis, INP Grenoble, March 1986.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
40. Mercier P, Tochon P. Analysis of turbulent ow and heat transfer in compact heat
exchangers by a pseudo-direct numerical simulation. In: Shah RK, ed. Compact Heat
Exchanger for the Process Industry. Begell House, 1997:223230.
41. Raju KSN, Bansal JC. Plate heat exchanger design. In: Kaka et al., eds. Low-
Reynolds-Number-Flow Heat Exchanger. Hemisphere, 1983:913932.
42. Shah RK, Focke WW. Plate heat exchangers and their design theory. In: Shah et al.,
eds. Heat Transfer Equipment Design. Hemisphere, 1988:227254.
43. Shah RK, London AL. Laminar Flow Forced Convection in Ducts. New York:
Academic Press, 1978.
44. Manglik RM, Bergles AE. Heat transfer and pressure drop correlations for the
rectangular offset strip n compact heat exchanger. Experiments in Thermal Fluid
Sci 1995; (10):171180.
45. Sobhan C, Garimella S. A comparative analysis of studies on heat transfer and uid
ow in microchannels. Microscale Thermophys Eng 2001; 5:293311.
46. Agostini B, Watel B, Bontemps A, Thonon B. Experimental study of single-phase
ow friction factor and heat transfer coefcient in mini-channels. CHE Symposium,
Grenoble: Edizioni ETS, August 2002, 8589.
47. Mller-Steinhagen HM. Fouling in plate and frame heat exchangers. In: Panchal CB,
ed. Fouling Mitigation of Industrial Heat Exchange Equipment. Begell House, 1997:
101112.
48. Clarke RH, Pritchard AM. Design of compact heat exchangers with practically no
resistance. In: Proceedings of Advances in Industrial Heat Exchangers, HEE96,
Birmingham, 1719 April, 1996.
49. Thonon B, Grillot JM. Fouling mitigation in plate heat exchanger by a proper design.
In: eds. Understanding Heat Exchanger Fouling and Its Mitigation, Lucca, Italy,
1997.
50. Thonon B, Grandgeorge S, Jallut C. Effect of geometry and ow conditions on par-
ticulate fouling in plate heat exchangers. Heat Transfer Eng 1999; 20(3):1224.
51. Carey VP. Two-phase ow in small-scale ribbed and nned passages for compact
evaporators and condensers. Nucl Eng Design 1993; 141:249268.
52. Kreissig G, Mller-Steinhagen HM. Frictional pressure drop for gas/liquid two-
phase ow in plate heat exchangers. Heat Transfer Eng 1992; 13(4):4252.
53. Margat L, Thonon B, Tadrist L. Heat transfer and two-phase ow characteristics dur-
ing convective boiling in a corrugated channel; In: Shah R.K., ed. Compact Heat
Exchangers for the Process Industry. Begell House, 1997:323329.
54. Winkelmann D, Thonon B, Auracher H, Bontemps A. Two-phase ow characteristics
of a corrugated channel. Proceedings of the 20th International Congress of Refriger-
ation, IIR/IIF, Sydney, 1999.
55. Haseler LE, Butterworth D. Boiling in compact heat exchangeers: industrial practice
and problems. In: Chen JC, ed. Convective Flow Boiling. Begell House, 1996:
5760.
56. Thonon B, Feldman A, Margat L, Marvillet C. Transition from nucleate boiling to con-
vective boiling in compact heat exchangers. Int J Refrigeration 1997; 20(8):592597.
57. Wambsganss MW, et al. Vaporization in compact heat exchangers. Proceedings of
the Experimental Heat Transfer, Fluid Mechanics and Thermodynamics Conference,
Brussels, 1997.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
58. Lunsford K. Understand the use of brazed heat exchangers. Chem Eng Prog 1996;
(Nov):4453.
59. Prasad B. The thermal design and rating of multistream platen heat exchangers.
In: Shah RK, ed. Compact Heat Exchangers for the Process Industry. Begell House,
1997:79100.
60. Wadekar VV. Flow boiling of heptane in platen heat exchanger passage. Compact
Heat Exchanger for Power and Process Industries. ASME, HTD Vol. 201, 1992:16.
61. Watel B, Thonon B. Flow boiling of propane in a platen heat exchanger. In:
European Heat Transfer Conference. Heidelberg: Edizioni ETS, 2000:11711176.
62. Feldman A, Marvillet C, Lebouch M. An experimental study of boiling in platen
heat exchangers. 2d European Thermal Sciences Conference, Rome, 1996:445450.
63. Kew P, Cornwell K. Conned bubble ow and boiling in narrow spaces. Proceedings
of the 10th International Heat Transfer Conference, paper 18-FB-12, New York:
Taylor and Francis, 1994:473478.
64. Tran TN, Wambsganss MW, France DM. Small circular- and rectangular-channel
boiling with two refrigerants. International J Multiphase Flow 1996; 22(3):489498.
65. Agostini B, Watel B, Bontemps A, Thonon B. Experimental study of ascendant boil-
ing ow in mini-channels. Zero LeakageMinimum Charge, IIR/IIF, Stockholm,
August 2002.
66. Thonon B, Chopard F. Condensation in plate heat exchangers: assessment of a general
design method. Eurotherm 47, Heat Transfer in Condensation. Elsevier, 1996:1018.
67. Srinavasan V, Shah RK. Condensation in compact heat exchangers. J Enhanced Heat
Transfer 1997; 4:237256.
68. Thonon B, Bontemps A. Condensation of pure hydrocarbons and their mixtures in
cross corrugated heat exchangers. Heat Transfer Eng 2002; 23(6):317.
69. Thonon B, Mercier P. Flow structure, thermal and hydraulic performances of com-
pact geometries used as integrated heat exchanger reactor. Process Intensication
Conference, Antwerp, October 1999.
70. Shah RK, Heikal M, Thonon B, Tochon P. Performances of compact heat exchanger
surfaces with emphasis on numerical analysis. Adv Heat Transfer 2000; 34:363444.
71. Fauconnier JC, Goreno F, Thomas R. A shell-and-plate heat exchanger for the cat-
alytic reforming unit at O.M. renery Karlsruhe. Eurotherm 33, Recent Develop-
ments in Heat Exchanger Technology, Paris: E.E.T.I., 1994:313320.
72. Shibuya H, Morohashi M. Fouling tests using a pilot-scale Packinox heat exchanger
with untreated straight-run gas oils. In: Panchal CB, ed. Fouling Mitigation of Indus-
trial Heat Exchange Equipment. Begell House, 1997:525536.
73. Morgenroth B, Austmeyer KE, Mauch W. Experiences with the falling-lm plate
evaporator and concept for energy-efcient process schemes in the cane sugar indus-
try. Zuckerindustrie 1995; 120.
74. Trambouze P. Energy saving in the petrochemical industry. In: Pilavachi PA, ed.
Energy Efciency in Process Technology. Elsevier Applied Science, 1991:6172.
75. Lyon H, Jachuck R, Ramshaw C. Compact heat exchangerscomes Out on top: results
of a survey. Heat Exchange Engineering, European Research Meeting, Birmingham,
AL, April 1996.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
76. Urban et al. Dephlegamator for ethylene plantmodeling of dephlegmation. In: Shah
RK, ed. Compact Heat Exchangers for the Process Industry. Begell House, 1997:
525532.
77. Nakaiwa M et al. Potential energy saving in an ideal heat-integrated distillation col-
umn. Appl Thermal Eng 1998; 18:10771087.
78. Phillips CH, Lauschke G, Peerhossaini H. Intensication of batch processes using
integrated chemical reactorsheat exchangers. Appl Thermal Eng 1997; 17(8.10):
809824.
79. Jachuck RJ, Ramshaw C. Developments in compact heat exchangers. Heat Exchange
Engineering. European Research Meeting, Birmingham, AL, April 1996.
80. Arakawa ST, Mulvaney RC, Felch DE, Petri JA, Vandenbussche K, Dandekar HW.
Increase productivity with novel reactor design. Hydrocarbon Processing 1993;
(March):93100.
81. Rebrov EV, Croon MHJM, Schouten JV. Design of a microstructured reactor with
integrated heat-exchanger for optimum performance of a highly exothermic reaction.
Catalysis Today 2001; 69:183192.
82. Shah RK, Thonon B, Benforado DM. Opportunities for heat exchanger applications
in environmental systems. Appl Thermal Eng 2000; 20:631650.
83. Green A. Process intensication: the key to the survival in global markets Chem
Industry1998; (March):168172.
84. Shah RK, ed. Compact Heat Exchangers for the Process Industry. Begell House, 1997.
85. Shah RK et al., eds. Compact Heat Exchangers and Enhancement Technologies for the
Process Industry. Begell House, 1999.
86. Shah RK et al., eds. Compact Heat Exchangers and Enhancement Technologies for the
Process Industry. Begell House, 2001.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
5
Process Intensication Through
Microreaction Technology
Wolfgang Ehrfeld
Ehrfeld Mikrotechnik AG, Wendelsheim, Germany
1. MICROTECHNOLOGY AS A KEY FOR THE ADVANCED
DESIGN OF CHEMICAL PLANTS
Since the middle of the 20th century, general technological progress has been
dominated essentially by a unique strategy of success, which constantly aims at
comprehensive miniaturization and integration of functional elements in technical
systems. The most outstanding development took place in microelectronics, where
integrated circuits with hundreds of millions or even billions of transistors have
become products of our daily lives. More recently, micromechanical, microoptical,
microuidic, and many other microdevices have become the basis for a multibillion
dollar business, the market for microtechnology (13). The products of microtech-
nology have achieved a key position in information, communication, entertain-
ment, automotive, and medical technologies.
In the chemical and pharmaceutical industries, biochemists were the rst or,
at least, the fastest to make an interdisciplinary move into the promising eld of
microtechnology. Terms like lab on a chip, microarrays, microuidics, and micro
total analysis systems have become familiar to all working in the life sciences and
at the front line of genomics, proteomics, glycomics, metabolomics, and all the other
omics in this area. They regard biomolecules to some extent like a source of data
and, consequently, have no problems applying information-based technologies to
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
innovations in their own eld. In the same way, large information technology (IT)
companies have started to enter the area of life sciences, utilizing their traditional
strengths in combination with the concepts of microreaction technology.
Researchers in chemical engineering are also intensively analyzing the pos-
sibilities potentially offered by the general strategy of miniaturization and inte-
gration to realize a radical change in design philosophy for modern chemical
plants. This research and development work started at ICI in the late 1970s, and
the term process intensication was used to characterize the novel concept. The
main intention was to achieve much lower investment, operating, and maintenance
costs for chemical plants, without decreasing their production capacity, by means
of a dramatic reduction in plant size; they aimed at a reduction factor of 100 or
even 1000 (4,5).
This intention may look more like a dream than a serious concept. However,
the technological progress even in standard plant items has proven, beyond doubt,
that this concept has a realistic basis. One may just consider, on the one hand, a
standard stirred-tank reactor with a cooling jacket having a volume of about 10 m
3
and, on the other hand, a potentially equivalent reactor for the same production
capacity consisting of a static mixer and a compact heat exchanger having a
volume of about 0.1 m
3
(6). This simple comparison demonstrates the superior-
ity of continuous operation over batch processing with regard to specic plant
volume and its importance in process intensication. Many other potential exam-
ples exist, such as spinning disk reactors, vortex scrubbers, reactor-mixing sys-
tems, and, of course, multifunctional reactors, which integrate reactions and unit
operations.
There is no doubt that the ultimate development of process intensication
leads to the novel eld of microreaction technology (Figure 1) (79). Because of
the small characteristic dimensions of microreaction devices, mass and heat trans-
fer processes can be strongly enhanced, and, consequently, initial and boundary con-
ditions as well as residence times can be precisely adjusted for optimizing yield and
selectivity. Microreaction devices are evidently superior, due to their short response
time, which simplies the control of operation. In connection with the extremely
small material holdup, nearly inherently safe plant concepts can be realized. More-
over, microreaction technology offers access to advanced approaches in plant design,
like the concept of numbering-up instead of scale-up and, in particular, the pos-
sibility to utilize novel process routes not accessible with macroscopic devices.
As a matter of fact, microfabrication methods have to be introduced into
chemical engineering in order to prot from the potential advantages of micro-
reaction technology. Although this is a difcult hurdle, a few chemical companies
have successfully started to utilize microreaction technology for commercial syn-
theses of ne and special chemicals. Nevertheless, much effort must still be spent
to transfer further promising research results into commercial application and to
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
get away from traditional strategies in chemical engineering. In the following,
a comprehensive analysis covering these aspects will be given.
2. EFFECT OF MINIATURIZATION ON UNIT OPERATIONS
AND REACTIONS
2.1. Enhancement of Heat Transfer
and Mass Transfer Processes
Diffusion, thermal conductivity, and viscosity are physically similar phenomena
that involve the transport of a physical quantity through a gas or liquid. The driv-
ing forces for the corresponding transport uxes of mass, energy, and momentum
are the gradients in concentration, temperature, and velocity, respectively, where
in all three cases the uxes are in the same direction as the gradients. For given
differences in these properties, a decrease in the characteristic dimensions results
in an increase in these gradients and, correspondingly, in higher mass and heat
transfer rates as well as in higher viscous losses. Accordingly, mixing and heat
exchange systems with extremely high transfer rates per unit volume can be real-
ized by miniaturization; on the other hand, however, the effect of viscous losses
has to be taken into account.
Besides the effect of decreasing linear dimensions on the corresponding
gradients, the effective surface area for exchange processes has to be considered.
With decreasing characteristic dimensions, the surface-area-to-volume ratio of
FIGURE 1 Evolutionary development through process intensication.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the system increases. This results in a corresponding enlargement of the specic
interface area, i.e., of the area per unit mass or unit volume, for transfer processes,
so, in connection with the enhancement of the gradients, i.e., the driving forces
for heat and mass transfer, extremely efcient mixers and heat exchangers can be
realized by miniaturization. Furthermore, the amount of material in a system is
reduced with the reciprocal third power of the characteristic dimensions, and,
consequently, the response time of the microdevice is extremely reduced so that
in most cases large differences concerning temperatures and concentrations are
diminished immediately.
It was demonstrated in many cases that highly exothermal reactions can be
performed under isothermal conditions using the channels of micro heat exchan-
gers as reaction volumes (Figure 2) (10). Pioneering work on this subject started
in the late 1980s, when micro heat exchangers with extremely high transfer rates
per unit volume were produced by means of advanced mechanical micromachin-
ing methods (Figure 3) (11). Meanwhile, specic heat transfer rates of more than
20 kW per cm
3
have been achieved, and a broad spectrum of materials has been
successfully applied.
A wide variety of micromixers are also available that allow mixing times in
the submillisecond range (8,12). They utilize mainly the concept of multilamination,
where two streams of uids are split into a large number of small substreams and fed
alternately into an interdigital ow system, where they merge into a joint stream
(Figure 4). Other concepts are based on the principle of splitting, side-to-side
arrangement, and further splitting to generate an increasing number of substreams
with different compositions, as known from large-scale static mixers. Vortex-type
micromixers have also abeen applied.
A wide range of applications for micromixers exists in the elds of gasliquid
suspensions and liquidliquid emulsions, with extremely small bubble and droplet
sizes, respectively. A high uniformity concerning size distribution is achievable;
in particular, the specic power consumption for generating suspensions and
emulsions is much lower than in the stirring devices or high-pressure jets usually
applied in the macroscopic range (8,13). Accordingly, micromixers are prom-
ising tools to improve the performance of phase transfer and other exchange
processes.
2.2. Inherent Process Restrictions in Miniaturized Devices
and Their Potential Solutions
As a matter of fact, miniaturization inevitably results in a number of process
restrictions, and completely new problems arise, too. There are, above all, the
problems of blockage of microstructures by solid particles and fouling effects.
Moreover, corrosion might be much more dangerous for microscopic than for
macroscopic devices.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 2 Microreactor for parallel screening of catalysts for partial oxidation of methane.
(Source: D. Hnicke, TU Chemnitz.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Nevertheless, if the solid particles are small enough, they will have no nega-
tive effect on the operation of a microreactor. On the contrary, microreactors can
even produce pigments of higher quality, i.e., smaller size and better uniformity,
than macroscopic devices. This positive result was obtained experimentally at
Clariant Company; consequently, a microreactor pilot plant for pigment production
is under construction (14). By means of highly efcient micromixers, Siemens Axiva
Company succeeded in improving the synthesis of acrylate resins. They could avoid
a detrimental portion of high-molecular-weight resin and, consequently, fouling
of the main continuously operating reactor. Evidently, there are at least concrete
chances to get around some of the problems resulting from small characteristic
dimensions.
There is, of course, no possibility of avoiding all problems inherently con-
nected with small dimensions. For instance, gravitational forces cannot be efciently
utilized to transport uids at small characteristic dimensions, since the effects of
FIGURE 3 Micro heat exchanger produced by means of mechanical
micromachining. (a) Platelet with grooves of 30-m depth and 70-m width.
(b) Assembly of crossow heat exchanger. (c) Final devices. (Source:
Forschungszentrum Karlsruhe.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
surface forces might far exceed those of mass or bulk forces. This problem is
immediately evident when regarding the reux in a miniaturized distillation col-
umn or the settler in a micromixer/microsettler system. To some extent, rotating
devices can be applied and centrifugal forces can be utilized for material transport.
This approach has been demonstrated successfully in microuidic systems, but it
is not a general solution. Consequently, other methods for phase separation are
required for miniaturized process devices, such as microltration to break emulsions
and the utilization of hydrophobic and hydrophilic surfaces or capillary effects.
Finally, surface effects will become more and more dominant in chemical reac-
tions when the characteristic dimensions are reduced, which may produce advan-
tages or disadvantages, depending on the respective type of reaction.
2.3. Consequences for the Selection of Reaction Routes
and Plant Design
The extreme enhancement in mass and heat transfer rates through miniaturization
of process devices results in fundamentally novel design possibilities with respect
to selecting alternative reaction routes and plant design. In contrast to macro
devices like large stirring tanks, the starting conditions for a chemical reaction can
be set precisely with respect to time and concentration because of the much faster
mixing of educts in a micromixer. The reaction starts at precisely dened time and
position with a spatially uniform composition. Thus, unfavorable reaction conditions
FIGURE 4 Micromixers. (a) Interdigital structure of a multilamination micro-
mixer. (b) Principle of split-and-recombine static micromixers. (Source: IMM.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
due to incomplete mixing are minimized that eventually result in undesired side
and secondary reactions and, consequently, losses in yield and selectivity.
The high heat transfer rates achievable in micro heat exchangers and reactors
avoid unfavorable reaction conditions resulting from hot spots or thermal runaway
effects. An optimum temperature or temperature prole for the reaction can be
chosen with respect to spatial distribution and time. Thus, a fast-owing uid ele-
ment can be cooled down or heated up very rapidly, in fractions of a millisecond.
Because of the small thermal mass of microdevices, a periodic change of tempera-
ture of the reactor can be realized, with a typical time constant of some seconds.
All these examples offer possibilities to improve yield and selectivity.
Since micro reactorsexcept for high-throughput screening in combinatorial
materials researchare usually operated under continuous conditions, it seems
simple to adjust the optimum residence time by means of a suitable delay loop or
channel that is also favorable with respect to yield and selectivity (Figure 5). How-
ever, the ow conditions in microdevices are generally characterized by a low
Reynolds number; consequently, a parabolic HagenPoiseuille prole will exist
in long channels and ducts. This ow prole results in an unfavorable broadening
of the distribution of residence time. Special channel congurations allow one to
reduce this effect.
2.4. Process Control and Safety
The inherent advantage of precise adjustment of the starting and boundary con-
ditions for chemical reactions and unit operations in microdevices provides a
novel basis for process control. Taking into account, in addition, the small holdup,
FIGURE 5 Process intensication by setting the optimum residence time.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
it is evident that an extremely short response time is a further inherent advantage
of microreaction devices with respect to process control.
As a result, there is a unique chance to utilize alternative reaction routes
for chemical synthesis that so far have not been applied commercially, for reasons
of safety or difculties in process control or because it is fundamentally impos-
sible to realize such reaction routes using macroscopic devices. This is the case, in
particular, for controlled reactions in the explosive regime (Figure 6) (15). This is
accessible by means of microreaction devices, since, due to their small characteris-
tic dimensions, they act like ame retention bafes. Moreover, the small dimen-
sions allow reactions to be performed at extremely high pressure, which is of
importance for chemical processes using supercritical solvents.
2.5. Sustainable Development by Numbering-Up
and Distributed Production
The safety problems connected with the storage of large quantities of educts and
products remain, of course, unchanged when a conventional plant is replaced by a
microreaction plant with the same production capacity. Nevertheless, this problem
may be reduced by replacing a large plant by several small plants for distributed
production. In contrast to conventional plants with macroscopic process devices,
where scale-up usually results in a considerable reduction of specic investment
costs, microreaction plants may instead prot from the mass production of micro-
devices in reducing specic investment costs. Scale-up for achieving the desired
production capacity can be done only at one site, while a plant comprising a large
FIGURE 6 Explosion-proof continuous synthesis in the explosive range. The
reaction system consists completely of ame-retarding microchannels.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
number of identical chemical microdevices according to the numbering-up concept
can be split up for production at several sites. As a result, microreaction technology
may contribute to the strategy of sustainable development by saving resources due
to a higher yield and, in particular, by exible production on site and on demand.
There are a number of further advantages to the numbering-up concept.
Research results can be transferred into production faster, plants can be constructed
in a shorter time, and the production capacity can be adjusted more exibly to
variations in demand. Since mass production of microdevices may result in rela-
tively a low cost per piece, novel cost-saving maintenance and repair concepts
based on disposable elements might be introduced.
3. FROM BASIC PROPERTIES TO TECHNICAL
DESIGN RULES
In contrast to microelectronics, where extremely powerful software tools and
detailed design rules exist for the development of ultralarge-scale integrated cir-
cuits, there are no corresponding comprehensive means in microreaction technol-
ogy available to date. Such design tools should comprise mathematical modeling
of ow and chemical reactions in miniaturized systems as well as specications
for suitable materials and simulation of manufacturing processes applicable to the
respective microreaction devices.
Since it will take several years to realize such an integral software toolbox,
individual approaches with separate steps have to be applied to meet gradually the
requirements of microreactor design. Standard software for computational uid
dynamics is directly applicable in this context, and there are also powerful software
tools for the simulation of special steps in microfabrication processes. However,
there has been rather little experience with materials for microreactors, optimiza-
tion of microreactor design, and, in particular, the treatment of interdependent
effects. Consequently, a profound knowledge of the basic properties and phenom-
ena of microreaction technology just described is absolutely essential for the suc-
cessful design of microreaction devices.
For instance, proper design rules must take into account that mixing and
heat exchange systems with extremely high transfer rates per unit volume can be
realized via miniaturization but that an increase in viscous losses may counter-
balance the positive effects. Accordingly, suitable gures of merit must be dened
for micromixers and micro heat exchangers that consider the ratio of mass or heat
uxes to pressure losses. However, the value of such a gure of merit should be
always considered in context with further boundary conditions of the process and
the interdependence of several process properties. Decreasing the characteristic
dimensions of a system results, as already explained, in a reduction in the material
holdup and a simultaneous enlargement of the surface-area-to-volume ratio of the
system. These aspects also determine the speed of mixing and heat transfer and,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
consequently, the degree of miniaturization required in a specic case. Such aspects
have to be considered for a favorable design of a microreaction system; in some
cases, extremely small dimensions are not necessary to avoid unfavorable re-
action conditions resulting from hot spots or thermal runaway effects.
If large amounts of materials have to be transported, a favorable design should
instead consider large pumps rather than arrangements with many micropumps,
which, in most cases, are commercially unattractive for cost reasons and technic-
ally less suitable because of their comparatively low efciency.
4. MICROFABRICATION OF REACTION
AND UNIT OPERATION DEVICES
4.1. General Requirements
Since the production of chemicals in a continuous process is inevitably connected
to a transport of material, three-dimensional microfabrication processes are required
in order to realize sufciently large cross sections for channels and ducts as well
as reaction volumes. Meanwhile, a wide variety of such processes as well as
design and test methods exist that all essentially originated from either semicon-
ductor technology or precision engineering. Thin-lm methods, applied to a large
extent in semiconductor technology, are less suitable for the generation of three-
dimensional microreaction devices but are widely used for surface processing and
protection as well as for manufacturing sensor elements.
Because of the extremely wide variety of reactions, educts, products, and
process conditions, a sufciently broad spectrum of materials is required to realize
suitable microdevices for chemical processes. Metals and metal alloys, plastics,
glass, ceramic materials, semiconductor materials like silicon, and various auxil-
iary materials for sealing, surface treatment, etc. have been successfully applied for
realizing microreaction devices.
Besides such basic aspects concerning the shape of and materials for micro-
reaction devices, costs play a major role in the selection of a microfabrication
process. In this respect, the number of pieces and the precision that is really
required, as well as aspects like availability and manufacturing experience, must be
taken into account. In contrast to the situation some years ago, the prerequisites for
cost-effective mass fabrication as well as small-scale production or rapid prototyp-
ing have essentially changed. Modern commercial equipment for the production of
microdevices is available that allows unreliable and uneconomic laboratory-scale
manufacturing devices to be replaced.
Mathematical modeling of the device function may also help to cut costs,
since it allows more realistic specications to be worked out with regard to func-
tional requirements. In addition, mathematical modeling of the process sequence
for microfabrication and assembly will be useful for cost saving. Such hard and
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
soft aspects will be considered in more detail in the following analysis of micro-
fabrication methods for reaction devices.
4.2. LIGA Technology
The LIGA technology allows the production of ultraprecise micro structures with
an extreme aspect ratio from a wide variety of materials (16,17). It is based on a
combination of deep lithography, electroforming, and molding processes. In the
rst step of the manufacturing sequence, a pattern from a mask or by means of a
serial beam-writing process is transferred into a thick resist layer on an electri-
cally conductive substrate. Ultraprecise microstructures with an extreme aspect
ratio can be generated by deep X-ray lithography. Using special epoxy resists
like SU 8, which utilizes intrinsic optical waveguide properties of irradiated
crosslinked regions, favorable results are also achievable by means of UV litho-
graphy.
In the second step, the three-dimensional relief-like structure of the resist
polymer generated by deep lithography is transferred into a complementary metal-
lic structure by means of electroforming, starting from the electrically conductive
substrate. Usually a nickel sulfamate electrolyte is applied, but there are also proven
electrolytes available for deposition of other metals and metal alloys.
The metal structure generated by means of electrodeposition may be the nal
product in some special cases. In general, however, it is used in a third step as a
master tool for a replication process, such as injection molding, casting, or emboss-
ing, for mass fabrication of microstructures. A wide variety of mold materials can be
applied for micromolding, e.g., organic polymers, preceramic polymers, and ceramic
and metallic powders with organic binders for subsequent sintering, so that most
material requirements for chemical microdevices can be favorably met.
It should be emphasized that the development of the LIGA technology orig-
inated from a special requirement in nuclear process engineering. Curved micro-
nozzles with characteristic dimensions in the micrometer range were needed as
mass products for aerodynamic separation of the uranium isotopes in the frame-
work of a large technological development work at the Karlsruhe Nuclear
Research Center (Figure 7). Today there are a number of LIGA products that evi-
dently have promising markets in the elds of micro-optics and integrated optics,
molecular biotechnology, and microactuators. More recently, LIGA components
and systems have been successfully applied to chemical engineering and
microreaction technology, respectively. A number of chemical companies and, of
course, research institutes utilize devices such as micromixers, micro heat
exchangers, and micro bubble columns as well as modular systems with integrated
functional elements for reaction, heat transfer, mixing, separation, and uid distri-
bution for process development. LIGA devices are also seriously being consid-
ered by the chemical industry for the production of ne chemicals.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
4.3. Wet and Dry Etching Processes
Wet etching processes are widely used to produce microstructures by means of
transferring resist patterns into various materials. However, for most materials only
isotropic etching processes exist, so, because of lateral underetching of the resist
pattern, only shallow microchannels or other shallow structures can be generated at
the surface of a bulk material. Three-dimensional structures can be manufactured
when the pattern is etched completely through thin foils, which then have to be
stacked in order to realize deep microchannels with a high aspect ratio (Figure 8).
Isotropic etching has been applied several times for manufacturing micro-
reaction devices. The technological expenditure is relatively low, but there are
some restrictions concerning accuracy, surface roughness, and geometrical
design. The product spectrum comprises various types of heat exchangers, micro-
mixers, separators, reaction units, and even integrated devices with several func-
tional elements.
Wet chemical anisotropic etching of monocrystalline silicon has been widely
applied in microtechnology (18,20). This method is based on the dependence of
etching velocity on crystal orientation, so only a few basic geometries can be
FIGURE 7 Double-deecting micronozzle for aerodynamic separation of ur-
anium isotopes manufactured by LIGA technology from nickel. The smallest
characteristic dimensions achieved in such devices are below 10 m. (Source:
Institute of Nuclear Process Engineering at the former Karlsruhe Nuclear
Research Center, now Forschungszentrum Karlsruhe, Siemens.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
realized. Besides silicon, there has been very little manufacturing experience with
other monocrystalline, inevitably very expensive, materials. Consequently, wet
chemical anisotropic etching is in general not very attractive for manufacturing
chemical microdevices because of strong restrictions with respect to shape and
material. Nevertheless, the technological expenditure is low, and material prob-
lems can also be solved via the deposition of protection layers. A number of
microuidic devices have been manufactured by means of this method, such as
micropumps, microvalves, and ow-distribution systems.
Besides anisotropic etching of monocrystalline materials, another wet
chemical etching process exists that uses a special type of photosensitive glass (19).
A wafer consisting of such glass is irradiated through a mask with UV light and
subsequently heated to a temperature between 800 and 900 K. This results in a
crystallization of the irradiated regions that can be dissolved much faster in hydro-
fluoric acid than the nonirradiated parts. This method has been successfully applied
to produce microreaction devices such as mixers, heat exchangers, and micro titer
plates from glass.
Precise microstructures with nearly any cross-sectional shape can be gen-
erated by means of anisotropic plasma-etching methods, where again silicon is the
most important and proven material (18,20). Usually, a mask pattern is transferred
into a thin layer consisting of a material resistant to plasma etching on a silicon
FIGURE 8 Microetched foil of stainless steel for manufacturing micro heat
exchangers by stacking and diffusion welding. (Source: Ehrfeld Mikrotechnik,
tztechnik Herz.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
wafer. Subsequently, silicon is etched by means of a uorine-containing low-
pressure plasma that generates gaseous silicon compounds.
In order to generate microstructures with an extremely high aspect ratio, the
directed etching process is connected with a subsequent deposition process from
the plasma where the walls oriented in parallel to the etching direction are covered
with a plasma polymer resistant to the reactive plasma (21). By means of multiple
repetition of directed etching and side wall passivation, channels and other structures
with nearly vertical walls can be realized; accordingly, extremely high aspect ratios
are achievable for nearly any cross-sectional shape (Figure 9).
FIGURE 9 Channel structure of a phase separator generated by ASE deep
etching of silicon. (Source: IMM.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
This so-called advanced silicon etching (ASE) process achieves etching
velocities on the order of 0.2 mm per hour. The ASE dry etching method has, of
course, limitations concerning, e.g., material selection and surface smoothness or
the brittleness of silicon, which makes it nearly impossible to use it directly as a
mold insert in micromolding processes. Nevertheless, it is possible to transfer
ASE silicon structures into complementary metal structures by electroforming.
For a number of applications, ASE is evidently a favorable alternative to LIGA in
manufacturing devices for microreaction technology.
4.4. Mechanical Micromachining
In the past few years, impressive progress has been made in so-called mechanical
micromachining, utilizing technologies based on so-called ultraprecision machining.
Complex three-dimensional microstructures have been generated with shape accur-
acies in the submicrometer range by means of milling, turning, and grinding
(11,22). Three- and ve-axis ultraprecision micromilling machines are available
as commercial products. Using diamond tools, an extremely low surface rough-
ness of a few nanometers is achievable for nonferrous materials. Progress has also
been made in machining stainless steel by using ultrane-grain hard metal tools
and novel technologies like vibration cutting. In addition, mechanical micro-
machining has been successfully applied with brittle materials. Micromixers,
micro heat exchangers, and reaction systems have been successfully produced by
means of this technology (Figure 3).
It is evident that there are hardly any limitations concerning the generation
of microstructures for chemical microdevices with complex geometries,
extremely high aspect ratio, and high precision from a wide variety of materials
by means of mechanical micromachining. Rather, restrictions may exist when
manufacturing closely packed channels or other structures, because of the nite
size of the tools. Also, manufacturing costs may become a problem in mass
fabrication; but in such a case, mechanical micromachining may be helpful for
manufacturing mold inserts for mass fabrication by means of micromolding.
Moreover, there are other mechanical methods for high-volume production, like
punching and embossing, that have been successfully applied in fabricating, e.g.,
micro heat exchangers.
4.5. Microelectrodischarge Machining
An interesting alternative to standard mechanical micromilling, turning, drilling,
and grinding methods is microelectrodischarge machining (EDM), which is virtu-
ally unlimited with respect to the geometrical shape of the work piece (23). Material
is removed in a discharge between the electrically conductive work piece and an
electrode by small sparks in a dielectric uid such as oil or deionized water. An
important advantage in micromachining is that the forces acting on the work piece
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
in EDM are extremely low. The disadvantages of micro EDM are a relatively large
surface roughness, limitations in miniaturization because of the nite size of the
electrodes and the spark gap in the electrical discharge, and very long machining
times, so this method is essentially used to manufacture mold inserts or prototypes.
The methods of mechanical micromachining and micro EDM have been
extensively applied to the fabrication of components such as micro heat exchangers,
mixers, and reaction channels as well as chemical microsystems with integrated
heat exchange, reaction, mixing, and distribution elements (Figure 10).
4.6. Micromachining by Means of Laser Radiation
Microfabrication by means of laser radiation covers a wide range of different
methods (24,25). On the one hand, these are processes where material is removed
in an intense electromagnetic eld by melting, evaporation, decomposition, photo-
ablation, or a combination of these phenomena. On the other hand, generating
processes exist where structures are built up from liquid resins, laminated layers,
or powders using, e.g., photochemically induced crosslinking of organic compounds
FIGURE 10 Micromixing element generated by microelectrodischarge machin-
ing. (Source: Ehrfeld Mikrotechnik, Zumtobel.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
in stereolithography or powder solidication by laser sintering. In addition, welding
by means of laser radiation is of major importance for the connection and assem-
bly of microdevices.
There are no restrictions worth mentioning concerning materials in micro-
machining by laser radiation, which is a real advantage for chemical microdevices
(Figure 11). However, limitations exist to achieving critical dimensions below
10 m and low surface roughness. Removal of material is also often connected with
the generation of debris, which reduces accuracy. Since laser-based microfabrication
processes, except lithography, are essentially serial rather than parallel machining
methods, their productivity is comparatively low. Nevertheless, they offer a huge
potential in rapid prototyping.
Laser-based micromachining processes have been applied to date only on a
relatively small scale for manufacturing chemical microdevices (27). This will
probably change relatively soon, since rapid prototyping will become more and
more important for developing novel microreaction devices.
5. IMPLEMENTATION OF MICROREACTION TECHNOLOGY
Microreaction technology has created a novel basis for:
Accelerating screening in combinatorial material development
Realizing extremely powerful tools for the evaluation of new reaction path-
ways
Implementing comprehensively the concept of process intensication for
the production of ne and special chemicals (Figure 12)
FIGURE 11 Part of a static micromixer manufactured by laser ablation from
aluminum oxide. (Source: Ehrfeld Mikrotechnik, Heidelberg Instruments
Microtechnologies.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Following the development route of miniaturization in the life sciences, the
implementation of microreaction technology in combinatorial material develop-
ment has been very successful. Companies like Symyx, located in Silicon Valley,
whose business is based on the highly effective synthesizing and screening of a
huge number of chemical compounds, have demonstrated that faster development
and cost savings are achievable by means of microreaction devices. Not only can
the amount of reactants, auxiliary substances, waste, energy, and space be mini-
mized, but all the other advantages of microreaction devices mentioned earlier can
also be favorably utilized (see, e.g., Ref. 27). The research work of such companies
is focused on more efcient catalysts, new polymers, high-performance phosphors
for illumination, and, of course, drug development and many other substances.
Promising work in this direction is also being done at universities and govern-
ment research centers (7,8,26,28).
Researchers at BASF have shown that microreactors can be utilized that
give access to operating conditions that cannot be realized by means of macroscopic
equipment. They succeeded in improving yield and selectivity in a highly exother-
mal two-phase reaction in connection with the synthesis of a vitamin precursor.
At Degussa company, a microreactor test facility for proprietary reactions is
under construction. The major focus in this context is the implementation of
microreaction devices as powerful tools for process development and, in particu-
lar, for the evaluation of new reaction pathways.
Companies like Clariant and Merck use microreactors for production, and
they are obviously convinced that the ultimate development of process intensi-
cation leads to microreaction technology. In contrast to other companies, Clariant
FIGURE 12 Microreaction technology aims at production of (a) information,
(b) tools for process development, and (c) chemicals.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
has reported about its work and its promising progress (14). Researchers at Clariant
assume that about 15% of future production facilities will be based on micro-
reaction technology.
However, microfabrication methods that are usually unfamiliar to chemical
engineers have to be introduced to prot comprehensively from microreaction
technology. This transition from standard manufacturing methods of plant com-
ponents to the development and production of microdevices is also inevitably
connected with the application of special materials that are not yet proven in chem-
ical engineering. In addition, novel design rules that have not existed until now
should be implemented for the long term to speed up the development of novel
devices.
Essential progress is to be expected from the introduction of so-called
modular microreaction systems. The system developed by Ehrfeld Mikrotechnik
comprises single functional elements for reactions, unit operations, transport,
FIGURE 13 Modular microreaction system consisting of functional elements
for reactions and unit operations arranged on a base plate. The cube-shaped
modules of stainless steel with built-in microstructures have a side length of
25 mm and can be operated at pressures up to 100 bar. (Source: Ehrfeld
Mikrotechnik.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
measurement, and control. The modules can be arranged and connected in a wide
variety of congurations and serve as a toolbox for realizing development platforms
similar to microplants (Figure 13). By means of such platforms, the optimum oper-
ation conditions of chemical processes as well as favorable plant congurations
can be determined and novel reaction routes tested. There is also a wide range of
applications in combinatorial chemistry. Since the microplants are usually set up
for continuous operation, they have a comparatively high productivity and can be
utilized directly for small-scale production of special chemicals.
6. CONCLUSIONS
Future progress in chemical engineering will be strongly determined by process
intensication through microreaction technology. It offers fundamentally novel
opportunities to save direct costs in the areas of development, investment, opera-
tion, and maintenance as well as to reduce indirect follow-up expenditures in
connection with storage, transport, and changes in demand or market trends.
A roadmap of microreaction technology for novel process routes and efcient
production is shown in Figure 14. Nearly all major chemical, chemical engineer-
ing, and pharmaceutical companies are interested in or even active in analyzing
the potential of microreaction technology. Moreover, there are a number of power-
ful three-dimensional microfabrication technologies that should meet nearly all
requirements concerning geometries as well as materials of microreaction devices
in prototyping and mass fabrication.
However, the implementation of a novel technology needs time. It is neces-
sary to prove carefully the potential advantages, to develop a sufciently broad
scientic basis, to implement reliable and cost-effective fabrication of chemical
microdevices on an industrial basis, to gain experience in the design, construction,
FIGURE 14 Roadmap of microreaction technology for novel process routes
and efcient production.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
and operation of microreaction plants, and nally to demonstrate real commercial
success. Meanwhile, a lot of effort has gone in this direction, but there is still a
multitude of tasks to solve until decisionmakers will be convinced enough of the
commercial prospects of microreaction technology to accept the inevitable nan-
cial risks of technological progress.
REFERENCES
A comprehensive overview of the international development work on microreaction tech-
nology can be found in the Proceedings of the International Conferences on Microreaction
Technology, which are listed in the following.
Ehrfeld W, ed. Proceedings of the 1st International Conference on Microreaction Technol-
ogy. Berlin: Springer, 1998.
Ehrfeld W, Rinard I, Wegeng R, eds. Process Miniaturization: 2nd International
Conference on Microreaction Technology, IMRET 2; Topical Conference Preprints.
AIChe, New Orleans, 1998.
Ehrfeld W, ed. Proceedings of the 3rd International Conference on Microreaction Technol-
ogy. Berlin: Springer, 2000.
Rinard I, ed. 4th International Conference on Microreaction Technology. Topical Confer-
ence Proceedings. AIChE Spring National Meeting, Atlanta, GA, March 59, 2000.
Matlosz M, Ehrfeld W, Baselt JP, eds. Proceedings of the 5th International Conference on
Microreaction Technology. Berlin: Springer, 2001.
Rinard I, ed. 6th International Conference on Microreaction Technology, Conference
Proceedings. AIChe Spring Meeting, New Orleans, March 1014, 2002.
The literature cited in this contribution is listed here.
1. Ehrfeld W, Ehrfeld U, Kiesewalter S. Progress and prot through microtechnologies.
Proceedings VDE World Microtechnologies Congress, MICRO.tec, Vol. 1, 2000: 917.
2. Market Analysis for Micro Systems II, 20002005. A NEXUS Task Force Report,
2002.
3. Bundesministerium fr Bildung und Forschung. Frderkonzept Mikrosystemtechnik
2000, Bonn, Germany, Jan 2000.
4. Stankiewicz AI, Moulijn JA. Process intensication: transforming chemical engin-
eering. Chem Eng Prog 2000; (Jan):2233.
5. Green A, Johnson B, John A. Process intensication magnies prots. Chem Eng
1999; (Dec):6673.
6. Wood M, Green A. A methodological approach to process intensication. IchemE
Symposium Series No. 144, 1998:405416.
7. Jensen KF, Hsing I-M, Srinivasan R, Schmidt MA, Harold MP, Lerou JJ, Ryley JF.
Reaction engineering for microreactor systems. Proceedings of the 1st International
Conference on Microreaction Technology. Berlin: Springer, 1998:29.
8. Ehrfeld W, Hessel V, Haverkamp V. Microreactors. In: Ullmanns Encyclopedia of
Industrial Chemistry. 6th ed. Weinheim: Wiley-VCH, 1999.
9. Jckel K-P. Microreaction TechnologyVision and Reality. Plenary Lecture,
ACHEMA 2000, Frankfurt.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
10. Mayer J, Fichtner M, Wolf D, Schubert K. A microstructured reactor for the catalytic
partial oxidation of methane to syngas. Proceedings of the 3rd International Confer-
ence on Microreaction Technology. Berlin: Springer, 2000:187196.
11. Schubert K, Bier W, Linder G, Seidel D. Herstellung und Test von kompakten
Mikrowrmebertragern. Chem Ing Tech 1969; 61:172173.
12. Lwe H, Ehrfeld W, Hessel V, Richter T, Schiewe J. Micromixing technology. Pro-
ceedings of the 4th International Conference on Microreaction Technology. AIChE
Spring National Meeting, Atlanta, GA, March 2000.
13. Bayer T, Heinichen H, Natelberg T. Emulsication of silicon oil in watercomparison
between a micromixer and a conventional stirred tank. Proceedings of the 4th Inter-
national Conference on Microreaction Technology. Atlanta, GA, AIChE Spring
National Meeting, March 2000:167173.
14. Wochner M. Mikroreaktorenkleine Ergnzung fr grosse Kessel, Clartext No. 3/
2002.
15. Hagendorf U, Jnicke M, Schth F, Schubert K, Fichtner M. A Pt/Al
2
O
3
coated
microstructured reactor/heat exchanger for the controlled H
2
/O
2
reaction in the
explosion regime. Proceedings of the 2nd International Conference on Microreaction
Technology, AIChE Spring Meeting, New Orleans, LA, March 1998, 8187.
16. Ehrfeld W, Mnchmeyer D. Three-dimensional microfabrication using synchrotron
radiation. Nucl Inst Meth Phys Res 1991; A303:523531.
17. Ehrfeld W, Ehrfeld U. Microfabrication for process intensication. In: Matlosz M,
Ehrfeld W, Baselt JP, eds. Proceedings of the 5th International Conference on
Microreaction Technology. Berlin: Springer-Verlag, 2001:312.
18. Koehler M, tztechniken. In: Ehrfeld W, ed. Handbuch Mikrotechnik. Mnchen:
Carl Hanser Verlag, 2001:279322.
19. Freitag A, Dietrich TR, Scholz R. Glass as a material for microreaction technology.
Proceedings of the 4th International Conference on Microreaction Technology. AIChE
Spring National Meeting, Atlanta, GA, March 2000:4854.
20. Rangelow IW, Kassing R. Silicon microreactors made by reactive ion etching. Pro-
ceedings of the 1st International Conference on Microreaction Technology. Berlin:
Springer, 1998:169174.
21. Laermer F, Schilp A (Robert Bosch GmbH). Method of Anisotropically Etching Silicon.
U.S. Patent No. 5501893, 1996.
22. Weck M. Ultraprecision machining of microcomponents. In: Weck M, ed. Proceed-
ings of the International Seminar on Precision Engineering and Microtechnology,
Aachen: European Society for Precision Engineering and Nanotechnology, July 2000.
23. Michel F, Ehrfeld W, Koch O, Gruber H-P. EDM for microfabricationtechnology
and applications. In: Weck M, ed. Proceedings of the International Seminar on
Precision Engineering and Microtechnology, Aachen, July 2000.
24. Bremus E, Gillner A, Hellrung D, Hcker H, Legewie F, Poprawe R, Wehner M,
Wild M. Laser processing for manufacturing microuidic devices. In: Proceedings of
the 3rd International Conference on Microreaction Technology. Berlin: Springer,
2000:187196.
25. Gillner A, Klotzbcher T. Lasermikrobearbeitung. In: Ehrfeld W, ed. Handbuch
Mikrotechnik. Mnchen: Carl Hanser Verlag, 2001:105143.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
26. Wiessmeier G, Schubert K, Hnicke D. Monolithic microreactors possessing regular
mesopore systems for the successful performance of heterogeneously catalysed re-
actions. In: Ehrfeld W, ed. Proceedings of the 1st International Conference on Micro-
reaction Technology., Berlin: Springer, 1998:2026.
27. Jandeleit B, Schaefer DJ, Powers TS, Turner HW, Weinberg WH. Combinatorial
materials science and catalysis. Angew Chem Int Ed 1999; 38:24942532.
28. Claus P, Hnicke D, Zech T. Miniaturization of screening devices for the combina-
torial development of heterogeneous catalysts. Catal Today 2001; 67:319339.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
6
Structured Catalysts and Reactors:
A Contribution to Process Intensication
Jacob A. Moulijn, Freek Kapteijn,
and Andrzej Stankiewicz
Delft University of Technology, Delft, The Netherlands
1. INTRODUCTION
In this book the chemical plant is focused upon. Therefore, the present chapter
emphasizes chemical reactors for the chemical process industry. But it should be
made clear that structured packings and catalysts also have a large potential in
consumer products. Chemical reactors form the heart of a (petro-)chemicals pro-
duction plant. Given the large variety of plants it is no surprise that a wide variety
of chemical reactors are used. Catalytic reactors can be roughly divided
into random and structured reactors. It is useful to start with a summary of the
major basic concerns (apart from high activity, selectivity, etc.) for catalytic
reactors:
Catalyst quality on a microscopic length scale (quality, number of active
sites)
Catalyst quality on a mesoscopic length scale (diffusion length, loading,
proles)
Ease of catalyst separation and handling
Heat supply and removal
Hydrodynamics (regimes, controllability, predictability)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Transport resistance (rate and selectivity)
Safety and environmental aspects (runaways, hazardous materials, selectivity)
Costs
On each of these, random and structured reactors behave quite differently. In
terms of costs and catalyst loading, random packed-bed reactors usually are most
favorable. So why would one use structured reactors? As will become clear, in
many of the concerns listed, structured reactors are to be preferred. Precision in
catalytic processes is the basis for process improvement. It does not make sense
to develop the best possible catalyst and to use it in an unsatisfactory reactor. Both
the catalyst and the reactor should be close to perfect. Random packed beds do
not fulll this requirement. They are not homogeneous, because maldistributions
always occur; at the reactor wall these are unavoidable, originating form the
looser packing there. These maldistributions lead to nonuniform ow and con-
centration proles, and even hot spots can arise (1). A similar analysis holds for
slurry reactors. For instance, in a mechanically stirred tank reactor the mixing
intensity is highly non-uniform and conditions exist where only a relatively small
annulus around the tip of the stirrer is an effective reaction space.
Catalytic conversion and separation are conventionally carried out in separ-
ate pieces of equipment. A combination of functions in single units is an elegant
form of process intensication. When one of the functions is a chemical reaction,
it is referred to as a multifunctional reactor. A good example is catalytic distilla-
tion technology from the CDTech Company. They have introduced elegant tech-
nology for desulfurization of oil (2). Structured reactors will play a key role in the
design of novel processes based on multifunctional reactors (3). A monolith is a
good example. Monolithic catalysts are shown in Figure 1.
FIGURE 1 Monolithic structures of various shapes. Square-channel cordierite
structures (1, 3, 5, 6), internally nned channels (2), washcoated steel mono-
lith (4).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Depending on ones point of view, a monolith can be considered a reactor
or a catalyst; the borders between catalyst and reactor vanish (4,5). Other struc-
tured reactors also deserve attention, but for the message it sufces to limit the
discussion to monolithic reactors.
2. OVERVIEW OF STRUCTURED REACTORS
Structured reactors and catalysts are encountered in a large variety (3,6).
Structured catalytic reactors can be divided into two categories. The rst involves
a structured catalyst, whereas the second one involves normal catalyst particles
arranged in a nonrandom way. In the rst category, the catalyst and the reactor are
essentially identical entities.
Because of their low pressure drop, structured reactors in practice dominate
the eld for treating tail gases. Figure 2 presents the major types of reactor. The
monolithic reactor represents the class of real structured catalytic reactors,
whereas the parallel-passage reactor and the lateral-ow reactor are based on a
structured arrangement of packings with normal catalyst particles.
Structuring is possible at all length scales. In structured reactors the level is
considered above that of a single particle. Structuring can be done based on dedi-
cated structured catalyst shapes in such a way that the catalyst is an integrated part
FIGURE 2 Low-pressure-drop reactors used for tail-gas treating.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
of the reactor shape. An alternative is to arrange catalyst particles in such a way
that a structured reactor is the result. Table 1 gives the subdivision together with
typical examples. By inspection of Figure 2, most of them can be recognized.
2.1. Monolithic Catalysts and Reactors
Monoliths usually are made from ceramics, but metals are also used. They can be
produced by extrusion of support material (often cordierite is used, but various
types of clays or typical catalyst carrier materials, such as alumina and titania, are
also used), a paste containing catalyst particles (e.g., zeolites, V-based catalysts)
or a precursor for the nal product (e.g., polymers for carbon monoliths).
Alternatively, catalysts, supports, or their precursors can be coated onto a mono-
lithic support structure (washcoating). Zeolites have been coated by growing
them directly on the support during the synthesis (7). The coating literature and
patents represent a large eld, and, in principle, a variety of preparation proced-
ures are available. All major catalyst support materials, ceramic and polymeric,
have been extruded as monolith (4,8). Metallic support structures are used for
automotive applications (9). The choice for a certain catalyst type will strongly
depend on the balance between maximizing the catalyst inventory and catalyst
effectiveness. For slow reactions, a high catalyst loading is desired and the pure
TABLE 1 Subdivision and Typical Examples of Structured Reactors
Structuring on the level of the catalyst Structuring exclusively on
and the reactor the level of the reactor
Monoliths Three-levels-of-porosity (TLP)
Extruded parallel-channel systems reactors
(honeycombs), usually ceramic Bead-string reactors
Emission reduction for cars Membrane-enclosed catalytic
Ozone decomposition in airplanes reactors
Selective catalytic reduction of NO
x
Arrays of corrugated plates
Arrays of bers
Gauzes
Ag
Methanol formaldehyde
Pt/Rh
NO production from ammonia
HCN production from methane
Foams
Catalytic membranes
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
catalyst-type monolith is desired; for fast reactions or if diffusion is slow, a thin
coating with a maximum geometric area is preferred.
Monoliths are the dominant catalyst structures for three-way catalysts in
cars (1013), selective catalytic reduction catalysts in power stations (1417) and
for ozone destruction in airplanes. What causes this popularity? The catalyst con-
sists of one piece, so no attrition due to moving particles in a vibrating case
occurs. The large open frontal area and straight channels result in an extremely
low pressure drop, essential for end-of-pipe solutions like exhaust pipes and stack
gases. The straight channels prevent the accumulation of dust. In all these appli-
cations the reaction system is relatively simple; a single uid phase (gas) has to
be treated at reasonable conditions. More demanding applications of monoliths
are now being investigated, fast reactions at high temperatures such as steam
reforming, partial oxidation of hydrocarbons to syngas, and oxidative dehydro-
genation (1820). These examples are limited to single-phase applications. As
will be discussed later, monoliths for multiphase applications have already proven
their value.
Monoliths are industrially produced in large quantities by extrusion. This
leads to the attractive situation that, although they are sophisticated structures,
they are commercially available at reasonable cost. Of course, monolithic cata-
lysts have disadvantages. They share with packed-bed catalysts the requirement
of sufcient stability or in any case good regenerability. With respect to mass
transfer and heat transfer characteristics, the major limitations are the laminar
ow through the channels, no interconnectivity between the channels, and a poor
radial heat conductivity. The latter two properties are much better for the foam-
type monoliths, but with a trade-off in a higher pressure drop and/or lower cata-
lyst loading (sites/m
3
). In principle, a laminar ow velocity prole is associated
with low mass transfer rates and a wide residence time distribution. Fortunately,
for gases, due to the small channel size and high diffusivity, this radial transport
in the channels is sufciently fast. Typical time scales for diffusion are given in
Table 2. In liquid phases the diffusivity is three orders of magnitude smaller,
which is one of the reasons that monoliths do not enjoy a high popularity in
liquid-phase operations. It will be shown that this is based on a misconception.
TABLE 2 Diffusion Time Scales in Catalytic Reactors (l
D
2
/2D)
D (m
2
/s) l
D
for 1 mm l
D
for 0.1 mm l
D
for 1 m
Gas 10
5
50 ms 0.5 ms 50 ns
Liquid 10
9
500 s 5 s 500 ns
Liquid in cat pore 10
10
5000 s 50 s 5 ms
Liquid in zeolite pore 10
11
50,000 s 500 s 50 ms
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The honeycomb-type monoliths are characterized by a very high geometric
surface area. Dependent on the cell density, this can exceed 3000 m
2
/m
3
reactor
!
Figure 3 shows the values for three different cell densities, i.e., for 200, 400, and
600 cpsi (cells per square inch). These examples are quite realistic. At present the
normal monolith for cars is a 400-cpsi monolith. The values for the geometrical
surface amount to 3440 m
2
/m
3
reactor
. In packed beds this value is much lower in
order to avoid unrealistic pressure drops. It is to be expected that future monoliths
will exhibit even larger geometric surface areas. That alone makes them highly
useful for process intensication programs.
Metal monoliths can be shaped rather freely. A good example is given in
Figure 4 (9), where it can be seen that in these parallel-channel systems the struc-
ture of the channels is such that the turbulence increases. The reasoning behind
that is the wish to counteract the low mass transfer rates associated with laminar
ow in the thin channels of the monolith.
2.2. Gauzes
The appearance of gauzes is illustrated by Figures 5 and 6 (9). The use of noble
metal gauzes goes back to the beginning of the 20th century for the oxidation of
ammonia into NO. This work followed up work of Ostwald, who applied plat-
inized asbestos and later a roll of corrugated strip of Pt. Probably, this was the rst
application of a structured reactor.
FIGURE 3 Geometric surface areas for three different cell densities.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2.3. Structured Packings
It is often suggested to coat structured packings of the type given in Figure 7
with catalysts, in the same way as monoliths. However, in normal applications
this does not lead to a satisfactory reactor. The geometric surface area is orders of
magnitude smaller than packed beds and monoliths. Of course, this problem can
be solved by packing the channels with catalyst particles. Also, they can be
applied as mixing device to be used for a good inlet distribution in the case of
FIGURE 4 Shaped channels in metal monoliths in order to increase mass
transfer in gas-phase applications.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
multiphase reactors. Later it will be seen that combinations of static mixers and
monolithic catalysts have a high potential in process intensication.
2.4. Foams
Foams are to some extent the negative images of packed beds. They can be used
when turbulent mixing is important. Figure 8 gives an example of a foam that is
used as a carrier for a molten salt catalyst in diesel soot trapping and combustion.
The openness and the mixing characteristics of foams have stimulated research in
the potential application in soot trapping. An advantage is the robustness of the
FIGURE 5 Pt/Rh gauze for the production of NO from ammonia.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 6 Details of a Pt/Rh gauze before (A) and after (B) use in the oxida-
tion of ammonia into NO.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
system: Plugging does not occur. A disadvantage is the relatively low trapping
efciency. In combustion foams result in stable combustion behavior.
2.5. Arranged CatalystsThree-Levels-of-Porosity (TLP) Reactors
Three-levels-of-porosity (TLP) reactors (2123) are alternatives for monolith
reactors in certain applications. Conventional catalyst particles can be arranged in
any geometric conguration. In such arrays, three levels of porosity can be dis-
tinguished: the pore space within the particles, the intraparticle space, and the
space between the arrays. An example of such a TLP reactor is the parallel-
passage reactor (PPR); see Figure 9 (24). The catalyst particles are conned
between wire gauze screens that divide the reactor into a large number of catalyst
layers with empty passages in between.
The gas ows along the catalysts layers instead of through the bed as in a
traditional xed-bed reactor. Because the gas ows through straight channels
FIGURE 7 Structured packing (Sulzer Katapak-K).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
(ca. 10 mm wide), the pressure drop over the PPR is much lower than over a
xed-bed reactor. Reactants are transferred from the gas to the catalyst inside the
gauzes, mainly by diffusion. The PPR is very suitable for treating dust-containing
gases, e.g., ue gases from power plants, because dust will not be collected on the
catalyst particles as a result of the straightness of the gas passages.
Bead-string reactors represent the limit of parallel-passage reactors: They
contain single-catalyst-particle subunits. Figure 10 gives a schematic representa-
tion (25).
Bead-string reactors have the advantages of lateral-ow reactors but not the
disadvantage of the low mass transfer rates in the units of the lateral-ow reactors.
FIGURE 8 Foam as a catalyst support (alumina impregnated with Cs
2
SO
4
.V
2
O
5
).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The disadvantage, of course, is the high cost, due to the difcult, labor-intensive
production. In a recent patent of ABB, an arrangement is claimed that combines
the advantages of the bead-string reactor with an easily produced arranged catalyst
conguration: Monolith channels are packed with catalyst particles, resulting in
strings of particles. This was described as a structured packed bed (26).
The reactor internals, consisting of structured packings packed with catalyst
particles, are also examples of arranged catalysts, e.g., the Sulzers Katapak-S type.
Multifunctional reactors often are also structured reactors. A good example
is the membrane reactor (27,28). Two types can be distinguished, those based on
a catalytic membrane and those in which the membrane only provides a selective
separation function without being catalytically active itself. The former is an
example of a structured catalyst, while the latter belongs to the category of
arranged catalysts. The reactor containing a nonactive membrane is referred to as
a membrane-enclosed catalytic reactor (MECR). In the following, an example of
a MECR is described.
2.6. Membrane-Enclosed Catalytic Reactor (MECR)
Catalytic membrane reactors are not yet commercial. In fact, this is not surpris-
ing. When catalysis is coupled with separation in one vessel, compared to separ-
ate pieces of equipment, degrees of freedom are lost. The MECR is in that respect
more promising for the short term. Examples are the dehydrogenation of alkanes
in order to shift the equilibrium and the methane steam reforming for hydrogen
production (29,30). An enzyme-based example is the hydrolysis of fats described
in the following.
FIGURE 9 Example of the TLP reactor: parallel-passage reactor (PPR). (Adapted
from Ref. 24.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2.6.1. Production of Fatty Acids by Fat Hydrolysis in a Membrane
Reactor
A recent development at laboratory scale is the application of an enzyme (lipase)
to catalyze the hydrolysis: Water and fat are mixed at low temperature (300 K) in
a continuous stirred-tank reactor (CSTR). The water phase contains the enzyme.
A much purer glycerol solution is obtained than in the conventional process. The
disadvantage is that the equilibrium is not favorable.
An elegant solution has been proposed based on a membrane reactor con-
sisting of a module with hollow cellulose bers [see Fig. 11 (31)]. The enzyme is
placed at the inner side of the bers, to which the fat is fed. Water passes at the
FIGURE 10 Schematic (a) and reactor conguration (b) of the bead-string
reactor.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
outside and diffuses through the membrane to react at the fat/lipase interface. The
fatty acid formed stays in the oil phase, whereas the glycerol formed is trans-
ported through the membrane into the water phase. Laboratory studies show
nearly complete conversions.
3. GAS-PHASE REACTIONS
It is fair to state that by and large the most important application of structured
reactors is in environmental catalysis. The major applications are in automotive
emission reduction. For diesel exhaust gases a complication is that it is overall
oxidizing and contains soot. The three-way catalyst does not work under the con-
ditions of the diesel exhaust gas. The cleaning of exhaust gas from stationary
sources is also done in structured catalytic reactors. Important areas are reduction
of NO
x
from power plants and the oxidation of volatile organic compounds
(VOCs). Structured reactors also suggest themselves in synthesis gas production,
for instance, in catalytic partial oxidation (CPO) of methane.
3.1. Environmental Catalysis
Converters for cars are usually ceramic monoliths and occasionally metal based.
Without much exaggeration, they can be claimed to be one of the major successes
of recent decades in the area of chemical engineering and catalysis. In the begin-
ning, the catalytic converter was placed underbody, where sufcient space was
available and where the temperature was expected to be mild. There was no need
FIGURE 11 Membrane reactor for the production of fatty acids. (Adapted
from Ref. 31.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
for process intensication! Later, performance became critical, mainly because of
the observation that under steady-state conditions the converter works well but
cold start emission is relatively large. Options that are offered include a catalyst
close to the engine, electrically heated catalysts, and combinations of catalyst and
adsorbent.
Initially, packed beds were also used. They, however, were no success, and
at present monoliths are applied exclusively. This should not be misunderstood.
Monolith means literally a single stone. However, metal-based analogues are
also included in the denition of monolith. In fact, for catalytic converters in cars,
in addition to ceramics, metal-based monoliths have been and still are used. A
major advantage of metal was the thin wall thickness that could be achieved.
Later, industry succeeded in manufacturing ceramic structures of comparable
wall thickness. In view of their higher resistance against corrosion, ceramic
monoliths are now more generally applied than metal ones.
Structured catalysts are also essential in diesel exhaust gas purication.
State-of-the-art solutions are marketed by PSA and by Johnson Matthey. The truck
market is dominated by diesel engines. In that application, space requirement is
a major issue, and intensication is badly needed. Space velocities exceeding
100,000 h
1
are demanded. Reactive structured lters are the way to go.
In the wake of the spectacular application of monoliths in the treatment of
automobile exhaust gas, the potential of monoliths in other applications was stud-
ied. Gas-phase reactions were the major area. Catalytic oxidation has received a
lot of attention. Low-NO
x
burners based on monoliths were designed, catalytic
oxidation of VOCs also benets from structured catalysts, basically because of
the low pressure drop and the resistance against dust.
Originally, packed-bed reactors were applied in selective catalytic reduc-
tion (SCR). They could be used only in low-dust applications (15). They were
successfully replaced by several types of structured catalysts, viz., honeycombs,
plate-type catalysts, and parallel-ow systems. Also, this technology is without
doubt successful. Volatile organic compounds are destroyed by combustion in
structured catalysts usually containing Pt or Pd. Compared to automotive appli-
cations, the size of the reactors is large. Figure 12 explains the engineering for the
destruction of VOCs of the large gas ows in industry (9).
3.2. Production of Syngas
In the production of syngas, the following reactions are usually undesired. The
desired reaction is the production of CO/H
2
mixtures according to
2CH
4
O
2
2CO 4H
2
whereas sequential oxidation giving CO
2
and H
2
O is not desired. This calls for
short residence times (ms), short diffusion length (as small as possible a diameter
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 12 Industrial unit for SRC containing metal monolith units.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
of the catalyst particle), and the absence of nonuniformity with respect to temp-
erature and concentrations. Moreover, the pressure drop in this type of applica-
tion should be minimal. It is obvious that a structured reactor should be used. This
leaves three candidates:
Monolith
Gauze
Foam
Foams have the highest turbulence and the highest pressure drop. Prob-
ably because of the rst phenomenon they are the most suited, although gauzes
also might be good. Monoliths have the advantage of being well dened, but
the absence of radial heat transport will lead to scale-up problems: When a cata-
lyst in a channel would die, the temperature will drop, and so will the vis-
cosity, leading to a leak in the reactor. It is clear that radial heat transfer is a key
issue (as it is in packed beds). Advanced designs have been described in the liter-
ature. By adapting the geometry, turbulence can be enhanced. Figure 4 illustrates
this.
Gauzes are the state of the art for many millisecond-reactions performed in
industry. The best-known examples are the oxidation of ammonia to NO for the
production of nitric acid and the Andrussov process, in which HCN is produced
from methane and ammonia (32):
NH
3
CH
4
1.5O
2
HCN 3H
2
O
The temperature in this process is quite high, 11001200C. It is not surprising
that under these severe conditions extended reorganization of the alloys takes
place. This is shown in Figure 6 for the oxidation of ammonia into NO.
Many more options are imaginable. A good example is the crosscurrent
monolith (Figure 13). In theory such a system allows ideal heat exchange
between adjacent channels. Such an elaborate structure might look improbable.
However, Corning recently led a patent claiming the direct extrusion of cross-
current structures. So these advanced reactor types might be applied in practice
in the future. Naphtha cracking, as a large-scale endothermic reaction, might be
a good case for such a reactor.
3.3. Scale-Up
Scale-up of structured reactors is usually easier than for packed-bed reactors. The
major point is that the hydrodynamics are independent of the scale of the reactor
(assuming a good inlet device). When the radial temperature prole is also inde-
pendent of the scale, scale-up is straightforward. This is the case for millisecond
reactors. In these reactors, rates are very high; as a consequence, in exothermic
reactions they operate adiabatically. So they scale easily.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
4. MULTIPHASE REACTIONS
Various types of reactors are being used commercially for multiphase applica-
tions, the major ones being the slurry reactor, the bubble-column reactor, and the
trickle-bed reactor (5). Figure 14 gives a schematic of these three types of reac-
tor. Each reactor has its own advantages and disadvantages. Slurry catalysts are
small (typically 50 m), while trickle-bed particles are larger (millimeter scale),
in view of the allowable pressure drop over the bed. The particle size is a crucial
parameter. In general it can be stated that larger particles are less efcient and,
even more important, are less selective in those reactions where the desired prod-
uct is subject to the following undesired reaction (A B C, with B as the
FIGURE 13 Crosscurrent monolithic structure.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
desired product). In that often-encountered case, the slurry reactor is more select-
ive than the trickle bed reactor. In terms of process intensication, a mechanically
stirred-tank reactor often is not a good choice. In practice it is no exception that
gasliquid mass transfer is rate determining. This implies that only the part of the
space close to the tip of the stirrer(s) is well used. A large part of the reactor does
not contribute much to the productivity and, depending on the kinetics, will lead
to low selectivity. Moreover, the major disadvantages of the slurry reactor are the
separation of product and catalyst and catalyst attrition. The trickle-bed reactor is
much more convenient, but large particle sizes are unavoidable. An important
limitation of trickle-bed reactors is that, in practice, they are nearly always oper-
ated cocurrently, to avoid liquid entrainment by the gas (ooding). Some
important commercial applications, however, would benet from a countercur-
rent operation, especially for equilibrium-limited reactions and in the case of
strong product inhibition (33). Examples are hydrotreating processes like
hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrocracking.
Only for large particles or low ow rates could this operational mode be achieved
in a packed bed [Synsat process (34)]. Deep desulding is a good example of a
reaction where the concentration prole in countercurrent operation is more opti-
mal from a reaction kinetics point of view (2,35). Also, more active catalysts
(e.g., noble metals) can be used in the last part of the reactor (catalyst proling)
that are more susceptible to H
2
S poisoning and, as a consequence, are not suit-
able for cocurrent operation. Overall, countercurrent operation leads to deeper
desulfurization with smaller catalyst units or to larger throughputs (21). In all
FIGURE 14 Schematic representations of three basic gasliquidsolid reactor
systems.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
three reactor types, in principle a runaway is possible because when hot spots
would be formed, large amounts of reactants can reach the hot spot, leading to a
classical runaway. It will be shown that structured reactors based on monoliths are
imaginable that do not possess the unfavorable properties mentioned. In current
practice, one application is known. AKZO-NOBEL (previously EKA-NOBEL)
operates ve plants based on the anthraquinone process, in which the reduction
step is carried out in monolith reactors (36,37). Many multiphase reactions have
been carried out at laboratory scale, and in industry interest is also increasing, as
is apparent from patents (26,3846). Recently, monolith structures have been
tried in photocatalysis. This might well be an important application in the future.
4.1. Hydrodynamics and Mass Transfer in Monoliths
4.1.1. Cocurrent Operation
For cocurrent gasliquid ow, several ow regimes can occur. The preferred one
is usually the so-called Taylor, or slug, ow (4749). This type consists of gas
bubbles and liquid slugs owing consecutively through the small monolith chan-
nels. The gas bubble lls up the whole space of the channel, and only a thin liq-
uid lm separates the gas from the catalyst (Figure 15). For two reasons, the rate
of mass transfer is large. First, the liquid layer between bubble and catalyst coat-
ing is thin, increasing mass transfer. Second, the liquid slugs show an internal
recirculation during their travel through a channel. Because of this, radial trans-
fer of mass is increased. Moreover, the gas bubbles push the liquid slugs forward
as a piston, and a type of plug ow is created. Compare this with single-phase liq-
uid ow through the channels. Because of the low channel diameter, the ow will
be laminar and, as a consequence, the radial transport will be extremely slow,
leading to very poor reactor performance: Rates are slow and the reactor exhibits
strong nonplug-ow behavior. For multiphase operation under slug-ow condi-
tions, the mass transfer increase is an order of magnitude larger than for single-
phase liquid ow, whereas the increase in frictionthat is, pressure dropis
much less [Figure 16 (50)]. A fortunate nding is that Taylor ow conditions are
easily realised under practical conditions.
Ideally, in contrast to packed beds, scale-up of monolithic reactors is very
simple. When we know the behavior of one channel, we should be able to predict
the whole reactor. Is this really true? Compared to a packed bed, a monolithic reac-
tor differs in radial transport. When the initial distribution of liquid in the radial
direction is nonideal, going down through the reactor, this unfavorable distribution
does not change. In a packed-bed reactor this happens to a certain degree. Therefore
in scale-up, the reactor inlet system has to be designed well so that the distribution
of the liquid in the top of the reactor is ideal. We found that if a bubble emulsion on
top of the monolith is present, a satisfactory distribution seems to be guaranteed, as
found for trickle-bed reactor operation. We carried out a large experimental pro-
gram and dened the conditions where this happens to be the case. It appeared that
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the ow rate has to be above a specied minimal value. Stacking of monolith pieces
on top of each other or with some spacing in between, to allow some radial mixing,
does not seem to have a negative impact on the ow characteristics.
So the ow rates have to be sufciently high (linear velocities > 0.1 m/s) in
order to guarantee a good distribution of liquid over the cross section of the reac-
tor. One might wonder if upow of gas and liquid is not to be preferred, because
lower ow rates might be applied. This appeared not to be the case. Again, high
ow rates are needed to establish a good gasliquid ow distribution. It might be
worthwhile to investigate whether systems can be developed or conditions estab-
lished that allow low ow rates. Combinations of monolithic catalyst packages
with the Sulzer type of contactors are being conceptually investigated in our
group. They might increase the window of operability toward lower ow rates.
FIGURE 15 Taylor ow through a single tube. Left: picture of airwater ow;
middle: schematic representation of the gas and liquid slugs; right: CFD
velocity pattern in a liquid slug showing the liquid recirculation.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Moreover, they might lead to exibility, allowing more compact reactor systems.
The rst results are promising.
4.1.2. Mass Transfer
Mass transfer was studied experimentally in various ways. Nonreactive studies
involved the uptake or release of oxygen by the liquid for the measurement
of gasliquid transfer (5153), while in reactive studies the overall gassolid or
liquidsolid transfer could be determined. As an example of the performance, a
monolith in the hydrogenation of -methylstyrene was compared with a trickle-
bed reactor under identical reaction conditions in cocurrent mode. Per unit reac-
tor volume, the washcoated 400-cpsi monolith yielded a hydrogenation rate more
than four times higher. For a reaction that is mass transfer controlled, this stresses
the better mass transfer in the monolith. Overall, the Ni was used 40 times more
efciently in the monolith than in the trickle-bed reactor, even in spite of the use
of an eggshell catalyst in both cases. In spite of the high rates observed, it was felt
that not all the Ni in the washcoat layer was optimally used (5,54). In subsequent
work a more eggshell type of coating was realized and the rates observed were an
order of magnitude higher. Mass transfer is usually expressed as the factor k
l
a, the
mass transfer coefcient times the exposed surface area per unit volume a. Values
of k
l
a depend strongly on the gas and liquid properties, but for many systems val-
ues of 0.5 s
1
are found, and values even much larger than 1 s
1
possibly apply.
FIGURE 16 Relative increase of friction and mass transfer due to gasliquid
Taylor ow, compared to developed laminar ow in small tubes. repre-
sents the dimensionless length of a liquid slug, Re the Reynolds number
based on the liquid.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
This is one order of magnitude higher than in conventional reactor types (1),
which underlines the process intensication potential of monolithic reactors.
In Table 3 the three common reactor types are compared. Obviously, the
monolithic reactor in the Taylor-ow regime leads to a high degree of process
intensication. When these numbers are recalculated into production rates, values
of 40 mol/m
3
reactor
-s were found. Figure 17 illustrates the high value in relation to
the Weisz window of reality. This demonstrates the attractiveness of using
monoliths in fast catalyzed gasliquidsolid reactions.
4.1.3. Countercurrent Operation in Monoliths
and Arranged Packings
Under practical conditions, countercurrent operation in a packed bed reactor is
not feasible, because ooding occurs (55,56). The reason is that in the small inter-
stitial space, extended momentum transfer takes place between the liquid owing
down and the gas owing upward. At velocities used in industry this would imply
TABLE 3 Comparison of Gas-to-Liquid
Mass Transfer in Three Common
Three-Phase Reactor Types
Reactor type k
l
a (s
1
)
Trickle bed 0.050.2
Slurry 0.10.3
Monolith 1
FIGURE 17 High productivity of multiphase monolith reactors.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
that the particle size has to be increased by an order of magnitude. This leads to
unacceptable internal diffusion limitations. Clearly, momentum transfer has to be
decreased while maintaining high rates. This can be done by structuring the cata-
lyst or by clever arranging of the catalyst particles in the reactor.
Various arranged catalyst structures are used or can be envisaged. Figure 18
gives an overview of the most important ones. The principle of these structures is
that relatively large channels are present, leaving space for countercurrent ow
without extended momentum transfer. In catalytic distillation a lot of experience
has already been gained in packings based on particles arranged in bales (2).
From an extensive study, it appeared that in structured reactors as well, counter-
current operation is possible at industrially relevant conditions. The breakthrough
was the design of optimal monolithic structures and dedicated inlet and outlet
systems. For example, good results were obtained by cutting the monolith under
an angle of 70 as the optimal value (57) or by a special outlet construction, guid-
ing the liquid away from the exit (Figure 19). Finned tubes exhibit outlet ood-
ing mainly only, whereas the unnned tube also exhibits inlet ooding. The
unnned tube has a larger hydraulic diameter due to the absence of the ns and
hence a wider ooding-free region. Injecting the gas via a capillary and guiding
away the liquid through quartz wool plugs even enlarges this region for the nned
channel. This graph illustrates that current operating region for trickle bed reac-
tors (HDS) is well covered by the nned monoliths (58).
FIGURE 18 Various arranged particle packings.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
4.1.4. Monolith Reactors
The catalyst to be used in a reactor operation can be coated as a thin layer on the
channel walls, and, hence, the reactor can be described as a frozen slurry reac-
tor. The diffusion length is small and well controllable.
The catalyst loading often is relatively small, but using thicker coatings or
using a monolith extruded from the catalyst support, e.g., an all-alumina mono-
lith, can increase it. The high cell density of the monoliths creates a high geo-
metric surface area. Using a packed bed, unrealistically small particles would be
needed to achieve this. Catalyst separation and handling are as convenient as in a
common packed bed.
Scale-up is in principle straightforward. Larger channel geometries (e.g., in
the internally nned monolith channels) allow countercurrent operation of gas
and liquid. Monolith reactors are intrinsically safer. The monolith channels have
no radial communication in terms of mass transport, and the development of run-
away by local hot spots in a trickle-bed reactor cannot occur. Moreover, when the
feed of liquid or gas is stopped, the channels are quickly emptied.
From the foregoing it should be evident that monolithic reactors (and other
structured reactors) in many respects are superior to classical reactors. Indeed, for
FIGURE 19 Flow map for countercurrent gasliquid ow (n-decane/air) through
finned channels with different outlet geometries. Indicated are the ooding
limits for single tubes. Finned tubes exhibit mainly only outlet ooding,
whereas the unnned tube also exhibits inlet ooding. The unnned tube has
a larger hydraulic diameter due to the absence of the ns and hence a wider
ooding-free region. Injecting the gas via a capillary and guiding away the
liquid through quartz wool plugs even enlarges this region for the nned
channel. This graph illustrates that current operating region for trickle-bed
reactors (HDS) is well covered by the nned monoliths (From Ref. 58.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
several reactions, monolithic catalysts have been reported, although, except for
one case, only at the bench or pilot scale. The interesting points are to demon-
strate that the theoretically outlined advantages are indeed present. Compared
to classical reactors they in fact boil down to a larger reactor productivity, a
better selectivity control, and a higher efciency. The rst point also implies a
better catalyst utilization. Obvious is the fact the catalyst is xed in a reactor and
pressure drops are low.
Highly exothermal reactions can be applied by external heat exchange
(1,39). If a CSTR-type reactor is not desired, the horizontal reactor with inter-
stage cooling is an attractive alternative.
The hydrogenation step in the anthraquinone process of AKZO-Nobel is an
industrial realization of a monolithic reactor and includes a lot of pioneering work
from the Anderson group (5963). More examples of the use of monoliths can be
found in Refs. 5 and 64.
In our own group, in cooperation with a chemical industry, we have studied
the selective hydrogenation of pyrolysis gasoline, a by-product of the naphtha
cracking that can be upgraded to gasoline by selectively removing gum-forming
dienes and styrene-like molecules, leaving intact the internal alkenes. This study
(65) demonstrated the plug-ow behavior needed for such a selective conversion
and the efcient use of the active phase, which was at least a factor of 34 better
than in a trickle-bed operation. The hydrogenation of -methylstyrene, men-
tioned earlier, is an even more appealing example of better active-phase utiliza-
tion and conrms the good mass transfer properties.
An attractive property of monolithic reactors is their exibility of applica-
tion in multiphase reactions. These can be classied according to operation in
(semi)batch or continuous mode and as plug-ow or stirred-tank reactor or,
according to the contacting mode, as co-, counter-, and crosscurrent. In view of
the relatively high ow rates and fast responses in the monolith, transient oper-
ations also are among the possibilities.
The cocurrent monolith reactor, with its plug-ow characteristics, can in
principle be used in downow, upow, and horizontal-ow modes, provided a
good gasliquid distribution is secured (66). The last mode might solve a major
problem in practical applications of monoliths: Because, for hydrodynamic rea-
sons, high ow rates are needed, the reactor length tends to be very large. The
process intensication potential of horizontal conguration, the so-called in-line
monolithic reactor (ILMR), has recently been demonstrated by Stankiewicz (67)
for one of the large-scale hydrogenation processes of DSM. It has been shown
that the conventional reactor system, consisting of a stirred-tank reactor and a
packed-bed reactor, could be replaced by an ILMR ca. 30100 times smaller
(depending on the type and thickness of the washcoat) (Figure 20). Research with
respect to this type of reactor is in progress. An important outcome of the research
might be that coupling of monolithic elements, mixing units and heat exchangers,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 20 Process intensication in the in-line monolithic reactor, ILMR.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
leads to exible cascade reactor setups, enabling multistep synthesis in one pass.
Further extension of the in-line monolithic reactor concept on other unit oper-
ations could possibly lead in the future to much more compact, safer, and envir-
onmentally friendly chemical plants, in which pipelines would not only serve for
sending gases and liquids, but be made functional and used for reactions or sep-
arations (68).
The best studied mode is cocurrent downow. It can be envisaged in two
ways, with either a controlled ow of gas or a free recirculation due to entrain-
ment by the liquid at the entrance of the monolith (Figure 21). This reactor is an
alternative to the bubble-column reactor often used in biotechnological applica-
tions. Since high reactor types are being used and large gas-ow rates are
required, the energy input to introduce and compress the gas for injection at the
bottom is relatively high. In the downow monolith reactor, this gas injection is
automatically achieved. The cocurrent reactor type can easily be used as a stirred
reactor type by a large recirculation ow without extremely high energy input due
to the low pressure drop. An external heat exchanger can be scaled independent
of the reactor to deliver the required heat duty (1,5).
Of course, monoliths have disadvantages. They are at this moment more
expensive than particle catalysts. In xed-bed operation, they will have to exhibit
FIGURE 21 Conguration of a cocurrent downow monolith reactor with free
gas recirculation. Only liquid is recirculated, and an external heat exchanger
can be scaled independent of the reactor to deliver the required heat duty.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
a sufciently long lifetime. In quickly (irreversibly) deactivating reactions, they
will not be used. Of extreme importance is that the inlet distribution should be
secured. In cocurrent ow, both gas and liquid have to be in contact evenly with
the catalyst at the monolith walls.
Countercurrent operation is appealing in many respects and is already exe-
cuted in practice. An example is the desulfurization process of Syn Tech, where
co- and countercurrent operation are combined (see Figure 22).
Apart from the GLS-type, LLS- and GLLS-type catalytic reactions are also
possible using monoliths. The attractive property is to bring reactants efciently
in contact with the solid catalyst. But there is more. They can be applied in stripping,
extraction, evaporation, drying, and distillation, in co- as well as in countercurrent
modes. Monoliths are then used as low-pressure-drop and low-energy-consuming
contacting devices. The combination with catalysis is then obvious to arrive at a
multifunctional reactor system in which reaction and controlled reactant addition
or product removal is achieved. These applications are not restricted to gaseous
or liquid phases, but also work in solid phases. The straight channels are ideal for
xed- or moving-bed applications (Figure 23), the former to combine an opti-
mized catalyst inventory and liquid holdup while still having a relatively low ow
resistance of a single pellet-string reactor. Moreover, existing catalysts can be
applied. The use of nned channels gives even more freedom. This could be
FIGURE 22 Cocurrent/countercurrent Syn Technology process scheme.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
considered a structured trickle-bed reactor, where longer residence times can be
achieved than in a straight-channel monolith. Blocks of monoliths lled with par-
ticles may nd application in catalytic distillation or three-levels-of-porosity
reactors (26), replacing the catalyst bales (5).
Channels lled with a single particle string have much better solid ow char-
acteristics than a packed bed, so application of monoliths as the moving-bed reac-
tor internal is seducing. This opens a wide range of applications, covering
moving-bed adsorption processes, moving-bed applications for deactivating cata-
lysts (reforming, hydrodemetallization, dehydrogenation), solid trickle-ow reac-
tors, and regenerative processes where a moving catalyst is alternatingly subjected
to different atmospheres and transport reaction intermediates and/or heat (FCC,
butane to maleic anhydride oxidation). The channel structure also works as a ow
straightener, providing better plug-ow characteristics in large-diameter entrained-
ow reactors, which suffer from back-mixing of catalyst at the reactor wall.
Evaluating the properties of catalytic reactors, there are three important
aspects that strongly determine the overall performance: the amount of catalyst and
intrinsic kinetics, the transport phenomena (diffusion inside and outside the catalyst),
and the hydrodynamics in the reactor. In classical reactors these are strongly inter-
related and cannot be dened and designed independently. As an example, for fast
FIGURE 23 Monolith structure packed with catalyst particles (catalyst bale)
for structured xed-bed or moving-bed applications.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
reactions small catalyst particles are desired from the point of view of catalyst effect-
iveness, but a packed bed with small particles will result in an unacceptable pressure
drop. Therefore an optimum has to be sought for the particle size. The elegance of
structured reactors is that these three aspects can be designed and optimized fairly
independently, resulting in an optimized reactor performance. Figure 24 shows the
situation for a monolith channel in a gasliquid reaction. The zeolite catalyst should
be very small to take advantage of its high activity. It is embedded in a washcoat
layer on the wall of the monolith channel of a thickness that yields the required cata-
lyst effectiveness and selectivity. The channel diameter determines the type of ow,
in this case Taylor ow, which optimizes the mass transfer from the gas and liquid
phases to the solid catalyst. The straight monolith channels already ensure a low
pressure drop across the structure. This is a structured system covering about 10
orders of magnitude, from nanometers to several meters.
If the aim of the catalytic process is to optimize yield and selectivity, one
can distinguish two extremes: fast reactions and slow reactions (Figure 25). In
slow reactions, the intrinsic reaction kinetics control the process, so the catalyst
inventory should be as high as possible. Increasing the wall thickness of a mono-
lith can have the desired effect. In fact the degree of variation in this way is vir-
tually from 1090 volume %, whereas a packed bed will always yield an
inventory of around 60% or lower if hollow catalyst particles are used.
In fast reactions, mass transfer or intraparticle diffusion becomes control-
ling. Thinner catalyst coatings, Taylor ow, etc. can be applied to optimize these
FIGURE 24 Schematic representation of the operation of a monolith channel,
washcoated with a zeolite catalyst, under Taylor-ow conditions.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
requirements. If mass transfer is controlling, the productivity is proportional to
the geometric surface area of the monolithic structure. Increasing cell densities
are recommended, without yielding unacceptable pressure drops. These examples
exemplify the potential power of the application of monolithic structures in cata-
lytic reactors.
5. CONCLUSIONS
Monolithic and other structured catalysts exhibit favorable properties with respect
to practical convenience, high rates, high selectivity, and low energy consump-
tion. From an engineering point of view, the easy scale-up and the potential of
high safety are also appealing. This is not limited to single-phase processes, but
they are also well placed for multiphase processing.
Monoliths exhibit a large exibility in operation. They are well suited for
optimal semibatch, batch, continuous, and transient processing. Catalytic conver-
sion can be combined with in situ separation, catalytic reactions can be combined,
heat integration is possible, and all lead to process intensication. In the short term,
catalytic monoliths will be applied to replace trickle-bed reactor and slurry-phase
FIGURE 25 Aspects controlling the performance of a three-phase catalytic
reactor, indicating the exibility of the use of monolithic catalysts.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
operations in view of the better overall conversion and selectivity performance.
Monoliths allow efcient use of small catalyst particles, e.g., zeolites, and have a
substantial exibility with respect to catalyst inventory in a reactor. Multifunc-
tional reactor operations like reactive stripping and distillation are challenging
applications that are not too far away. Several options exist for applications in the
oil renery and the chemical process industry.
The essence of the use of a structured reactor is that it allows the decoup-
ling of intrinsic reaction kinetics, transport phenomena, and hydrodynamics. In
this way those phenomena that control the overall behavior of a catalytic reactor
can be optimized independently, giving rise to excellent reactor performance.
REFERENCES
1. Heiszwolf JJ, Engelvaart LB, Gvd Eijnden M, Kreutzer MT, Kapteijn F, Moulijn JA.
Hydrodynamic aspects of the monolithic loop reactor. Chem Eng Sci 2001; 56:
805812.
2. Dautzenberg FM. Novel reactor concepts in hydrotreating. Cattech 1999; 3:5463.
3. In: Cybulski A, Moulijn JA, eds. Structured catalysts and reactors. New York: Marcel
Dekker, 1998:670.
4. Cybulski A, Moulijn JA. Monoliths in heterogeneous catalysis. Catal Rev Sci Eng
1994; 36(2):179270.
5. Kapteijn F, Heiszwolf JJ, Nijhuis TA, Moulijn JA. Monoliths in multiphase catalytic
processesaspects and prospects. Cattech 1999; 3:2441.
6. Cybulski A, Moulijn JA. Monoliths in heterogeneous catalysis. Catal Rev Sci Eng
1994; 36:179270.
7. Jansen JC, Koegler JH, Bekkum Hv, Calis HP, Bleek CM, Kapteijn F, Moulijn JA,
Geus ER, Puil Nvd. Zeolitic coatings and their potential use in catalysis. Microporous
Mesoporous Materials 1998; 21:213226.
8. Gulati ST. Ceramic catalyst supports for gasoline fuel. In: Cybulski, A Moulijn JA,
eds. Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:1558.
9. Twigg MV, Webster DE. Metal and coated-metal catalysts. In: Cybulski A, Moulijn JA,
eds. Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:5990.
10. Twigg MV, Wilkins AJJ. Autocatalystspast, present and future. In: Cybulski A,
Moulijn JA, eds. Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:
91120.
11. Heck RM, Farrauto RJ. The automobile catalyst. Cattech 1997; 1:117124.
12. Marin GB, Hoebink JHBJ. Kinetic modeling of automotive exhaust catalysis.
Cattech 1997; 2:137148.
13. Misono M. Catalytic reduction of nitrogen oxides by bifunctional catalysts. Cattech
1998; 2:5369.
14. Beretta A, Orsenigo C, Tronconi E, Forzatti P, Berti F. Analysis of plate-type mono-
lith SCR-DeNO(x) catalysts. Kinet Catal 1998; 39:646648.
15. Beretta A, Tronconi E, Groppi G, Forzatti P. Monolithic catalysts for the selective
reduction of NO
x
with NH
3
from stationary sources. In: Cybulski A, Moulijn JA, eds.
Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:121148.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
16. Tronconni E, Forzatti P. Adequacy of lumped parameter models for SCR reactor with
monolith structure. AIChE J 1992; 38:201210.
17. Topse N-Y. Catalysis for NO
x
abatement. Cattech 1997; 1:125136.
18. Iordanoglou DI, Bodke AS, Schmidt LD. Oxygenates and olens from alkanes in a
single-gauze reactor at short contact times. J Catal 1999; 187:400409.
19. OConnor RP, Schmidt LD. Catalytic partial oxidation of cyclohexane in a single-
gauze reactor. J Catal 2000; 191:245256.
20. Beretta A, Ranzi E, Forzatti P. Production of olens via oxidative dehydrogenation
of light parafns at short contact times. Catal Today 2001; 64:103111.
21. Hasselt BWv, Lebens PJM, Calis HP, Kapteijn F, Sie ST, Moulijn JA, Bleek CMvd.
A numerical comparison of alternative three-phase reactors with a conventional
trickle-bed reactor. The advantages of countercurrent ow for hydrodesulfurization.
Chem Eng Sci 1999; 54:47914799.
22. Hasselt BWv, Calis HP, Sie ST, Bleek CMvd. Pressure drop characteristics of the
three-levels-of-porosity reactor. Chem Eng Sci 1999; 54:37013708.
23. Hasselt BWv, Calis HP, Sie ST, Bleek CMvd. Liquid holdup in the three-levels-of-
porosity reactor. Chem Eng Sci 1999; 54:14051411.
24. Sie ST, Calis HP. Parallel passage and lateral-ow reactors. In: Cybulski A, Moulijn JA,
eds. Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:323354.
25. Calis HP, Takcs K, Gerritsen AW, Bleek CMvd. Bead-string reactor. In: Cybulski A,
Moulijn JA, eds. Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:
355392.
26. Strangio VA, Dautzenberg FM, Calis HP, Gupta A. Fixed-Bed Catalytic Reactor.
Patent WO 99/48604, World, 1999.
27. Falconer JL, Noble RD, Sperry DP. Catalytic membrane reactors. In: Noble RD,
Stern SA, eds. Membrane Separations Technology. Principles and Applications.
Amsterdam: Elsevier, 1995:669712.
28. Hsieh HP. Inorganic Membranes for Separation and Reaction. Amsterdam: Elsevier,
1996:1591.
29. Thomas S, Schafer R, Caro J, Seidel-Morgenstern A. Investigation of mass transfer
through inorganic membranes with several layers. Catal Today 2001; 67:205216.
30. Kikuchi E. Membrane reactor application to hydrogen production. Catal Today 2000;
56:97101.
31. Moulijn JA, Makkee M, Diepen AEv. Chemical Process Technology. West Sussex,
UK: Wiley, 2001:453.
32. Bodke AS, Olschki DA, Schmidt LD. Hydrogen addition to the Andrussow process
for HCN synthesis. Appl Catal A General 2000; 201:1322.
33. Sie ST, Lebens PJM. Monolithic reactors for countercurrent gas-liquid operation. In:
Cybulski A, Moulijn JA, eds. Structured Catalysts and Reactors. New York: Marcel
Dekker, 1998:305321.
34. Maxwell IE. Innovation in applied catalysis. Cattech 1997; 1:513.
35. Schanke D, Bergene E, Holmen A. FischerTropsch synthesis. Patent WO 98/38147,
U.S., 1998.
36. Bengtsson E. Process in the production of hydrogen peroxide. Patent EP 0 384 905,
European, 1990.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
37. Berglin T, Herrmann W. A method in the production of hydrogen peroxide. Patent EP
0 102 934, European, 1983.
38. Schanke D, Bergene E, Holmen A. FischerTropsch synthesis. Patent WO 98/38147,
World, 1998.
39. Machado RM, Parillo DJ, Boehme RP, Broekhuis RR. Use of a monolith catalyst
for the hydrogenation of dinitrotoluene to toluendiamine. Patent US6,005,143, US,
1999.
40. Schanke D, Bergene E, Holmen A. FischerTropsch synthesis. Patent US6,211,255,
US, 2001.
41. Reesink BH, Vaarkamp M. Chemical process in reactor with structured catalyst.
Patent EP 1 121 976 A1, Europe, 2000.
42. Cornelison RC, Alcorn WR, Baillie IC. Process for hydrogenation of organic com-
pounds. Patent EP 0 233 642 A2, Europe, 1987.
43. Edvinsson RK, Moulijn JA. Monolietreactor. Patent application NL 1004961, The
Netherlands, 1999.
44. Makkee M, Kapteijn F, Moulijn JA. Reactorvat. Patent NL93/00231, The Netherlands,
1999.
45. Sie ST, Moulijn JA, Cybulski A. Internally finned channel reactor. Patent
PCT94901066.4, International (Europe), 1999.
46. Sie ST, Cybulski A, Moulijn JA. Process for catalytically reacting a gas and a liquid.
Patent EP 0 667 807 B1, Europe, 1998.
47. Irandoust S, Andersson B. Simulation of ow and mass transfer in Taylor ow through
a capillary. Computers Chem Eng 1989; 13:519526.
48. Thulasidas TC, Abraham MA, Cerro RL. Axial dispersion of bubble-train ow in
capillaries. Chem Eng Sci 1996.
49. Thulasidas TC, Abraham MA, Cerro RL. Flow patterns in liquid slugs during
bubble-train ow inside capillaries. Chem Eng Sci 1997; 52:29472962.
50. Kapteijn F, Nijhuis TA, Heiszwolf JJ, Moulijn JA. New nontraditional multiphase
catalytic reactors based on monolithic structures. Catal Today 2001; 66:133144.
51. Heibel AK, Heiszwolf JJ, Kapteijn F, Moulijn JA. Inuence of channel geometry on
hydrodynamics and mass transfer in the monolith lm-ow reactor. Catal Today
2001; 69:153163.
52. Lebens PJM, Stork MM, Kapteijn F, Moulijn JA. Hydrodynamics and mass transfer
issues in a countercurrent gasliquid internally nned monolith reactor. Chem Eng
Sci 1999; 54:23812389.
53. Lebens PJM, Heiszwolf JJ, Kapteijn F, Moulijn JA. Gas-liquid mass transfer in an
internally nned monolith operated countercurrently in the lm-ow regime. Chem
Eng Sci 1999; 54:51195125.
54. Nijhuis TA, Kreutzer MT, Romijn ACJ, Kapteijn F, Moulijn JA. Monolithic catalysts
as more efcient three-phase reactors. Catal Today 2001; 66:157165.
55. Lebens PJM, Meijden Rvd, Edvinsson RK, Kapteijn F, Sie ST, Moulijn JA.
Hydrodynamics of gasliquid countercurrent ow in internally nned monolithic
structures. Chem Eng Sci 1997; 52:38933899.
56. Lebens PJM, Kapteijn F, Sie ST, Moulijn JA. Potentials of internally nned
monoliths as a packing for multifunctional reactors. Chem Eng Sci 1999; 54: 13591365.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
57. Lebens PJM, Edvinsson RK, Sie ST, Moulijn JA. Effect of entrance and exit geo-
metry on pressure drop and ooding limits in a single channel of an internally nned
monolith. Ind Eng Chem Res 1998; 37:37223730.
58. Lebens PJM, Edvinsson RK, Sie ST, Moulijn JA. Effect of entrance and exit geo-
metry on pressure drop and ooding limits in a single channel of an internally nned
monolith. Ind Eng Chem Res 1998; 37:37223730.
59. Andersson B, Irandoust S, Cybulski A. Modeling of monolith reactors in three-phase
processes. In: Cybulski A, Moulijn JA, eds. Structured Catalysts and Reactors.
Chemical Industries, Vol. 71. New York: Marcel Dekker, 1998:267304.
60. Hatziantoniou V, Andersson B, Schn N-H. Mass transfer and selectivity in liquid-
phase hydrogenation of nitro compounds in a monolithic catalyst reactor with seg-
mented gasliquid ow. Ind Eng Chem Process Des Dev 1986; 25:964970.
61. Hatziantoniou V, Andersson B. The segmented two-phase ow monolithic catalyst
reactor. An alternative for liquid-phase hydrogenations. Ind Eng Chem Fundam
1984; 23:8288.
62. Irandoust S, Andersson B. Mass transfer and liquid-phase reactions in a segmented
two-phase ow monolithic catalyst reactor. Chem Eng Sci 1988; 43:19831988.
63. Irandoust S, Andersson B. Monolithic catalysts for nonautomobile applications.
Catal Rev Sci Eng 1988; 30:341392.
64. Cybulski A, Moulijn JA. The use of monolithic catalysts for three-phase reactions.
In: Moulijn JA, Cybulski A, eds. Structured Catalysts and Reactors. New York: Marcel
Dekker, 1998:239266.
65. Smits HA, Stankiewicz A, Glasz WC, Fogl THA, Moulijn JA. Selective three-phase
hydrogenation of unsaturated hydrocarbons in a monolithic reactor. Chem Eng Sci
1996; 51:30193025.
66. Stankiewicz A, Moulijn JA. Process intensication: transforming chemical engineer-
ing. Chem Eng Prog 2000; 96:2234.
67. Stankiewicz A. Process intensication in in-line monolithic reactor. Chem Eng Sci
2001; 56:359364.
68. Stankiewicz A, Moulijn JA. Proces intensication. Ind Eng Chem Res 2002; 41:
19201924.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
7
Inline and High-Intensity Mixers
Andrew Green
BHR Group Limited, Craneld, England
1. INTRODUCTION
High-intensity inline devices are often used to mix uids in the process industries.
Such devices include simple pipes, bafed pipes, tees, motionless mixers, dynamic
mixers, centrifugal pumps, ejectors, and rotor/stator mixers. In addition to their
traditional application in physical processes such as mixing and dispersion, such
devices can provide very effective environments for mass transfer and chemical
reaction to take place. Furthermore, combining effective inline mixing with heat
transfer is the basis of combined heat exchanger reactors (HEX reactors).
The chapter provides insight on the importance of mixing and how it relates
to process intensication using inline mixers. Design information for inline
devices such as motionless mixers, T mixers, ejectors, and HEX reactors is provided.
This should assist the reader to: (a) understand the advantages and disadvantages
of these devices as process tools for single-phase, gasliquid, and liquidliquid
applications, (b) evaluate manufacturers bids, and (c) identify opportunities for
intensifying processes, as either a retrot for existing plant or as a new process.
1.1. Why Is Mixing Important?
Consider a simple chemical reaction, where two reactants A and B come together
and produce a product R:
A B R
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The reaction will have an intrinsic kinetic rate, usually dependent on the local
concentrations of A and B. Often it will produce heat (exothermic reaction) or
require heat input (endothermic reaction). If this is not removed (or supplied) fast
enough, the temperature will rise (or fall), possibly by tens or even hundreds of
degrees. Clearly this could have disastrous consequences, particularly because
the rate of reaction will increase with temperature, potentially leading to a run-
away reaction. For the reaction to take place, A and B need to be brought together;
the reactor must be mixed. This is usually not a problem in a chemists beaker,
where mixing can be very rapid. However, if it scaled up to a batch stirred vessel,
mixing inevitably becomes slower and may take several minutes in a typical
production-scale vessel. If this mixing time is slower than the reaction time, the
reaction will be articially slowed down. It becomes mixing, rather than kinetic,
limited. In other words, process inefciency is built in. For highly exothermic
reactions, matters become even worse. As a vessel is scaled up, the ratio of heat
transfer area to volume reduces, so its ability to remove heat reduces. To cope, a
process design chemist will alter conditions to slow the reaction down. This might
involve running at lower concentrations (i.e., more solvent) or operating semi-
batchfeeding B in slowly over many minutes or hours so that the system can
cope with the heat release. If a chemical reaction that would naturally take
place in a few seconds is slowed down to take 12 hours or more, it is clearly
inefcient.
Reactions are rarely as simple as this. There will often be other reactions
competing with the desired reaction; for example,
In other words, the desired product R reacts with reactant B to form by-product S.
If the second reaction is much slower than the rst, there should not be too much
S formed. However if mixing is slow, the rst reaction can be articially slowed
down, which will then tend to favor production of Sand yield will reduce. The
ow pattern in the reactor will also inuence the production of S. For back-
mixed ow, as occurs in a stirred vessel, the product stream from the reaction
zone will be continually recirculated back into contact with the reactant stream,
exposing R to fresh B. In a plug ow reactor, reactants are brought together in
the reaction zone and then removed, reducing the likelihood of the formation of
S. To summarize, production of R will be optimized by ensuring that mixing is
faster than the desired reaction step and that the reactor operates in plug ow.
The reactor is the nucleus of the process. Getting the uid dynamics right
in the reactor means improved safety, productivity, and selectivity, which in turn
inuences upstream (reduced raw material costs) and downstream (reduced sep-
aration and waste treatment costs); see Figure 1.
A B R
R B S
d
H
4
Area open to flow
Wetted perimeter
TABLE 1 Ratios of Hydraulic Diameter to Pipe
Diameter for Motionless Mixers
Manufacturer Mixer type d
H
/d
p
(%)
Sulzer/Koch SMV 725
SMX 33
SMXL 48
Chemineer Kenics KMS 48
HEV 86
T1
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
which is the ratio of the pressure loss in one diameters length of pipe to the mean
velocity pressure:
(4)
For fully turbulent ow (generally Re
H
10,000), f
M
is roughly constant. For
laminar ow (Re
H
1000), the product f
M
Re is a constant. Between these val-
ues (transitional ow), f
M
is a function of Re.
Approximate fully turbulent friction factors for motionless mixers are given
in Table 2. (Note: These gures are approximate and for comparison purposes
only; they should not be used for design. The true friction factors vary slightly
with Re and scale.)
The other friction factors in common use are the Newton number and
Fannings friction factor. The relationship between the three is:
(5)
Moodys Newton number Fannings
2.3.2. Pressure Drop and Energy Dissipation:
Turbulent Flow
For motionless mixers, energy is extracted from mean ow. Data can be correl-
ated using an analogy with a rough pipe:
(6)
This can then be used to determine the total energy dissipation rate in the mixer
(in W/kg):
(7)
Q p
V
f u
d
m
M
3
2
Re
p
p p
u d
f f
M F
2 4 Ne
f
p d L
u
M
p m
p
2
2
( / )
I
d
7
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The term slow needs to be used with care in PI applications. With mixing
times typically well below 1 second, reactions of only a few seconds duration can
be considered slow for a motionless mixer.
3.2. Fast Reactions
For a fast reaction, the time scales for mixing and reaction are of the same order
(i.e., ), so mixing and reaction are no longer consecutive processes but
simultaneous:
For fast reactions, the mixing rate can limit the product rate of formation
and, as described in the next section, product quality/yield.
3.3. Multiple Fast Reactions
Chemical processes often involve multiple, competing reactions. A common situ-
ation is that of a competitive-consecutive reaction, such as that described in
Section 1.1, where reactant A and the desired product R are competing for react-
ant B. The selectively for waste product S can be dened as
(10)
With very fast mixing ( ), the distribution of products is deter-
mined by the relative kinetics of the two reactions: If the desired reaction is much
faster than the undesired reaction, X
s
will tend toward zero. However, slow mix-
ing compared to the fastest reaction (i.e., ) slows down the desired
reaction, leading to high waste selectivities, X
s
1. It should be noted that in this
analysis, is the maximum of the three mixing time scales (
macro
,
meso
,
micro
).
Dependent on the mixing conditions, geometry, and chemistry, any one mixing
time scale can be rate determining.
4. MIXING PERFORMANCE OF INLINE MIXERS
4.1. Macromixing (or Blending) Performance
Measurements of macromixing by, for example, a motionless mixer are based
on the coefcient of variation (CoV), which is a statistical measure of radial
homogeneity at the macroscale. It is dened as the standard deviation of con-
centration measurements made at the exit of a mixer divided by the mean
concentration:
t
m 1 2 /
t t
m 1 2 1 2 / /
>>
t t
m 1 2 1 2 / /
<<
X
c
c c
S
S
R S
2
2
t t
m r 1 2 1 2 / /
,
Component mixing and reaction products
t t
m r 1 2 1 2 / /
c c n
c c
i
i
n
2
1
1
1
]
1
1
meso
macro
, then the process is micromixing controlled. Micromixing
is a complex phenomenon (Section 2.4), but for most liquids engulfment is the
longest step. In this case, micromixing time is the inverse of engulfment rate (E)
and can be estimated by
(21)
micro
1 1
0 058
1 2
E .
/
_
,
1 3 /
meso
2 17
1 3
.
/
Q
n u
B
f
_
,
_
,
1 3 /
d k d
new old
3 7 /
l
d
d
l
new
new
old
old
_
,
_
,
0 5 .
TABLE 4 Application of Chemineer Kenics and
Koch/Sulzer SMV Mixers
Mixer type
Situation Kenics SMV
p constraint
Space constraint
Solids present
Energy efciency important
Need for heat removal
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
where t
MT
and t
R
are the time constants for mass transfer and reaction, respectively.
The lower the value of Ha, the faster the mixing relative to the intrinsic reaction
rate. Ha can be calculated from
(29)
Reactions are often classied into four categories:
Ha 0.02 slow reaction
0.02 Ha 2 moderately fast reaction
Ha 2 very fast or instantaneous reaction
For Ha 0.02, there is a considerable scope for process intensication. If a reac-
tion is intrinsically fast (a large reaction rate constant) the design aim is to
provide sufciently intense mixing to move it into the slow reaction regime
(Ha 0.02) such that the reaction is limited by the intrinsic reaction rate rather
than the mass transfer rate.
In order to establish the reaction regime and to design equipment, the fol-
lowing need to be known:
Flow pattern
Mass transfer coefcient
Bubble sizes
These can be determined from gasliquid ow rates, the energy dissipation rate
(driven by the pressure drop), and the physical properties of the uids.
5.6. Design Guidelines and Correlations
5.6.1. Flow Patterns
Gasliquid ows are much more complicated than single-phase ows, due to the
existence of the gasliquid interface. The phases can be present in a range of pos-
sible ow regimes (ow patterns), which are dependent upon the physical prop-
erties of both phases, the ow rates, and the equipment size and orientation. The
most commonly noted ow patterns are (7):
Annular owa liquid lm on the walls and a continuous gas phase, con-
taining a mist of liquid droplets, in the core
Intermediate slug owlarge gas voids containing liquid droplets
Bubble owcontinuous liquid ow with a dispersion of gas bubbles
Figure 6 shows the various ow patterns in horizontal ow, and similar pat-
terns can be seen in vertical upow or downow. In general, bubble ow develops
under high liquid-ow rates and low gas-ow rates; annular ow develops under
Ha
D
k
k C C
n
A
L
AB AL
n
BL
n
A
A B
2
1
0 5
2
1
( )
.
_
,
G
X
2
L
(33)
Ejector. Gas chamber pressure needs to be known in order to
calculate ejector power input. A semiempirical equation was developed by
Henzler (10) that related the entrainment ratio to other system variables:
(34)
Gas chamber pressure, p
s
, can be calculated from this equation through iteration.
Factor B depends on the mixing tube/nozzle diameter ratio for a given ejector
type and needs to be determined experimentally.
Q
Q
B
D
D
p
p
p p
u
G
L
m
n
L
G s
s
L j
1 0 38 1
2
0 09
2
1 6
2
2
.
( )
. /
_
,
_
,
1
]
1
1
L
X X
( . . . )
. . .
4 6 12 5 0 65
1 78 0 68 0 5
p p p
L L G G
2 2
FIGURE 8 Lockhart and Martinelli parameters for pressure drop in multi-
phase ow.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The nozzle pressure, which determines the selection of the liquid pump, is
given by
(35)
5.6.3. Power Input
The power input, required for calculation of the mass transfer coefcient, is cal-
culated from Eqs. (36) and (37). For a motionless mixer, the power comes from
the gas and liquid phases; for the ejector, power comes from the liquid only.
In a motionless mixer:
(36)
In an ejector:
(37)
Generally, k
L
a values at the same power input are similar between the two de-
vices (11).
5.6.4. Mass Transfer Coefcients
The amount of gas transferred is proportional to the product of the mass transfer
coefcient (k
L
) and the specic area (a). Because most measurement techniques
measure this product, many correlations for k
L
a appear in the literature. However,
caution is advised, because they can give different predictions for the same oper-
ating conditions. Equations (38) and (39) are two examples from independent
investigators for motionless mixers, from Refs. 12 and 8, respectively:
(38)
(39)
The majority of reported correlations for ejectors are for loop-type cong-
urations, e.g., (13):
(40)
with very little reported on the stand-alone conguration.
k a
P
V
L
0 044
0 76
.
.
_
,
k a
P
m
L G
0 64
0 75
.
.
_
,
k a
P
V
L
1 74 10
4
0 8
.
.
_
,
P Q p Q p
p
p
Q u u
L G
G
L L L
av
ln
2
1
2
2
2
1
2
_
,
( )
P Q p Q p
p
p
Q u u
L G L L L
av
ln
1
2
1
2
2
2
1
2
_
,
( )
p p u
D
D
s L j
n
1
2
1
4
1
2
1
_
,
1
]
1
1
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Comprehensive correlations for motionless mixers and ejectors have been
developed as part of BHR Groups HILINE Consortium, but these are available
only to members.
5.6.5. Bubble-Size Calculations
When a gas stream is introduced into a turbulent liquid ow in a motionless
mixer, the gas is broken up into bubbles. The breakup is due mainly due to the
turbulent shear force of the liquid but, for motionless mixers, also partly to the
collision between the gas and the leading edge of an element. Gas dispersion is a
physical process and involves bubble breakup and coalescence, which can both
take place in the same mixer/reactor.
Bubble breakup and coalescence are both complex processes. In a turbulent-
ow eld, bubbles are broken up mainly due to the turbulent shear force, and the
eventual bubble size is a balance between this force and the surface tension force.
For a given gasliquid system and ow eld, a maximum bubble size exists. Any
bubbles larger than this size will be broken up. According to theory (14), this max-
imum bubble size relates to gasliquid physical properties and ow characteristics:
(41)
We
crit
is the modied critical Weber number, which is close to 1.
Coalescence occurs when two bubbles approach each other, collide, and
become one bigger bubble. Two important factors are:
Frequency of collision
Efciency of coalescence
The frequency of collision relates to the ow pattern and gas volume fraction: The
more random the ow pattern or the higher the gas volume fraction, the higher
the frequency. The efciency of coalescence relates to physical properties of the
gasliquid system. Some systems, such as airwater, have a high efciency of
coalescence and are often called coalescing systems. Other systems, such as
gasalcohol or gassalt solution, have a low efciency of coalescence and are
called noncoalescing systems.
5.6.6. Characterization of Bubble-Size Distribution
It is useful to dene an appropriate average to characterize bubble-size distribu-
tion. For heat and mass transfer, the Sauter mean diameter (d
32
) is generally used:
(42) d
n d
n d
i i
i i
32
3
2
d
c d
max
.
.
.
.
We
2
crit
_
,
( )
0 6
0 6
2
0 2
0 4
k
d
32
d
p
/4 (46)
We
c p p
u d
2
/
a
d
6
32
d C
n
c
L G
32
0 6
0 6
2
2
0 4
2
We
_
,
( )
_
,
.
.
.
k
(v
3
/)
1/4
(47)
6.2.1. Kenics Mixer
Two very similar correlations have been developed for Kenics mixers (15,16) of
the form
(48)
where C 0.45 for the former and 0.49 for the latter. These are valid for fully tur-
bulent ow in a pipe (Re
p
12,000), inviscid drops (
d
c
) and were measured
with water as the continuous phase. The dispersed-phase fraction has little effect up
to a value of 0.25. Equilibrium drop size is achieved with only eight mixer elements.
For viscous drops (
d
up to 200 mPa) in turbulent ow, Berkman and
Calabrese (16) developed the correlation further to give
(49)
where
(50)
For higher viscosity ratios, more elements were needed (24 in these experiments).
6.2.2. Sulzer (Koch) Mixers
Sulzer published correlations in the open literature for drop size. An early correl-
ation for the SMV is (3)
(51)
where We is the Weber number based on hydraulic diameter, i.e.,
(52)
The correlation was developed for ve 50-mm SMV elements (d
H
8 mm) and
covered Reynolds numbers (Re
H
) in the range 20020,000 and dispersed-phase
volume fraction up to 0.25.
We
c
u d
p H
2
d
d
H
H
32 0 5 0 15
0 21
.
. .
We Re
Vi
d p
c
d
u
_
,
_
,
1 2 /
d
d
d
d
p p
32 32
1 3
0 6
0 49 1 1 38
. .
/
.
We Vi
0.6
_
,
_
,
d
d
C
p
32
We
0.6
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
More recent work (17) has covered viscous drops in turbulent ow, over
a wide range of mixer types (SMV, SMX, SMXL, SMR, SMF), diameters (up to
80 mm), lengths, and dispersed-phase viscosities (up to 70 mPa):
(53)
where We
c
1.8 and Vi is the viscosity number [Eq. (50)].
6.3. Comparison Between Motionless Mixers
and Stirred Tanks
Comparison between drop sizes for a motionless mixer and a (well-) stirred tank
under typical operating conditions yields an interesting result that similar drop
sizes can be obtained in both despite very different average energy dissipation
rates. This is down to the extremely inhomogeneous energy dissipation in a stirred
tank, where the peak rate (usually close to the impeller tip) can be similar in mag-
nitude to that in the more homogeneous motionless mixer. However, a stirred tank
may take hours of operation to achieve an equilibrium drop size, whereas a motion-
less mixer will achieve it with a few elements and in less than a second. This has
implications for two-phase applications when it is important to rapidly achieve
mass transfer to complete fast chemical/physical reactions or to minimize by-
product formation from complex fast reactions.
6.4. Scale-Up/Scale-Down
When scaling up or scaling down a liquidliquid process in turbulent ow, the
energy dissipation rate needs to be kept constant, giving
(54)
However, checks should be made that ow is fully turbulent at both scales and
that the drop size remains within the inertial subrange of turbulence [Eq. (46)].
As a minimum, residence time should be maintained, i.e.,
(55)
This suggests that fewer elements will be required at a larger scale; however, for
a conservative design on scale-up, the same number of elements should be main-
tained. On scaling up or scaling down, the same mixer type and feed arrangement
should be maintained.
l
d
d
l
new
new
old
old
_
,
1 3 /
d Q Q d
new new old old
( / )
/ 3 7
d k
B
d
c
c
c
d
32
0 6
0 6 0 1
0 4
0 65 1
1
2
. ( )
( )
.
. .
.
Vi We
_
,
_
,
_
,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
7. COMBINED HEAT EXCHANGER-REACTORS (HEX REACTORS)
7.1. HEX Reactor: Concepts
The mixers discussed in Sections 46 are particularly suitable for reactions where
the required heat input (endothermic reaction) or heat production (exothermic
reaction) is modest (i.e., temperature changes on reaction would be only a few
degrees in the absence of any heat transfer). HEX reactors can be used for rapid,
highly exothermic (or endothermic) reactions; not only are the mixing rate and
residence time of a reactor matched to the kinetic rate and reaction time, but heat
transfer performance is also matched to heat production (Figure 9).
7.2. HEX Reactor Types
HEX reactors generally fall into three basic types (18).
a. Jacketed motionless-mixer reactors (Figure 10): Motionless mixers
provide a highly effective and efcient mixing environment for rapid
reactions. Heat transfer capacity can be provided by utilizing either
single mixers in jackets or multiple mixers in a shell-and-tube geometry.
The FlexReactor (Figure 4) has been designed to package motionless
mixers in a highly recongurable unit with effective heat transfer.
b. Compact heat exchangers: There is a wide variety of commercially
available compact heat exchangers available (e.g., enhanced shell and
tube, plate and frame, platen, and diffusion-bonded). Such devices
provide extremely effective heat transfer but have not been optimized
as reactors, compromising their efciency.
FIGURE 9 HEX reactors: principle of operation.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
TABLE 5 HEX Reactor Considerations
Attribute Bespoke HEX Motionless mixer FlexReactor
Typical heat U 1500 W/m
2
-K U 800 W/m
2
-K U 600 W/m
2
-K
transfer
coefcient
HT density 5000 m
2
/m
3
900 m
2
/m
3
900 m
2
/m
3
Material of Limited Wide Wide
construction
Scale-up Use more units Increase tube Increase tube
procedures in parallel length/ length/
diameter diameter
Cost High Low Medium
Mixing Low High High
Multipoint feed Yesbut xed Yesbut Yesvariable
once xed once
constructed constructed
Availability Low High Medium
Residence time Low High High and
variable
Flexibility Low Low High
FIGURE 10 Jacketed motionless mixer.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
c. Bespoke HEX reactors: A good example is the Marbond
TM
reactor,
supplied by Chart Industries, which has been designed specically as a
heat exchanger-reactor, combining high heat transfer with effective
mixing (although its high surface area results in relatively low
micromixing efciencies). Passageways are typically of the order of a
few millimeters. Its diffusion-bonded construction is very robust, and it
can be constructed to provide an optimized feed arrangement.
The choice of reactor will be very dependent on the requirements of the
chemical reaction scheme, the relative importance of mixing and heat transfer, and
practical considerations (e.g., the effect of solids in the process; materials of con-
struction; exibility). A comparison of the typical performance of different designs
is given in Table 5. HEX Reactors are discussed in more depth in Chapter 4.
NOMENCLATURE
Symbol Explanation Units
a Interfacial area m
1
c
i
Concentration of species i mol-m
3
c Mean concentration mol-m
3
CoV Coefcient of variation
Cn Constant 0.6
C*
AL
Equilibrium concentration of A mol-m
3
C
BL
Bulk liquid concentration of B mol-m
3
D Stirred-tank impeller or rotor diameter m
D
AL
Diffusion coefcient of A in liquid m
2
-s
1
D
m
Molecular diffusivity m
2
-s
1
D
ta
, Dax Axial turbulent dispersion coefcient m
2
-s
1
D
tr
Radial turbulent dispersion coefcient m
2
-s
1
d Droplet diameter m
d
B
Feed pipe diameter m
d
H
Hydraulic diameter of motionless mixer m
d
max
Maximum stable drop size m
d
n
nozzle diameter m
d
p
Internal pipe diameter m
d
32
Sauter mean diameter m
E Engulfment rate coefcient s
1
E
B
Ratio of viscous to interfacial forces
E
p
Rate of direct energy dissipation W-kg
1
f
M
Moodys friction factor
g Acceleration due to gravity ms
2
K
L
Overall mass transfer coefcient ms
1
k Second-order reaction rate constant m
3
-mol
1
-s
1
k
L
Liquid-side mass transfer coefcient ms
1
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
L
c
Concentration integral length scale m
L
e
Length of one mixer element m
L
m
Length of motionless mixer m
L
R
Length of reaction zone m
m mass kg
N Impeller rotational speed rps
N
A
Mass transfer rate mol/s
N
i
Total number of moles of species i mol
n Number of sampling positions used in
CoV measurement
n
e
Number of motionless mixer elements
n
f
Number of additive feed tubes
P Power W
P
1
Inlet pressure Pa
P
2
Exit pressure Pa
P
s
Gas chamber or suction pressure Pa
p Pressure drop over motionless mixer Pa
Q Volumetric ow rate m
3
-s
1
T Dimensionless time
Stirred-tank diameter m
t Time s
u
p
Supercial pipe velocity m-s
1
v Velocity m s
1
V Liquid volume m
3
X Lockhart and Martinelli parameter
X
i
Selectivity for product i
z Ratio of mixer friction factor to pipe
friction factor
Greek Symbols
Flow rate ratio (Q
A,C
/Q
B
)
Shear rate s
1
Turbulent energy dissipation rate W-kg
1
Efciency of turbulence generation
Voidage of a motionless mixer
Turbulence-generating length scale m
k
Kolmogorov microscale m
Dynamic viscosity mPa-s
Kinematic viscosity m
2
-s
1
Fluid density kg-m
3
Standard deviation
Interfacial tension N-m
1
Characteristic time scale s
Total energy dissipation rate W-kg
1
Dispersed phase volume fraction
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Dimensionless Groups
Da Damkohler number (k
2-o
c
B0
/E)
Re Reynolds number (u
p
d
p
/v)
Sc Schmidt number (v/D
m
)
We Motionless-mixer Weber number (
c
u
p
2
d
p
/)
Stirred-tank Weber number (
c
N
2
D
3
/)
We
crit
Critical Weber number (0.61.6)
Ha Hatta number
Subscripts
1 At inlet
2 At exit
av Average
c Continuous phase
d Dispersed phase
E Engulfment
G Gas
H Based on hydraulic diameter
j Jet
L Liquid
MT Mass transfer
m Motionless mixer
macro Macromixing
meso Mesomixing
micro Micromixing
mix Slowest mixing step
p Empty pipe
Q Competitive-parallel reactions
R Radial
R Reaction
T Tangential
1/2r Reaction half-life
REFERENCES
1. Henzler HJ, Chem Ing Tech, 1980; 52:659661.
2. Hesketh RP, Russel T, Etchells AW. R&D notes. AIChE J 1987; 33(4):663667.
3. Streiff FA. Sulzer Tech Rev 1977; 3.
4. Knight CS. Experimental investigation of the effects of a recycle loop/static mixer/
agitated vessel system on fast, competitive-parallel reactions. PhD dissertation, Univer-
sity of Arkansas, 1994.
5. Baldyga J, Bourne JR. Principles of micromixing. J Fluid Mechanics 1986; 1:147.
6. Middleton JC. In: Harnby N, Edwards MF, Nienow AW, eds. Mixing in the Process
Industries. 2d ed. London: Butterworth Heineman, 1992:Chapter 15.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
7. Drahos J, Cermak. Chem Eng Processes 1989; 26:147.
8. Roes AWM, Zeeman AJ, Bukkems FHJ. I Chem E Symposium Series, 1984; (87):
231238.
9. Lockhart RW, Martinelli RC. Chem Eng Prog 1949; 45:39.
10. Henzler HJ. Chem Eng Tech 1980; 52:659661.
11. Zhu M. Proc. 1st International Conference on Process Intensication, Antwerp,
Belgium, December 68, 1995, organized by BHR Group, Craneld, UK, 5159.
12. Middleton JC. AIChE 71st Annual Meeting, Miami Beach, Paper 74E, 1978.
13. Dutta NN, Raghavan KV. Chem Eng J 1987; 36:111121.
14. Hinze JO. AIChE J 1955; 1:289295.
15. Middleman S. Ind Eng Proc Des Dev 1974; 13:78.
16. Berkmann PD, Calabrese RV. AIChE J 1988; 34(4).
17. Streiff FA, Mathys P, Fischer TU. New fundamentals for liquidliquid dispersion
using static mixers. Rcents Progrs en Gnie des Procds 1997; 11(51):307314.
18. Green A, Johnson B, Westall S, Bunegar M, Symonds K. Combined chemical reactor/
heat exchangers: validation and application in industrial processes. 4th International
Conference in Process Intensication, Brugge, Belgium, September 2001.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
8
Reactive and Hybrid Separations:
Incentives, Applications, Barriers
Andrzej Stankiewicz
DSM Research, Geleen, The Netherlands
1. INTRODUCTION
Integration of various steps/operations presents one of the most promising ways
for intensifying (bio)chemical processes. It can be achieved either by combining
reaction and separation in a single reactive separation step or by combining two
(or more) separation techniques in a hybrid separation unit. Such an integration
may bring a number of advantages to the process under consideration, not just a
decrease in the size of equipment.
This chapter provides a general overview of the reactive and hybrid sep-
arations and discusses their place in the intensication of (bio)chemical processes.
Written from an industrial point of view, it focuses on the application aspects of
those integrative technologies. Potential application elds are reported, along
with already existing commercial-scale operations. Special attention is given to
the barriers that hamper a broader introduction of the reactive and hybrid separ-
ations into industrial practice and the ways to overcome those barriers. The mod-
eling and design aspects of three reactive separation methods (reactive
distillation, reactive absorption, and reactive extraction) are discussed in more
detail in Chapter 9.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2. REACTIVE SEPARATIONSWHY INTEGRATE?
In the simplest case, integration of reaction and separation may take place on the
purely equipment level, without introducing any new functional interrelations
between the operations involvedthe reaction does not inuence the separation,
nor has the separation process any effect upon the reaction. The aimed result of
such combination can be:
Lower investment costs (compact plant layout, integral design)
Smaller inventory (safety aspects)
Improved heat management/energy utilization.
The Urea 2000plus technology, developed by Stamicarbon B.V. (1) and
described further in Chapter 12, presents a typical example of such a noninter-
relating integration. The integration resulted here in a considerably smaller and
cheaper plant, with much less high-pressure equipment/piping needed and less
energy consumption. Yet the interrelations between the reaction and other oper-
ations remained basically the same as in the conventional technology.
In most cases, however, the reaction and separation are integrated in order
to benet from the interaction effect between those two, for instance,
To improve yield/selectivity (e.g., via equilibrium shift)
To facilitate separation (e.g., azeotrope problems)
For other reasons, e.g., to extend the catalyst lifetime
One speaks in those cases about reactive separations or separative reactors.
The industrially important reactive separations include:
Reactive distillation
Membrane-based reactive separations
Reactive adsorption
Reactive absorption
Reactive extraction
Reactive crystallization
2.1. Reactive Distillation
In most industrial applications the reactive distillation is used to improve the
yield/selectivity of the required product. Figure 1 shows three examples of indus-
trial processes, in which combination of reaction and distillation shifts the equil-
ibrium of the reaction A B C D in the required direction (2). The length
of the reacting, distillation, and stripping zones as well as the positioning of the
reactant inlets vary in each particular case, depending on the process requirements.
On the other hand, in selective hydrogenations of dienes and aromatics (3), reactive
distillation is used to remove the single-hydrogenated product from the reaction
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
zone, thus preventing its further hydrogenation and increasing its yield. In the
methyl acetate technology of Eastman Chemical, integration of reactive distillation
with extractive distillation in a single unit totally solved the azeotrope problem (4).
Reactive distillation can also be used as a powerful separation method in case
of mixtures containing reactive and inert components with close boiling points.
The method is schematically depicted in Figure 2. Here, a reactive entrainer is
introduced to the rst reactive distillation column, to form an intermediate prod-
uct having a boiling point much more distant from the boiling point of the inert
components. In the rst column, inert components are therefore easily separated,
while the intermediate product is fed to the second reactive distillation step,
where the reversed reaction takes place and the original reactive component is
recovered and separated from the entrainer. Stein et al. (5) investigated the appli-
cation of this principle to the separation of close-boiling i-butene and n-butene,
using methanol as a reactive entrainer.
Obviously, reactive distillation may lead to signicant savings on energy.
Hydrolysis of methyl acetate presents an industrial example of such energy savings.
FIGURE 1 Examples of industrial processes employing reactive distillation:
(a) methyl tert-butyl ether (MTBE) from isobutene and methanol; (b) cumene
via alkylation of benzene with propylene; (c) ethylene glycol via hydration of
ethylene oxide.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The heat requirements of the reactive distillation-based process are ca. 50% lower
than in the conventional technology. In the alkylation of benzene to cumene reac-
tive distillation effectively eliminated the hot spots and reduced the oligomeriza-
tion of propylene (6).
Table 1 gives an overview of the possible applications of reactive distillation
reported in the literature. Very few of them have been realized so far on the com-
mercial scale. One of the common factors that hinders a broader application of
reactive distillation is a small feasible operation window. The overlap region in the
pressuretemperature domain, in which chemical reaction and separation and appa-
ratus design are feasible, is usually quite narrow (see Figure 2 in Chapter 9). A
possible remedy for this limitation is sought in the development of new types of
catalysts that would allow one to signicantly broaden the feasible operation win-
dow for chemical reaction.
2.2. Membrane-Based Reactive Separations
Sirkar et al. (64) give an interesting overview of various functions that a mem-
brane may play in a chemical reactor. Those functions are schematically shown
in Figure 3 and summarized in Table 2.
FIGURE 2 Separation of reactive and inert components with close boiling
points, facilitated by reactive distillation. (From Ref. 5.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
TABLE 1 Reported Existing and Potential Applications of Reactive
Distillation
Product/process Selected refs.
Butyl acrylate from butanol and acrylic acid 7
n-Butyl acetate from n-butanol and acetic acid 8
Ethyl acetate from ethanol and acetic acid 9,10
Methyl acetate from methanol and acetic acid 11,12
Hydrolysis of methyl acetate 13
2-Methylpropylacetate from 2-methylpropanol 14
and acetic acid
Amyl acetate from amyl alcohol and acetic acid 15
Ethyl pentenoate from ethanol and pentenoic acid 16
Esterication of fatty acids 17
Methylal from formaldehyde and methanol 18,19
TAME (tertiary amyl ether) 2022
MTBE (methyl tert-butyl ether) 23,24
ETBE (ethyl tert-butyl ether) from ethanol and 25,26
isobutene
ETBE (ethyl tert-butyl ether) from bioethanol and 27
tert-butylalcohol
Diisopropyl ether from propene 28
TAA (tert-amyl alcohol) via hydration of isoamylene 29
Isopropanol via hydration of propene 30
Cyclohexanol via hydration of cyclohexene 31,32
Phenol from cumene 33
Ethylene glycol via hydration of ethylene oxide 34,35
Isobutene via dehydration of tert-butanol 3638
Isoamylenes via dehydration of 2-methyl-1-butanol 39
Isophorone from acetone 40
MIBK (Methyl iso-butyl ketone) from acetone 41,42
Diacetone alcohol (DAA) and mesityl oxide (MO) via 43,44
aldol condensation of acetone
Acetone via dehydrogenation of propanol 45
Tetrahydrofuran from butanediol 46
Xylenes via toluene disproportionation 47
Hydrogenation of unsaturated hydrocarbons 48,49
Isomerization of C5-C6 parafns 50
Isobutene via hydroisomerization of C4 alkenes 51
Cumene via alkylation of benzene with propylene 52
Ethylbenzene via alkylation of benzene with ethylene 53,54
Cyclopentane and/or cyclopentene from 55
dicyclopentadiene
Purication of hydrouorocarbons 56
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Among all the membrane functions listed in Table 2, catalytic membranes
probably attract the most attention. The scientic literature on catalytic membrane
reactors is exceptionally rich and includes many interesting ideas, such as heat- and
mass-integrated combination of hydrogenation and dehydrogenation processes in
a single membrane unit. Yet practically no large-scale industrial applications of
catalytic membrane reactors have been reported so far, perhaps with the excep-
tion of the Russian vitamin K technology (65). The primary reason for this is the
relatively high price of membrane units, although other factors, such as low per-
meability, sealing problems, as well as mechanical and thermal fragileness of the
membranes, also play an important role. Further developments in the eld of
material engineering will surely change this picture.
Possible application areas of catalytic membrane reactors include:
Dehydrogenations, e.g., ethane to ethene, ethylbenzene to styrene, methanol
to formaldehyde
Methane steam reforming
Watergas shift reaction
Selective oxidations, e.g., propane to acroleine, butane to maleic anhydride,
ethylene to ethylene oxide
Oxidative dehydrogenations of hydrocarbons
Oxidative coupling of methane
Methane oxidation to syngas
An excellent review of all potential applications of catalytic membrane reactors
studied so far can be found in the 2002 book by Sanchez Marcano and Tsotsis (66).
On the other hand, membranes are frequently employed in combination with
a bioreactor, for instance, in enzymatic pharmaceutical processes. An example
Naphtha desulfurization 57
Dihydroxy polyether polyol via alkanolysis of 58
corresponding diesters
Glycine from glycinonitryle 59
DEC (diethylcarbonate) via carbonylation of ethanol 60
with dimethylcarbonate
Polyamides (e.g., Nylon 6) via hydrolytic 61
polymerization of amino nitriles
Nylon 66 via polycondensation 62
Propylene oxide from propylene chlorohydrin 63
and calcium hydroxide
TABLE 1 (cont.)
Product/process Selected refs.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 3 Membrane functions in chemical reactor. (Reproduced with per-
mission from Sirkar et al. (64), copyright (1999) American Chemical Society.)
of such an application of an ultraltration membrane-reactor system for the pro-
duction of s-ibuprofen is discussed further in Chapter 12.
2.3. Reactive Adsorption
The vast majority of possible applications of reactive adsorption aim at the improve-
ment of the product yield by shifting the equilibrium in the required direction. In
contrast to the nonreactive adsorption techniques, such as simulated moving beds
and pressure-swing adsorption, and despite its great potential [for example, a
12-fold higher conversion per pass in oxidative methane coupling (67)], the
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
TABLE 2 Membrane Functions in Chemical Reactor Systems
Function Examples
Separation of products from In situ product removal from enzymatic
the reaction mixture reactor via a nanoltration or
ultraltration membrane
Removal of selected enantiomer via
a liquid membrane
Removal of water in esterication
reactions via a pervaporation
membrane
Hydrogen removal in catalytic
dehydrogenation reactions
Separation of a reactant from Separation of oxygen from air for
a mixed stream for intro- oxidizing methane to syngas
duction into the reactor Separation of hydrogen from
dehydrogenation reaction to oxidize
it with oxygen on permeate side
Separation of organic priority
pollutants from wastewater for
biological purication
Controlled addition of one Controlled oxygen addition in partial
reactant or two reactants oxidation reactions (to increase
selectivity)
Controlled air introduction in oxidative
dehydrogenations
Nondispersive phase contacting, Emulsion-free enzymatic splitting of
with reaction at the phase fats
interface or in the bulk phases Bubble-free oxygen/ozone supply in
wastewater treatment via hollow-
ber membranes
Segregation of a catalyst Segregation of enzymes with respect
(and cofactor) in a reactor to molecular weight on ultraltration
membranes
Immobilization of a catalyst Immobilization of enzymes or cells on
in (or on) a membrane polymeric membranes
Immobilization of metals (Pd, Pt) on
ceramic membranes
Membrane is the catalyst Cation exchange membranes for
esterication reactions
Palladium membranes for
hydrogenation/dehydrogenation
reactions
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Membrane is the reactor Reactions in ow-through membrane
systems (pore ow-through
reactors)
Solid electrolyte membrane Solid electrolyte membranes such as
supports the electrodes, H
and O
2
conductors in fuel cells
conducts ions, and achieves
the reactions on its surface
Transfer of heat Membranes coupling endo- and
exothermic reaction zones (e.g.,
hydrogenationdehydrogenation)
Immobilizing the liquid Supported liquid membranes (SLM) for
reaction medium homogeneous catalytic processes
Source: Ref. 64.
TABLE 2 (cont.)
Function Examples
industrial-scale applications of adsorptive reactors remain to be seen. Challenges
involve materials development of catalysts/adsorbents and matching of process
conditions (same temperature) for both reaction and adsorption so that high yields/
selectivities can be achieved. Reactive adsorption processes investigated in the
bench or pilot scale are numerous, as shown in Table 3.
One of the more promising types of adsorptive reactors is the so-called gas
solidsolid trickle-ow reactor (GSSTFR), in which ne adsorbent trickles through
the xed bed of catalyst (Figure 4), removing selectively in situ one or more of
the products from the reaction zone. In the case of methanol synthesis this led to
conversions signicantly exceeding the equilibrium conversions under the given
conditions (98). The economics of the methanol process based on the gassolid
solid trickle-ow reactor was evaluated and compared with the conventional low-
pressure Lurgi process (99). For the production scale of 1000 tons per day, the new
technology offered considerable reductions in cooling water consumption (50%),
recirculation energy (70%), raw materials (12%), and catalyst amount (70%).
Further improvement of the GSSTFR concept could be seen in applying a mov-
ing bed of adsorbent through straight, parallel channels of a monolithic catalyst,
similar to the one shown in Figure 23 of Chapter 6.
2.4. Reactive Extraction
Similar to reactive adsorption, the reactive extraction can be applied primarily in
multireaction systems, for improvement in yields and selectivities to desired prod-
ucts. The combination of reaction with liquidliquid extraction can also be used
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
TABLE 3 Processes Investigated in Reactive Adsorption Systems
Process Selected refs. Reactor type
Esterication of glycerin with acetic acid 68 Simulated moving bed chromatographic reactor
(SMBCR)
Methyl tert-butyl ether (MTBE) synthesis 69,70 SMBCR
Hydrolysis of methyl formate 71 Discontinuous chromatographic reactor
Oxidative coupling of methane 67,72 SMBCR
Enzymatic production of L-amino acids 73 Centrifugal partition chromatographic reactor
Oxidation of phenols 74 Chromatographic reactor
Ethyl acetate from ethanol and acetic acid 75 Chromatographic reactor
Enzymatic inversion of sucrose 76 SMBCR
77 Rotating cylindrical annulus chromatographic
reactor (RCACR)
Dehydroisomerization of n-butane 78 Chromatographic pulse reactor
to isobutene
Mesitylene hydrogenation 72 SMBCR
Hydrogenation of 1,3,5-trimethylbenzene 79,80 SMBCR
Biosynthesis of dextran polymer 81 Chromatographic pulse reactor
from sucrose
Dissociation of dicyclopentadiene 82,83 SMBCR
Dehydrogenation of cyclohexane 84 Chromatographic pulse reactor
85 RCACR
Ascorbic acid synthesis 86 SMBCR
Regioselective enzymatic 87 SMBCR
diol esterication
88 Batch and xed-bed adsorptive
reactors
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Oxidation of lean VOC mixtures 89 SMBCR
Hydrolysis of methyl formate 90 RCACR
Enzymatic production of lactosucrose 91 SMBCR
from sucrose and lactose
Diethylacetal from ethanol and 92 Fixed-bed adsorptive reactor
acetaldehyde
Steam methane reforming 93 Pressure-swing adsorptive reactor (PSAR)
Propene metathesis to ethene 94 PSAR
and 2-butene
1-Butene dehydrogenation to 95 Rapid PSAR
1,3-butadiene
Sulfur from H
2
S (Claus process) 96 Reverse-ow adsorptive reactor
HCN from carbon monoxide 96 Reverse-ow adsorptive reactor
and ammonia
6-Aminopenicillanic acid from 97 Trickle-ow uidized-bed reactor
penicillin G
Methanol synthesis 98,99 Gassolidsolid trickle-ow reactor (GSSTFR)
TABLE 3 (cont.)
Process Selected refs. Reactor type
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 4 Gassolidsolid trickle-ow reactor. (From Ref. 98.)
for the separation of waste by-products that are hard to separate using conven-
tional techniques (100,101). An overview of processes studied in reactive extrac-
tion systems is shown in Table 4.
In 2002, an interesting concept was proposed for coupling a CO
2
-based
supercritical extraction with air oxidation in order to remove and decompose pol-
lutants from gases or liquids (134). An exemplary process scheme according to
this preliminary concept is shown in Figure 5. Possible (future) environmental
applications of such an integrated supercritical extraction-reaction system include
treatment of liquid efuents, regeneration of catalysts and adsorption materials,
and soil decontamination.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
2.5. Reactive Crystallization/Precipitation
Reactive crystallization/precipitation plays a role in a number of industrially
relevant processes, such as liquid-phase oxidation of para-xylene to produce
technical-grade terephthalic acid, the acidic hydrolysis of sodium salicylate to
salicylic acid, and the absorption of ammonia in aqueous sulfuric acid to form
ammonium sulfate (135). Reactive crystallization/precipitation is also widely
applied in the pharmaceutical industry, to facilitate the resolution of the enan-
tiomers (diastereomeric crystallization). Here, the racemate is reacted with a spe-
cic optically active material (resolving agent) to produce two diastereomeric
derivatives (usually salts) that are easily separated by crystallization:
( ) ( ) ( ) ( ) ( ) ( )
DL L D L L L - - - - -
racemate resolving agent -salt -salt
-A A A
n p
TABLE 4 Some Processes Studied in Reactive Extraction Systems
Product/process Selected refs.
Penicillin G recovery 102106
Downstream separation of 1,3-propanediol 107
Separation of lactic acid 108111
Separation of organic acids from the products of 112
partial oxidation of parafns
Separation of salicylic acid 113,114
Separation of D,L-phenylalanine 113,115
Separation of citric acid 116
Separation of aspartic acid 117
Cephalosporin C recovery 118
Separation of metals (e.g., zinc) 119121
Phenolic wastewater treatment 122
Separation of dicarboxylic acids (e.g., oxalic, malonic, 123
succinic, adipic acid)
Recovery of gallium from coal y ash 124
Recovery of palladium, platinum, rodium from 125
leaching solutions
Fractionation of amino acids 126
Recovery of 7-ACA (7-aminocephalosporanic acid) 127
Recovery of erythromycin 128
Removal of toxic heavy metals from wastewater streams 129,130
Production of dioxolane from aldehyde 131
Recovery of aldehydes and ketones from hydrocarbon 132
mixtures
Production of cyclic ester oligomers from linear polyesters 133
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Diastereomeric crystallization is commonly used in the production of a number
of pharmaceuticals, such as ampicillin, ethambutol, chloramphenicol, diltiazem,
fosfomycin, and naproxen (136).
Somewhat similar are the so-called adductive crystallization processes,
often (wrongly) called extractive crystallization, where reactions of complex/
adduct formation are used to separate compounds that are otherwise difcult to
separate. Examples of adductive crystallization include separation of p- and m-
cresols (137), separation of o- and p-nitrochlorobenzenes (138), separation of
quinaldine and isoquinoline (139), separation of nonaromatic compounds from
naphtha-cracking rafnate (140), and separation of p-cresol from 2,6-xylenol
(141). Other examples of reactive crystallization/precipitation reported in the lit-
erature are listed in Table 5.
Reactive crystallization/precipitation can also be conducted in high-gravity
(Higee) elds using rotating equipment. In China this technique has been used
successfully for the production of nano-size particles of CaCO
3
. Ultrane particles
FIGURE 5 Countercurrent supercritical extraction coupled with air oxidation
to remove and decompose pollutants from gases and liquids. (From Ref.
134.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
with the mean size of 1540 nm and a very narrow size distribution were pro-
duced by carbonation of a lime suspension in a rotating packed-bed reactor (RPBR)
(158). The reaction times in RPBR were 4- to 10-fold shorter than the correspon-
ding reaction times in a conventional stirred-tank unit. A similar technique was
used for the production of nanobrils of aluminum hydroxide with a diameter of
110 nm and 50300 nm long as well as nanoparticles of SrCO
3
with a mean size
of 40 nm (159).
2.6. Reactive Absorption/Stripping
Reactive absorption is very old as a processing technique and has been used for
production purposes in a number of classical bulk-chemical technologies, such as
nitric or sulfuric acid. The Raschig process for the production of hydroxylamine,
an important intermediate in classical caprolactam technologies (Stamicarbon,
Inventa), is also an example of a multistep reactive absorption process. Here,
water, ammonia, and carbon dioxide react together in an absorption column to
give a solution of ammonium carbonate, which subsequently forms an alkaline
TABLE 5 Examples of Reactive Crystallization/Precipitation
Selected
Product refs. Remarks
Calcium carbonate 142,143 Liquidliquid and gasliquid
reaction systems
Methyl -methoximino 144
acetoacetate
Magnesium hydroxide 145,146
Calcium phosphate 147,148
Magnesium ammonium 149 Removal of ammonium and
phosphate phosphate ions from
wastewater
Lead sulfate 150
Magnesium carbonate 151
Nickel hydroxide 152
ZiprasidoneHClH
2
O 153 Conducted in impinging
uid jet stream system
Barium carbonate 154 To remove CO
2
from waste
gas
Boric acid 155 Reaction of borax solution
with solid oxalic acid
Procaine benzylpenicillin 156
Sulfamic acid 157 From urea and fuming H
2
SO
4
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
solution of ammonium nitrite by reactive absorption of nitrous oxide at low tem-
perature. In a further step, the ammonium nitrite is converted to hydroxylamine
disulfonate with sulfur dioxide. The hydroxylamine disulfonate solution is drawn
off and the salt is hydrolyzed and neutralized to give hydroxylamine sulfate and
ammonium sulfate as coproduct.
Carbon dioxide removal by reactive absorption in amine solutions is also
applied on the commercial scale, for instance, in the treatment of ue gas (see
later in this chapter). Another possible application eld of the technique is gas
desulfurization, in which H
2
S is removed and converted to sulfur by means of
reactive absorption. Aqueous solutions of ferric chelates (160162) as well as
tetramethylene sulfone, pyridine, quinoline, and polyglycol ether solutions of
SO
2
(163,164) have been proposed as solvents. Reactive absorption can also be
used for NO
x
reduction and removal from ue or exhaust gases (165,166). The
separation of light olens and parafns by means of a reversible chemical com-
plexation of olens with Ag(I) or Cu(I) compounds in aqueous and nonaqueous
solutions is another very interesting example of reactive absorption, one that
could possibly replace the conventional cryogenic distillation technology (167).
3. HYBRID SEPARATIONS
Generally speaking, hybrid separations can be described as processing methods that
integrate two or more different separation techniques in a single operation, making
use of the synergy between them. The industrially most important (or promising)
hybrid separations include:
Extractive distillation
Adsorptive distillation
Membrane distillation
Membrane absorption/stripping
Adsorptive membranes (membrane chromatography)
Membrane extraction
3.1. Extractive Distillation
Extractive distillation is probably the oldest and most widely applied type of
hybrid separation, particularly useful in close-boiling-point problems or in sys-
tems in which components form azeotropes. In the method, an extra component
(solvent) is added to the system, which does not form azeotropes with feed com-
ponents. The solvent alters the relative volatility of original feed components,
allowing one to distill overhead. The solvent leaves the column with the bottom
products and is separated in a binary column. Energy savings represent the most
important advantage of extractive distillation over the conventional (nonhybrid)
separation methods (168,169).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Originally, extractive distillation was limited to two-component problems.
However, recent developments in solvent technology enabled applications of
this hybrid separation in multicomponent systems as well. An example of such
application is the BTX process of the GTC Technology Corp., shown in Figure 6,
in which extractive distillation replaced the conventional liquidliquid extraction
to separate aromatics from catalytic reformate or pyrolysis gasoline. This led to a
ca. 25% lower capital cost and a ca. 15% decrease in energy consumption (170).
Some other examples of existing and potential applications of the extractive dis-
tillations are listed in Table 6.
Solvents used for extractive distillation vary considerably, but in almost all
cases solvent selection presents a trade-off between its selectivity and solvency
(194). The effectivity of the solvent can sometimes be improved by the addition
of a salt (195).
3.2. Adsorptive Distillation
Although considered by some authors a novel process, adsorptive distillation is
a relatively old hybrid separation, originating in the early 1950s (196). It is a
FIGURE 6 Scheme of aromatics separation via extractive distillation in the
BTX process of the GTC Technology Corp.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
three-phase mass transfer operation in which distillation is carried in presence of
a solid selective adsorbent. The adsorbent usually consists of a ne powder (parti-
cle size in the 10-m range), uidized and circulated by an inert carrier. The
process is typically carried in two columns: an adsorptive distillation column for
increasing separation ability, and a distillative desorption column for enhancing
TABLE 6 Reported (Potential) Applications of Extractive Distillation
Selected
Separation process refs. Remarks
High-purity cyclohexane 171 Close-boiling-point problem
from petroleum
Benzene and toluene 172,173 Close-boiling-point problem
from nonaromatics
Isopropyl ether from acetone 174 Azeotrope problem
Methyl acetate from 175 Azeotrope problem
methanol
Anhydrous ethanol from 176 Azeotrope problem
fermentation broth
Ethyl acetate from 177 Azeotrope problem
ethanol/water
Ternary acetatealcoholwater 178 Azeotrope problem
systems (propyl, butyl,
amyl, hexyl)
m-Xylene from o-xylene 179 Close-boiling-point problem
MTBE from impurities 180 Close-boiling-point problem
Binary mixtures of 181 Close-boiling-point problem
lower-boiling alcohols
Binary mixtures of 182,183 Close-boiling-point problem
phenolic compounds
(chlorophenol, phenol,
cresol, xylenol)
Acetone from water 184 Azeotrope problem
Ethanol dehydration 185 Azeotrope problem
C
2
alcohols from water 186 Azeotrope problem
Cyclohexane-cyclohexene- 187 Close-boiling-point problem
benzene
MTBE from ethanol 188 Azeotrope problem
Methylcyclohexane from 189 Close-boiling-point problem
toluene
Anhydrous ethanol recovery 190 Azeotrope problem
from wastewater streams
Propylene from propane 191 Close-boiling-point problem
1-Butene from 1,3-butadiene 192,193 Close-boiling-point problem
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the regeneration of the adsorbent. As in the case of extractive distillation, adsorp-
tive distillation also can be used for the separation of mixtures containing close-
boiling components or to bypass the azeotrope. Another interesting potential
application eld is the removal of trace impurities in the production of ne chem-
icals. The simplest scheme of an adsorptive distillation system for separating a
binary mixture of azeotrope-forming components is shown in Figure 7. Here,
adsorbent S carried by an inert uid carrier enters the adsorptive distillation col-
umn, selectively adsorbs component B from the feed, and ows to the desorption
(stripping) column, in which separation and enrichment of B takes place. Figure 8
shows another variant of adsorptive distillation, as proposed in a patent by Shell
(197), for improved separation of closely-boiling hydrocarbon mixtures. Here an
extra stripping medium (e.g., pentane) is used to remove the adsorbate in the
stripping column.
Despite an almost 50-year history, no large-scale commercial processes
using adsorptive distillation have been reported so far. Some potential application
elds for this hybrid separation are listed in Table 7.
FIGURE 7 Scheme of an adsorptive distillation system for the separation of
azeotrope-forming components A and B (Sadsorbent).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
3.3. Membrane Distillation
Membrane distillation is considered a promising separation method applicable pri-
marily in environmental technologies. In membrane distillation a microporous and
hydrophobic membrane separates aqueous solutions at different temperatures and
compositions, as shown in Figure 9. The temperature difference existing across the
membrane results in a vapor pressure difference. The molecules are transported
through the pores of the membrane from the high-vapor-pressure side to the low-
vapor-pressure side. At least one side of the membrane remains in contact with the
liquid phase. Benets offered by membrane distillation include (202):
100% (theoretical) rejection of ions, macromolecules, colloids, cells, and
other nonvolatiles
Lower operating temperatures than conventional distillation
Lower operating pressures than conventional pressure-driven membrane
separation
Reduced chemical interaction between membrane and process solutions
Less demanding membrane mechanical property requirements
Reduced vapor spaces compared to conventional distillation
FIGURE 8 Simplied scheme of an adsorptive distillationbased separation
of closely boiling hydrocarbon mixtures. (From Ref. 197.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
TABLE 7 Potential Application Fields of Adsorptive Distillation Reported
in the Literature
Selected
System refs. Remarks
Toluenemethylcyclohexane 196 Suitable adsorbents: silica gel,
mixtures and other activated carbon, coconut
closely boiling charcoal, bauxite,
hydrocarbons activated alumina
Naphtha reformate and 197 Silica gel as adsorbent
other close-boiling
hydrocarbons
o-Xylenem-xylene mixture 198 Modeling study
Ethanolwater and ethyl 199,200 Zeolite (4A molecular sieve)
acetatewatern-butanol as adsorbent, glycol as
mixtures carrier
p-Xylenem-xylene mixture 201 Zeolite (NaY molecular sieve)
as adsorbent, n-decane as
carrier
Membrane distillation systems may be classied into four different cat-
egories (203):
Direct contact membrane distillation (DCMD), in which the membrane is
in direct contact with the liquid phase on both sides
Air-gap membrane distillation (AGMD), in which an air gap is interposed
between the membrane and the condensation surface
Vacuum membrane distillation (VMD), in which the vapor phase is evacu-
ated from the liquid through the membrane and the condensation takes
place in a separate apparatus
Sweeping-gas membrane distillation (SGMD), in which a stripping gas,
instead of vacuum, is used as a carrier
Currently, the most important application area for membrane distillation is
water desalination technology. Figure 10 shows one of the water desalination
processes developed by a Japanese organization, the Water Re-Use Promotion
Center, in cooperation with Takenaka Corporation and Organo Corporation (204).
The process uses solar energy and can therefore be installed at locations without
an electricity supply. Other application areas for membrane distillation reported
in the literature are summarized in Table 8.
In 2002, the TNO Environment, Energy and Process Innovation institute
in the Netherlands developed a membrane-based distillation concept that radically
improves the economy and ecology of existing desalination technology for
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 9 Scheme of a membrane distillation process.
seawater and brackish water. This so-called Memstill
technol-
ogy, compared to the classical desalination techniques, is shown in Figure 11b.
An academic-industrial consortium is currently developing and improving the
Memstill
process concept and module design (226). The same TNO Institute
has also developed a concept of another membrane-based distillation technology
for fractionation of non-water-based systems (227). The technology, called
MEMFRAC, offers high energy efciency in compact equipment. The study car-
ried out for fractionation of benzene from toluene showed that with MEMFRAC
technology a HETP between 5 and 10 cm could be obtained. Additional advan-
tages of the MEMFRAC technology include: lack of entrainment, ooding, foam-
ing, or channeling (due to indirect gasliquid contact), independent gas/liquid
control, and the possibility for modular plant design. Such a modular MEMFRAC
distillation unit is schematically presented in Figure 12.
On the other hand, a pervaporation membrane can be coupled with a con-
ventional distillation column, resulting in a hybrid membrane/distillation process
(228,229). Some of the investigated applications of such hybrid pervaporation
membrane/distillation systems are shown in Table 9. In hybrid pervaporation/
distillation systems, the membrane units can be installed on the overhead vapor
of the distillation column, as shown in Figure 13a for the case of propylene/
propane splitting (234), or they can be installed on the feed to the distillation column,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 10 Scheme of the demonstration test plant for water desalination using solar energy and membrane distillation.
(Courtesy: CADDET, Center for Renewable Energy, Harwell, UK).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
TABLE 8 Application Areas of Membrane Distillation
Selected
System/process refs. Remarks
Concentration of H
2
SO
4
, 205207
H
3
PO
4
, NaOH, HNO
3
, and
HCl solutions
Concentration of 2,3-butanediol 208 VMD process
from fermentation broths
Wastewater treatment in 209 Integrated reverse
the textile industry osmosis/membrane
distillation process
Radioactive wastewater 210 Integrated reverse
treatment osmosis/membrane
distillation process
Removal of benzene traces 211 VMD process
from water
Concentration of protein solutions 212
Removal of halogenated VOCs 213 VMD process
Concentration of oilwater 214
emulsions
Concentration of sugar/sucrose 215,216 DCMD and AGMD
solutions processes
Separation of water and glycols 217 DCMD process
Ethanolwater separation 218 AGMD process
Acetone and ethanol removal 219 AGMD process
from aqueous solutions
Propanone removal from 220 AGMD process
aqueous streams
Acetonebutanolethanol 221 AGMD process
(ABE) solvent recovery
Fermentative ethanol 222,223 Integration of MD in
production fermentation resulted
in ca. 2 increase of
production rate
Concentration and purication 224
of uosilicic acid
Removal of trichloroethylene 225 VMD process
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 11 Memstill
technology of seawater desalination developed at the TNO institute: (a) principle of the
process; (b) cost comparison with other desalination techniques. (From Ref. 226.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
as shown in Figure 13b for the case of aromatic/aliphatic hydrocarbon separation
(235). Shortcut design methods for hybrid pervaporation/distillation processes
can be found in Ref. 236.
3.4. Membrane Absorption/Stripping
Membrane absorption is one of the processes that Mother Nature had invented long
before engineers did. Human lungs and intestines present perfect examples of
membrane absorption systems. In the simplest case a gaseous component is selec-
tively transported via a membrane and dissolved in the absorbing liquid, as shown
in Figure 14. It is also possible to carry a membrane-based absorption-desorption
process, with two liquids on both sides of the membrane (237), or a membrane
stripping process, in which selected components are removed from the liquid phase
through the membrane by a stripping gas (238). An important characteristic feature
FIGURE 12 Scheme of a modular MEMFRAC distillation unit for fractionation
of non-water-based systems, developed at the TNO Institute. (From Ref. 227.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
of membrane absorption is that it proceeds without creating a real gasliquid inter-
face in the form of bubbles. Such a bubbleless gasliquid mass transfer can be of
advantage in certain processes, for instance, in shear-sensitive biological systems.
One of the most important application areas of the membrane absorption is
the capture of CO
2
from ue gas. Kvrner has recently developed a membrane
absorptionbased technology for the removal of CO
2
from turbine exhaust gases in
offshore applications (239). The process, based on membrane-facilitated CO
2
absorption in amine, followed by membrane-facilitated stripping with steam, is
schematically shown in Figure 15. The expected cost reduction, in comparison with
a conventional amine separation process, ranges between 30 and 40%, for both
investment and operating costs. The new membrane-based process also offers a very
signicant reduction in the weight and size of equipment (7075% and 65%, respec-
tively; see Figure 16), a great advantage in the case of offshore technology. Some
other possible applications of membrane absorption/stripping are shown in Table 10.
3.5. Membrane Chromatography (Adsorptive Membranes)
Membrane chromatography is a separation technique used almost exclusively in
the downstream processing of proteins. Traditionally, most chromatographic
purication steps in the downstream processing of proteins take place in columns
packed with bead-shaped particles. Membrane chromatography presents a hybrid
combination of liquid chromatography and membrane ltration based on micro-
porous or macroporous membranes that contain functional ligands attached to
their inner pore structure, which act as adsorbents. The main feature and advan-
tage of this technique, compared to the conventional ones, is the absence of pore
TABLE 9 Possible Applications of Hybrid Pervaporation/Distillation
Systems
System/process Selected
investigated refs. Remarks/effects
Benzenecyclohexane 230 Combination of extractive distillation
separation and one-stage pervaporation;
high-purity (99.299.5%) products;
estimated cost savings of 20%
Ethanol dehydration 231 Simulation study; 50% cost
reduction in comparison with
conventional azeotropic distillation
Propylene/propane 232 Pilot-plant studies; 2050% savings
splitting on operating costs
Propylene/propane 233 2630% savings on capital
splitting investment
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 13 Combined distillation/pervaporation systems for (a) propylene/ propane splitting and (b) aromatic/aliphatic
hydrocarbon separation. (Part a from Ref. 234; part b from Ref. 235.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
diffusion, which is the main transport resistance in traditional chromatography.
Dissolved molecules are carried directly to the adsorptive sites in the membranes
by convective ow (Figure 17), which increases the throughput of the process.
Membrane chromatography presents a process-intensive option for the protein A,
G, or L afnity chromatography (247253), as well as for metal afnity, ion-
exchange, hydrophobic interaction or reversed-phase chromatography (254258).
In recent years some new potential application elds for membrane chromato-
graphy have been demonstrated. Those are listed in Table 11.
FIGURE 14 Membrane absorption.
FIGURE 15 Membrane absorptionbased technology for removal of CO
2
from turbine exhaust gases, developed by Kvrner Process Systems.
(Courtesy: Kvrner.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 16 Plant-size reduction in Kvrners technology for CO
2
removal
from exhaust gases: (a) conventional process; (b) membrane absorption
process. (Courtesy: Kvrner.)
3.6. Membrane Extraction
In membrane extraction, the treated solution and the extractant/solvent are sep-
arated from each other by means of a solid or liquid membrane. The technique is
applied primarily in three areas: wastewater treatment (e.g., removal of pollutants
or recovery of trace components), biotechnology (e.g., removal of products from
fermentation broths or separation of enantiomers), and analytical chemistry (e.g.,
online monitoring of pollutant concentrations in wastewater). Figure 18a shows
schematically an industrial hollow berbased pertraction unit for water treat-
ment, according to the TNO technology (263). The unit can be integrated with a
lm evaporator to enable the release of pollutants in pure form (Figure 18b).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Other more promising possible applications of membrane extraction, reported in
the literature, are listed in Table 12.
3.7. Other Hybrid Separations
In extractive crystallization (nonadductive), the driving force for the separation
process is created by altering the solidliquid phase relationships via the addition
of a third component (usually liquid solvent) to the system. The solvent is chosen
in such a way that it binds strongly at the crystallization temperature but separates
easily at another temperature, where it is usually regenerated via distillation.
Examples of such dened extractive distillations include separation of m- and p-
cresols using acetic acid as the solvent (297), separation of o- and p-nitrochloro-
benzenes using p-dichlorobenzene (298), separation of lithium sulfate and lithium
formate using n-butanol or 2-propanol (299), and separation of p-xylene from
m-xylene using pentene (300).
TABLE 10 Reported Possible Applications of Membrane Absorption/
Stripping
System/process Selected
investigated refs. Remarks/effects
Ammonia absorption/ 240 Pilot-plant study in a polypropylene
desorption from hollow-ber column; ammonia is
ammonia water absorbed in diluted sulfuric acid
CO
2
and/or SO
2
removal 241 Absorption in NaOH, K
2
CO
3
,
alkanolamines, and Na
2
SO
3
using
hydrophobic microporous hollow-
ber modules
Cyanide recovery from 242 Recovery via a gas-lled membrane
wastewater (GFM) placed between the waste-
water and a chemical stripping
solution
H
2
S removal from gas 243 Asymmetric hollow-ber modules
streams coupled with concentrated
alkaline solution
CO
2
production for the 244 Possible energy saving of more
horticultural industry than 30% reported
(greenhouses)
H
2
S and SO
2
removal 245 Polyvinylidene uoride (PVDF)
hollow bers and concentrated
NaOH solution used
VOC removal from 246 Air stripping process via a
wastewater polypropylene hollow-ber module
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Smith, Bryson, and Valsaray (301,302) investigated solvent sublation, an
adsorptive bubble process, combining the transport mechanisms of liquid/liquid
extraction and gas stripping. The technique exploits the surface-active nature of
organic compounds in their removal from water systems. The mechanism of solvent
sublation is shown in Figure 19a. Gas bubbles are used to transport adsorbed solute
from the bulk solution to the solvent layer. Solvent sublation is particularly prom-
ising in the removal of (hydrophobic) organic compounds from wastewater streams.
An exemplary process scheme is shown in Figure 19b. An important advantage of
the method is that the intimate contact between the extracting solvent and the waste-
water is prevented (no problem of residual solvent in the treated water).
Zeitsch (303) conducted a preliminary research on the removal of acetic
acid from the vapor stream of furfural reactors by means of extractive condensa-
tion. It is a hybrid vapor-phase extraction process, in which solvent (triethyl-
amine, TEA) forms a high-boiling complex with acetic acid. As a result, a fog
FIGURE 17 Comparison of transport mechanisms in (a) conventional chro-
matography and in (b) membrane chromatography.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
fraction is formed that can be separated via a coalescence lter or an electrostatic
separator. The technique is reported to be highly selective.
In 2002, Drioli and coworkers (304) investigated a process for obtaining
protein crystals by means of membrane crystallization, which actually combines
membrane distillation and crystallization techniques. The solvent evaporates at
the membrane interface, migrates through the pores of the membrane, and con-
denses on the opposite side of the membrane. The reported preliminary results
indicate interesting potentialities of this new method with respect to macromole-
cular crystallization.
4. BARRIERS AND FUTURE PROSPECTS
Despite many ongoing research activities in the eld and a number of successful
commercializations, there still exist numerous technical and nontechnical barriers
that hinder a wider introduction of reactive and hybrid separations into industrial
practice. Two workshops held in 1998 by the Center for Waste Reduction
Technologies of AIChE (305) identied some of the barriers for reactive separ-
ations and divided them into three categories:
a. Technical gaps, such as lack of simulation and scale-up capability, lack
of validated thermodynamic and kinetic data, lack of materials (e.g.,
TABLE 11 Reported New Potential Applications of Membrane
Chromatography
Selected
System/process investigated refs. Remarks/effects
Separation of polynucleotides 259 Supercoiled plasmid DNA
investigated as model
Separation of oligonucleotides 260
and peptides
Separation of small 260 Benzene, toluene, homologues
hydrophobic molecules of 4-hydroxybenzoate
investigated
Enantiomeric separation 261 Racemic mixtures of
tryptophan and thiophenal
investigated in microuidic-
based membrane
chromatography
Separation of trace metals 262 La-Ce-Pr-Nd-Sm separation
and Zr-Hf separation
investigated
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 18 Pertraction technology for wastewater treatment from the TNO
Institute: (a) scheme of the hollow-ber pertraction unit; (b) integration of
pertraction with lm evaporation. (Courtesy: TNO.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
R
TABLE 12 Reported Potential Applications of Membrane Extraction
Selected
System/process investigated refs. Remarks
Separation of acetic acid from aqueous solution 264 Microporous polypropylene membrane,
MIBK as solvent
Separation of (S)-naproxen from racemic 265 Reactive extraction via hollow-ber
naproxen thioesters membrane
Separation of D,L-alanine and D,L-phenylalanine 266,267 Hollow-ber zeolite membrane
racemic mixtures
Removal of sulfanilic acid from wastewater 268 Hollow-ber modules
Lactic acid purication and concentration 269 Emulsion liquid membranes (ELMs)
Enrichment of bisphenol A 270 Liquid membrane
Phenol recovery from aqueous solutions 271,272 Various liquid and solid membranes
Zinc(II) recovery from HCl solution 273 Bulk liquid and hollow-ber membranes
Hydrogen separation from methane steam 274 Palladium alloy membranes
conversion products
Separation of liquid olen/parafn mixtures 275 Nonporous polymeric membranes
Removal of 2-chlorophenol 276 Liquid membrane from aqueous solutions
Ethanol removal from aqueous solutions 277 Microporous polypropylene membrane
Separation of cephalosporin C from 278 Bulk and emulsion liquid membranes
fermentation broth
Separation of penicillin G 279 Supported liquid membrane
from aqueous streams (Amberlite LA-2)
Enrichment of amino acids 280 Supported liquid membrane (Aliquat 336)
Separation of cephalexin from a mixture of 7-ADCA 281 Supported liquid membrane (Aliquat 336)
Separation of butyric acid from fermentation broth 282 Liquid membrane
(continued)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Separation of propionic and acetic acid from 283 Polymeric membranes
fermentation broth
Separation of citric acid from fermentation broth 284 Liquid membrane
Separation of lactic acid from fermentation broth 285 Emulsion liquid membrane
Production of acetone, butanol, and ethanol 286 Polypropylene membrane
(ABE) from potato wastes
Separation of long-chain unsaturated fatty acids 287 Microporous membrane, MeCN
and n-heptane as solvents
(Heavy) metals recovery from wastewater 288292 Various membranes
Removal of organic contaminants from wastewater 293296 Various membranes
TABLE 12 (cont.)
Selected
System/process investigated refs. Remarks
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 19 Solvent sublation: (a) process mechanism and (b) an exemplary
process scheme. (From Refs. 301 and 302.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
integrated catalysts/sorbents, membrane materials), and lack of high-
level process synthesis methodology
b. Technology transfer barriers, such as lack of multidisciplinary team
approaches to process integration, lack of commonality of prob-
lems (technology is application-specic) and lack of demonstrations/
prototypes on a reasonable scale (reactive and hybrid separations are
still regarded more as a science than a technology)
c. General barriers, such as higher standards, to which new technologies
must be held, compared to conventional technologies, lack of informa-
tion on process economics (early economic and process evaluation),
and fear of risk in using new technologies.
Most of these barriers also hold for hybrid separations. Two more factors
that clearly play a hindering role in the commercial application of many reactive
and hybrid separations are: the already-mentioned small feasible operation win-
dows and the reduction of the degree of freedom caused by the integration of reac-
tion and separation or by the coupling of two separations in one processing unit.
Figure 20 shows an example of how the integration of reaction and membrane
separation reduces the degree of freedom in a membrane reactor, resulting in
decreased operational exibility (306).
FIGURE 20 Degree of integration versus degree of freedom, in an example of
a membrane reactor. (From Ref. 306.)
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Despite the existing barriers, the coming years are expected to bring a sig-
nicant increase in the number of industrially applied reactive and hybrid sep-
aration technologies. In particular, progress can be expected in the application of
reactive distillation, reactive adsorption, and membrane-based operations. In
hybrid separations, expansion of research activities on new product/process areas
has already been seen. Reactive and hybrid separations have enormous potential
for process intensication. Making full use of that potential will lead to substan-
tially smaller, cleaner, and more energy-efcient chemical and biochemical
plants.
REFERENCES
1. A low-cost design for urea. Nitrogen 1996; (222):2931.
2. Taylor R, Krishna R. Chem Eng Sci 2000; 55:51835529.
3. Gildert GR, Rock K, McGuirk T. In: Proceedings of the International Symposium on
Large Chemical Plants 10. Advances in process technology through catalytic distil-
lation. Antwerp, 1998:103113.
4. Siirola JJ. AIChE Symp Ser 1995; 91(304):222233.
5. Stein E, Kienle A, Sundmacher K. Chem Eng 2000; 107(13):6872.
6. Podrebarac GG, Ng FTT, Rempel GL. CHEMTECH 1997; 27(5):3745.
7. Schwarzer S, Hoffmann U. Chem Eng Technol 2002; 25:975980.
8. Steinigeweg S, Gmehling J. Ind Eng Chem Res 2002; 41:54835490.
9. Georgiadis MC, Schenk M, Gani R, Pistikopoulos RN. Computer-Aided Chem Eng
2001; 9:9971002.
10. Kenig EY, Bader H, Grak A, Bessling B, Adrian T, Schoenmakers H. Chem Eng Sci
2001; 56:61856193.
11. Siirola JJ. AIChE Symp Ser 1995; 91(304):222233.
12. Moritz P, Blagov S, Hasse H. Chem Ing Tech 2002; 74:12071218.
13. von Scala C, Gotze L, Moritz P. Sulzer Tech Rev 2001; 83(3):1215.
14. Smejkal Q, Hanika J, Kolena J. Chem Eng Sci 2001; 56:365370.
15. Chiang S-F, Kuo C-L, Yu C-C, Wong DSH. Ind Eng Chem Res 2002; 41:32333246.
16. Bollyn M, Wright AR. Chem Eng World 1999; 34(6):103108.
17. Omota F, Dimian AC, Bliek A. Computer-Aided Chem Eng 2001; 9:9463468.
18. Masamo J, Matsuzaki K. J Chem Eng Japan 1994; 27:15.
19. Kolah AK, Mahajani SM, Sharma MM. Ind Eng Chem Res 1996; 35:37073720.
20. Ward DJ. Etherication of isoamylenes by catalytic distillation. U.S. Patent 5196612,
UOP Inc., 1993.
21. Baur R, Taylor R, Krishna R. Computer-Aided Chem Eng 2001; 9:9398.
22. Baur R, Krishna R. Chem Eng Proc 2002; 41:445462.
23. Yeh A-I, Berg L. Chem Eng Commun 1992; 113:147153.
24. Preston KL. Use of reactive distillation in the manufacture of methyl tertiary-butyl
ether. U.S. Patent 5741953, Huntsman Specialty Chemicals Corp., 1998.
25. Tian Y-C, Zhao F, Bisowarno BH, Tade MO. J Proc Control 2002; 13:5767.
26. Al-Arfaj MA, Luyben WL. Ind Eng Chem Res 2002; 41:37843796.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
27. Quitain AT, Itoh H, Goto S. In: Abraham MA, Hesketh RP, eds. Reaction Engineer-
ing for Pollution Prevention. Amsterdam: Elsevier Science, 2000:237246.
28. Marker TL, Funk GA, Barger PT, Hammershaimb HU. Two-stage process for produc-
ing diisopropyl ether using catalytic distillation. U.S. Patent 5,744,645, UOP Inc., 1998.
29. Castor Gonzales J, Subawalla H, Fair JR. Ind Eng Chem Res 1997; 36:38453853.
30. Xu Y, Chuang KT, Sanger AR. Chem Eng Res Des 80:686694, 2002.
31. Watanabe R, Nakanishi A. Production of cyclohexanol from cyclohexene by reactive
distillation. JP 10287600, Mitsubishi Chemical Industries Ltd., 1998.
32. Steyer F, Qi Z, Sundmacher K. Chem Eng Sci 2002; 57:15111520.
33. Levin D, Santiesteban JG. Production of phenol using reactive distillation. WO
0146102, Mobil Oil Corp., 2001.
34. Kumar A, Daoutidis P. AIChE J 1999; 45:5168.
35. Monroy-Loperena R, Perez-Cisneros E, Alvarez-Ramirez J. Chem Eng Sci 2000;
55:49254937.
36. Knifton JF, Sanderson JR, Stockton ME. The use of reactive distillation in the catalytic
dehydration of teriary-butyl alcohol to produce anhydrous isobutylene. U.S. Patent
5,811,620, Huntsman Specialty Chemicals Corp., 1998.
37. Knifton JF, Sanderson JR, Stockton ME. Catal Lett 2001; 73:5557.
38. Abella LC, Gaspillo P-AD, Itoh H, Goto S. J Chem Eng Japan 1999; 32:742746.
39. Aiouache F, Goto S. J Chem Eng Japan 2002; 35:443449.
40. Yoshida Y. Preparation of isophorone from acetone by using a reactive distillation
column. JP 08245486, Daicel Chem, 1995.
41. Lawson KH, Nkosi B. Production of MIBK from acetone and hydrogen using catalytic
distillation technology. U.S. Patent 6,008,416, Catalytic Distillation Technologies, 1999.
42. Saayman N, Lund GJ, Kindermans S. Process for the production of MIBK using cata-
lytic distillation technology. WO 02022542, Catalytic Distillation Technologies, 2002.
43. Huang C, Yang L, Ng FTT, Rempel GL. Chem Eng Sci 1998; 53:34893499.
44. Podrebarac GG, Ng FTT, Rempel GL. Chem Eng Sci 1998; 53:10671075.
45. Gaspilla P-AD, Abella LC, Goto S. J Chem Eng Japan 1998; 31:440444.
46. Liu Q, Zhang F, Gao H. Huaxue Gongcheng (Xian China) 2002; 30(2):7578.
47. Stitt EH. Chem Eng Sci 2002; 57:15371543.
48. Maraschino MJ. Apparatus and process for the catalytic distillation of unsaturated,
nonaromatic C35 hydrocarbons. U.S. Patent 5,847,249, Catalytic Distillation Tech-
nologies, 1998.
49. Stanley SJ, Sumner C. Catalytic distillation and hydrogenation of heavy unsaturates
in an olens plant in the manufacture of ethylene and propylene. WO 9909118, ABB
Lummus Global Inc., 1999.
50. Lebas E, Jullian S, Travers C, Capron P, Joly J-F, Thery M. Process for the isomeriza-
tion of parafns by reactive distillation. EP 787786, Institut Franais du Ptrole, 1997.
51. Dorbon M, Chodorge JA, Cosyns JA, Viltard JC, Didillon B. Method for producing
high-purity isobutene through hydroisomerization reactive distillation and skeletal
isomerization of c4 alkenes. FR 2757506, Institut Franais du Ptrole, 1998.
52. Shoemaker JD, Jones EM Jr. Hydrocarbon Processing 1987; 66(6):5758.
53. Smith LA Jr, Arganbright RP, Hearn D. Preparation of ethylbenzene in a catalytic
distillation column reactor. U.S. Patent 5,476,978, Chemical Research and Licensing
Company, 1995.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
54. Zhang J, Li D, Fu J, Cao G. Process and apparatus for preparation of ethylbenzene
by alkylation of benzene with dilute ethylene contained in dry gas by catalytic distil-
lation. U.S. Patent Appl. 2001018545, 2001.
55. Silvergerg SE, Lattner JR, Sanchez LE. Use of hydrogenative catalytic distillation to
produce cyclopentane and/or cyclopentene from dicyclopentadiene. WO 0029358,
Exxon Chemical Patents Inc., 2000.
56. Cassel WR, Wuttke KG. Purication of hydrouorocarbons by reactive distillation.
WO 9640606, E.I. Du Pont de Nemours and Company, 1996.
57. Podrebarac GG, Gildert GR. Catalytic distillation for desulfurization of full-range
naphtha by thioetherication and hydrodesulfurization. WO 0266580, Catalytic Dis-
tillation Technologies, 2002.
58. Dorai S. Alkanolysis of polyether polyol esters by reactive distillation. WO 9723559,
E.I. Du Pont de Nemours and Company, 1997.
59. Aoki T, Otsubo K. Reactive distillation for manufacturing of glycine from glycinon-
itrile. JP 2001258586, Asahi Chemical Industry Co., Ltd., 2001.
60. Luo H-P, Xiao W-D. Chem Eng Sci 2001; 56:403410.
61. Leemann M, Hildebrandt V, Thiele H, Espig S. Production of polyamides by reactive
distillation. WO 9943732, BASF AG, 1999.
62. Grosser JH, Doherty MF, Malone MF. Ind Eng Chem Res 1987; 26:983989.
63. Bezzo F, Bertucco A, Forlin A, Barolo M. Sep Pur Technol 1999; 16:251260.
64. Sirkar KK, Shanbhag PV, Kovvali AS. Ind Eng Chem Res 1999; 38:37153737.
65. Gryaznov VM, Smirnov VS. Kinet Katal 1977; 18:579580.
66. Sanchez Marcano JG, Tsotsis TT. Catalytic Membranes and Membrane Reactors.
Weinheim: Wiley-VCH, 2002.
67. Bjorklund MC, Carr RW. Catal Today 1995; 25:159168.
68. Carvoli G, Gelosa D, Morbidelli M, Ranghino G, Ruggieri R, Tricella A. Process for
the esterication of alcohols in a chromatographic reactor. EP 1213278, La Chemial
Spa, 2002.
69. Zhang Z, Hidajat K, Ray AK. Ind Eng Chem Res 2002; 41:32133232.
70. Zhang Z, Hidajat K, Ray AK. Ind Eng Chem Res 2001; 40:53055316.
71. Falk T, Seidel-Morgenstern A. Chem Eng Sci 2002; 57:15991606.
72. Bjorklund MC, Kruglov AV, Carr RW. Ind Eng Chem Res 2001; 40:22362242.
73. den Hollander JL, Wong YW, Luyben KC, van der Wielen LAM. Chem Eng Sci
1999; 54:32073215.
74. Deng Z, Dieckmann GR, Langer SH. J Chem Soc Perkin Trans 2: Phys Org Chem
1998; (5):11231128.
75. Mazzotti M, Neri B, Gelosa D, Morbidelli M. Ind Eng Chem Res 1997; 36:31633172.
76. Meurer M, Altenhoener U, Strube J, Untiedt A, Schmidt-Traub H. Starch/Staerke
1996; 48:452458.
77. Herbstfhofer R, Bart H-J, Prior A, Wolfgang J. Recents Prog Genie Procedes 1999;
13(68):195203.
78. Sad MR, Querini CA, Cornelli RA, Figoli NS, Parera JM. Appl Catal A General
1996; 146:131143.
79. Ray AK, Carr RW, Aris R. Chem Eng Sci 1994; 49:469480.
80. Ray AK, Carr RW. Chem Eng Sci 1995; 50:21952202.
81. Zafar I, Barker PE. Chem Eng Sci 1988; 43:23692375.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
82. Langer SH, Patton JE. J Phys Chem 1972; 76:21592170.
83. Grifth TD, Chu AH, Langer SH. Chem Eng J 1987; 36:7391.
84. Schweich D, Villermaux J. Ind Eng Chem Fundam 1982; 21:4751.
85. Wardewell AW, Carr RW, Aris R. In: Wei J, Georgakis C, eds. Chemical Reaction
Engineering. Boston: ACS Symposium Series Vol. 196, 1982:297306.
86. Arumugam BK, Perri ST, MacKenzie EB, Blair LW, Zoeller JR. Process for the
preparation of ascorbic acid. U.S. Patent 6,476,239, Eastman Chemical Co., 2002.
87. Meissner JP, Carta G. Ind Eng Chem Res 2002; 41:47224732.
88. Migliorini C, Meissner JP, Mazzotti M, Carta G. Biotechnol Prog 2000; 16:600609.
89. Fissor D, Barresi AA. Chem Eng Technol 2002; 25:421426.
90. Cho BK, Carr RW, Aris R. Sep Sci Technol 1980; 15:679696.
91. Kawase M, Pilgrim A, Araki T, Hashimoto K. Chem Eng Sci 2001; 56:453458.
92. Silva VMTM, Rodrigues AE. AIChE J 2002; 48:625634.
93. Xiu G-H, Li P, Rodrigues AE. Chem Eng Sci 2002; 57:38933908.
94. Gomes VG, Yee KWK. Chem Eng Sci 2002; 57:38393850.
95. Sheikh J, Kershenbaum LS, Alpay E. Hung J Ind Chem 1999; 1:5255.
96. Elsner MP, Dittrich C, Agar DW. Chem Eng Sci 2002; 57:16071619.
97. van der Wielen LAM, Diepen PJ, Houwers J, Luyben KCAM. Chem Eng Sci 1996;
51:23152325.
98. Kuczynski M. The synthesis of methanol in a gassolidsolid trickle-ow reactor.
Ph.D. dissertation, University of Twente, Enschede, Netherlands, 1987.
99. Westerterp KR, Bodewes TN, Vrijland MS, Kuczynski M. Hydrocarbon Processing
1988; 67:6973.
100. Minotti M, Doherty M, Malone MF. Ind Eng Chem Res 1998; 37:47464755.
101. Samant KD, Ng KM. Chem Eng Technol 1999; 22:877880.
102. Patnaik PR. J Biotechnol 1992; 23:95101.
103. Yang C, Cussler EL. Biotechnol Bioeng 2000; 69:6673.
104. Likidis Z, Schgerl K. Biotechnol Lett 1987; 9:229232.
105. Mller B, Schlichting E, Bischoff L, Schgerl K. Appl Microbiol Biotechnol 1987;
26:206210.
106. Reschke M, Schgerl K. Chem Eng J 1984; 28:B25B29.
107. Malinowski JJ. Biotechnol Prog 2000; 16:7679.
108. Jarvinen M, Myllykoski L, Keiski R, Sohlo J. Bioseparation 2000; 9:163166.
109. Wasewar KL, Heesink ABM, Versteeg GF, Pangarkar VG. J Biotechnol 2002; 97:
5968.
110. Nurcan T, Bayraktar E, Mahmetoglu . J Chem Technol Biotechnol 2001;
76:764768.
111. Pai RA, Doherty MF, Malone MF. AIChE J 2002; 48:514526.
112. Crandall JW, Grimm RC. Separation of organic acids from the products of partial
oxidation of parafns by reactive extraction with amines. U.S. Patent 3,541,121,
Union Carbide Corp., 1970.
113. Schlichting E, Halwachs W, Schgerl K. Chem Eng Proc 1985; 19:317328.
114. Haensel R, Halwachs W, Schgerl K. Chem Eng Sci 1986; 41:135141.
115. Haensel R, Halwachs W, Schgerl K. Chem Eng Sci 1986; 41:18111815.
116. Bauer U, Marr R, Rueckl W, Siebenhofer M. Berichte der Bunsen-Gesellschaft 1989;
93:980984.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
117. Aliwarga L, Schgerl K. DECHEMA Biotechnol Conf 1988; 1:483488.
118. Hano T, Matsumoto M, Ohtake T, Hori F. J Chem Eng Japan 1992; 25:293297.
119. Bart HJ, Maier S, Marr R, Weiss S. Chem Tech (Leipzig) 1993; 45:107115.
120. Bart HJ. Reactive Extraction. Berlin: Springer-Verlag, 2001.
121. Bart HJ. Chem Eng Sci 2002; 57:16331637.
122. Verhoeven W, Sluyts D, Denecker G, van Osselaer T, Hinz J, Vaes J, van Herck W, de
Vos S. Treatment of phenolic wastewaters from manufacture of polycarbonates,
bisphenols or diphenyl carbonate by reactive extraction. DE 19510063, Bayer
Antwerpen N.V., 1996.
123. Cascaval D, Tudose R, Oniscu C. Hung J Ind Chem 1997; 25:245248.
124. Gutierrez B, Pazos C, Coca J. Waste Manag Res 1997; 15:371382.
125. Nowottny C, Halwachs W, Schgerl K. Sep Purif Technol 1997; 12:135144.
126. Cascaval D, Oniscu C, Galaction A-I. Biochem Eng J 2001; 7:171176.
127. Bora M, Dutta NN, Bhattacharya KG. Chem Eng Commun 2000; 179:1534.
128. Oniscu C, Cascaval D, Galaction A-I, Dumitru IF. Roumanian Biotechnol Lett 2000;
5:439447.
129. Kueke F. Procedure for the reactive extraction of chromium-containing substances
from aqueous feed solutions. DE 19943232, 2001.
130. Elshani S, Smart NG, Lin Y, Wai CM. Sep Sci Technol 2001; 36:11971210.
131. Grinbaum B, Adda M, Eidelman C. In: Cox M, Hidalgo M, Valiente M, eds. Solvent
Extraction for the 21st Century, Proc ISEC 99, Barcelona. London: Society of
Chemical Industry, 2001:549552.
132. Kuzmanovic B, Jallo R, Kuipers NJM, de Haan AB, Kwant G. In: International
Solvent Extraction Conference, Cape Town, South Africa, March 2002. Marshalltown:
South African Institute of Mining and Metallurgy, 2002:12711276.
133. Brugel EG. Production of cyclic ester oligomers from linear polyesters by reactive
extraction. WO 0268496, E.I. Du Pont de Nemours and Co., 2002.
134. Kruse A, Dahmen N, Dinjus E. Chem Eng Technol 2002; 25:882885.
135. Kelkar VV, Ng KM. AIChE J 1999; 45:6981.
136. Bayley CR, Vaidya NA. In: Collins AN, Sheldrake GN, Crosby J, eds. Chirality in
Industry. New York: Wiley, 1992:6977.
137. Chivate MR, Parikh NC. Indian Chem Eng 1966; 8:111115.
138. Tare JP, Chivate MR. AIChE Symp Ser 1976; 72(153):9599.
139. Tare JP. Inst Chem Eng Symp Ser 1978; 54:253256a.
140. Lee CH, Kim KJ, Ryu SK. J Chem Eng Japan 1992; 25:585591.
141. Jadhav VK, Chivate MR, Tavare NS. J Chem Eng Data 1991; 36:249251.
142. Tsuge H, Kotaki Y, Hibino S. J Chem Eng Japan 1987; 20:374379.
143. Kotaki Y, Tsuge H. Can J Chem Eng 1990; 68:435442.
144. Momonaga M, Yazawa H, Kagara K. J Chem Eng Japan 1992; 25:237242.
145. Tsuge H, Matsuo H. ACS Symp Ser 1990; 438:344354.
146. Tsuge H, Okada K, Yano T, Fukushi N, Akita H. ACS Symp Ser 1997; 667:
254256.
147. Tsuge H, Yoshiza S, Tsuzuki M. Chem Eng Res Des 1996; 74:797802.
148. Tsuge H, Tanaka Y, Yoshizawa S, Kuraishi T. Chem Eng Res Des 2002; 80:
105110.
149. Hirasawa I, Nakagawa H, Yosikawa O, Itoh M. ACS Symp Ser 1997; 667:267276.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
150. Hirasawa I, Katayama A, Kitayama M, Toyokura K. In: Proceedings of the 14th
International Symposium on Industrial Crystal, Cambridge, UK, 1999. Rugby: Insti-
tution of Chemical Engineers, 1999:916924.
151. Tsuge H, Takahashi Y, Fujiwara E. In: Proceedings of the 8th World Salt Symposium,
The Hague, 2000. Amsterdam: Elsevier Science, 2000:733738.
152. Ito T, Tsuge H, Fujita A, Fukatani M. In: Proceedings of the 14th International Sym-
posium on Industrial Crystal, Cambridge, UK, 1999. Rugby: Institution of Chemical
Engineers, 1999:15101517.
153. Am Ende DJ, Crawford TC, Weston NP. Reactive crystallization method to improve
particle size. EP 1157726, Pzer Products Inc., 2001.
154. Chen P-C, Kou KL, Tai HK, Jin SL, Lye CL, Lin CY. J Crystal Growth 2002;
237239 (Pt 3):21662171.
155. ZareNezhad B, Garside J, Tavare NS. In: Proceedings of the 14th International Sym-
posium on Industrial Crystal, Cambridge, UK, 1999. Rugby: Institution of Chemical
Engineers, 1999:13161330.
156. Lu J, Wang J. Chinese J Chem Eng 2000; 8:6873.
157. Toyokura K, Tawa K, Ueno J. J Chem Eng Japan 1979; 12:2428.
158. Chen J, Wang Y, Zheng C. In: Semel J, ed. 2nd International Conference on Process
Intensication in Practice. BHR Group Conf. Series, No. 28. London: Mechanical
Engineering Publications, 1997:157164.
159. Chen J-F, Wang Y-H, Guo F, Wang X-M, Zheng C. Ind Eng Chem Res 2000;
39:948954.
160. Diaz Z. H
2
S removal from gas streams. U.S. Patent 4,518,576, Shell Oil Company,
1983.
161. Demmink JF, Beenackers AACM. Ind Eng Chem Res 1998; 37:14441453.
162. Demmink JF, Mehra A, Beenackers AACM. Chem Eng Sci 2002; 57:17231734.
163. Hasebe N, Hasebe N. Desulfurization of a gas by absorption. U.S. Patent 5,389,351,
1995.
164. Hix RM, Lynn S. Ind Eng Chem Res 1991; 30:930939.
165. Gestrich W. Treatment of gaseous stream containing nitrogen oxide. DE 3640119,
1987.
166. Zapfel W, Marr R, Siebenhofer M. Sep Sci Technol 1997; 32:617640.
167. Safarik DJ, Eldridge RB. Ind Eng Chem Res 1998; 37:25712581.
168. Lucas K, Roth H, Radgen P. AES (ASME) 1993; 30:291297.
169. Sucksmith I. Chem Eng 1982; 89(13):9195.
170. Hairston D. Chem Eng 2001; 108(10):3139.
171. Tripathi RP, Sagar JM, Gulati IB. J Appl Chem Biotechnol 1973; 23:581588.
172. Berg L. AIChE J 1983; 29:961966.
173. Ruiz C, Coca J, Vega A, Dez FV. Ind Eng Chem Res 1997; 36:49344939.
174. Berg L, Yeh A-I. AIChE J 1984; 30:871874.
175. Berg L, Yeh A-I. Chem Eng Commun 1984; 30:113117.
176. Lee F-M, Pahl RH. Ind Eng Chem Process Des Dev 1985; 24:168172.
177. Berg L, Yeh A-I, Ratanapupech P. Chem Eng Commun 1985; 39:193199.
178. Berg L, Yeh A-I. Chem Eng Commun 1986; 48:93101.
179. Berg L, Yeh A-I. Chem Eng Commun 1987; 54:149159.
180. Berg L. Chem Eng Commun 1987; 52:105108.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
181. Berg L, Vosburgh MG, Christensen RW, Shanahan MJ. Chem Eng Commun 1988;
66:121.
182. Mahapatara A, Gaikar VG, Sharma MM. Sep Sci Technol 1988; 23:429436.
183. Gaikar VG, Sau GK. Sep Sci Technol 1996; 31:19791988.
184. Yeh A-I, Berg L, Warren KJ. Chem Eng Commun 1988; 68:6979.
185. Yeh A-I, Berg L. Chem Eng Commun 1992; 113:147153.
186. Liu F, Zhang C, Huang F, Zhang C. Fuel Sci Technol Int 1993; 11:15371550.
187. Vega A, Dez F, Esteban R, Coca J. Ind Eng Chem Res 1997; 36:803807.
188. Arce A, Rodil E, Soto A. Can J Chem Eng 1999; 77:11351140.
189. Tiverios PG, van Brunt V. Ind Eng Chem Res 2000; 39:16141623.
190. Schlovsky G, Loftus B. Chem Eng 2000; 107(2):9698.
191. Liao B, Lei Z, Xu Z, Zhou R, Duan Z. Chem Eng J 2001; 84:581586.
192. Lei Z, Zhou R, Duan Z. J Chem Eng Japan 2002; 35:211216.
193. Lei Z, Zhou R, Duan Z. Chem Eng J 2002; 85:379386.
194. Lee F-M. Chem Eng 1998; 105(11):112121.
195. Lei Z, Wang H, Zhou R, Duan Z. Chem Eng J 2002; 87:149156.
196. Herbst WA. Adsorptive distillation. U.S. Patent 2,665,315, Standard Oil Development
Company, 1954.
197. Marple S, Jr, Foecking NJ. Adsorptive distillation process. U.S. Patent 2,768,942,
Shell Development Company, 1956.
198. Rice RG. Chem Eng Commun 1981; 10:111126.
199. Ming Z, Chunjian X, Guocong YU. Prog Nat Sci 1995; 5(3):291298.
200. Yu KT, Zhou M, Yu CJ. A novel separation process. Distillation accompanied by
adsorption. In: Proceedings of the 5th World Congress on Chemical Engineering,
San Diego, Vol. 1, New York: AIChE, 1996:347352.
201. Zhou M, Xu CJ, Zhang GH, Yu KT. Study on the separation of p- and m-xylene by
adsorptive distillation. In: Proceedings of the 5th World Congress on Chemical
Engineering, San Diego, Vol. 1, New York: AIChE, 1996:962967.
202. Lawson KW, Lloyd DR. J Membrane Sci 1997; 124:125.
203. Velazquez A, Mengual JI. Ind Eng Chem Res 1995; 34:585590.
204. CADDET Center for Renewable Energy. A Solar Desalination System Using the
Membrane Distillation Process. Technical Brochure No. 46, 2001.
205. Kimura S, Nakao S-I. J Membrane Sci 1987; 33:285298.
206. Udriot H, Araque A, von Stockar U. Chem Eng J 1994; 54:8793.
207. Tomaszewska M, Gryta M, Morawski AW. J Membrane Sci 1995; 102:113122.
208. Qureshi N, Meagher MM, Hutkins RW. Sep Sci Technol 1994; 29:17331748.
209. Calabro V, Drioli E, Matera F. Desalination 1991; 83:209224.
210. Chmielewski AG, Harasimowicz M, Zakrzewska-Trznadel G. In: Howell JA, Noworyta
A, eds. Towards Hybrid Membrane and Biotechnology Solutions for Polish Environ-
mental Problems. Wroclaw, Poland: Wroclaw Technical University Press, 1995.
211. Banat FA, Simandl J. Chem Eng Sci 1996; 51:12571265.
212. Ortiz de Zrate JM, Rincn C, Mengual JI. Sep Sci Technol 1998; 33:283296.
213. Coufn N, Cabassud C, Lahoussine-Turcaud V. Desalination 1998; 117:233245.
214. Gryta M, Karakulski K. Desalination 1999; 121:2329.
215. Izquierdo-Gil MA, Garca-Payo MC, Fernndez-Pineda C. Sep Sci Technol. 1999;
34:17731801.
/ /
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
216. Izquierdo-Gil MA, Garca-Payo MC, Fernndez-Pineda C. J Membrane Sci 1999;
155:291307.
217. Rijncn C, Ortiz de Zrate JM, Mengual JI. J Membrane Sci 1999; 158:155165.
218. Banat FA, Simandl J. J Membrane Sci 1999; 163:333348.
219. Banat FA, Al-Rub FA, Shannag M. Heat Mass Transfer 1999; 35:423431.
220. Banat FA, Simandl J. J Chem Technol Biotechnol 2000; 75:168178.
221. Banat FA, Al-Shannag M. Bioproc Eng 2000; 23:643649.
222. Gryta M, Morawski AW, Tomaszewska M. Catal Today 2000; 56:159165.
223. Gryta M. Sep Pur Technol 2001; 24:283296.
224. Tomaszewska M. Ind Eng Chem Res 2000; 39:30383041.
225. Duan S, Ito A, Ohkawa A. J Chem Eng Japan 2001; 34:10691073.
226. TNO Environment, Energy and Process Innovation. Memstill
: Membrane Distilla-
tion. Technical information brochure, 2002.
227. TNO Environment, Energy and Process Innovation. MEMFRAC distillation: Modular-
Energy Efcient-Compact. Technical information brochure, 2002.
228. Moganti S, Noble RD, Koval CA. J Membrane Sci 1994; 93:3144.
229. Stephan W, Noble RD, Koval CA. J Membrane Sci 1995; 99:259272.
230. Rautenbach R, Albrecht R. J Membrane Sci 1985; 25:2554.
231. Goldblatt ME, Gooding CH. Ind Membrane Process 1988; 82:5159.
232. Davis JC, Valus RJ, Eshragi R, Velikoff AE. Sep Sci Technol 1993; 28:463476.
233. Al-Rabiah AA, Timmerhaus KD, Noble RD. Utilization of a hybrid membrane system
in olen production. In: Proceedings of the 5th World Congress of Chemical
Engineering, San Diego, Vol. IV, New York: AIChE, 1996:335340.
234. Ofce of Industrial Technologies, U.S. Department of Energy. Olen Recovery from
Chemical Industry Waste Streams. Chemicals Project Fact Sheet, 2000.
235. Ofce of Industrial Technologies, U.S. Department of Energy. Energy-Saving Sepa-
ration Technology for the Petroleum Industry. Petroleum Project Fact Sheet, 2000.
236. Bausa J, Marquardt W. Ind Eng Chem Res 2000; 39:16581672.
237. Shichang W, Shichang X, Yingjie Q. Chinese J Chem Eng 1993; 1:160170.
238. Mahmud H, Kumar A, Narbaitz RM, Matsuura T. J Mem Sci 2002; 209:207219.
239. Herzog H, Falk-Pedersen O. The Kvaerner membrane contractor. Lessons from a case
study in how to reduce capture costs. 5th International Conference on Greenhouse
Gas Control Technologies. Cairns, Australia, Aug 1316, 2000.
240. Shichang W, Shichang X, Yingjie Q. Chinese J Chem Eng 1993; 1:160170.
241. Nii S, Takeuchi H. Gas Sep Purif 1994; 8:107114.
242. Shen Z, Huang J, Qian G. Water Environ Res 1997; 69:363367.
243. Li K, Wang D, Koe CC, Teo WK. Chem Eng Sci 1998; 53:11111119.
244. Klassen R, Feron PHM, Jansen AE. Flue gas treatment with membrane gas absorp-
tion. In: Proceedings of the 1998 International Joint Power Geneneration Conference,
PWR-Vol. 33, ASME, Volume 2, 1998:309316.
245. Li K. Chem Eng Technol 2002; 25:203206.
246. Mahmud H, Kumar A, Narbaitz RM, Matsuura T. J Mem Sci 2002; 209:207219.
247. Thmmes J, Kula M-R. Biotechnol Prog 1995; 11:357367.
248. Bamford CH, Al-Lamee KG, McLaughlin PJ, Purbrick MD, Wear TJ. In: Kahovec J,
ed. Macromolecules. IUPAC 34th International Symposium on Macromolecules,
Utrecht, the Netherlands: VSP, 1994:431440.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
249. Malakian A. In: Street HG, ed. Highly Selective Separations in Biotechnology.
Glasgow: Blacki, 1994:3454.
250. Birkenmeier G, Dietze H. J Chromatography B 1997; 704:6368.
251. Berruex LG, Freitag R. In: Bernard A, et al., eds. Animal Cell Technology: Products from
Cells, Cells as Products. Dordrecht, Netherlands: Kluwer Academic, 1999: 223225.
252. Zou H, Luo Q, Zhou D. J Biochem Biophys Methods 2001; 49:199240.
253. Borcherding H, Hicke H-G, Jorcke D, Ulbricht M. Desalination 2002; 149:297302.
254. Reif O-W, Nier V, Freitag R. In: Alberghinia L et al., eds. ECB6: Proceedings of the 6th
European Congress on Biotechnology. Amsterdam: Elsevier Science, 1994:521524.
255. Ghosh R. J Chromatography A 2001; 923:5964.
256. Ltkemeyer D, Bretschneider M, Bntemeyer H, Lehmann J. J Chromatography
1993; 639:5766.
257. Ghosh R. J Membrane Sci 2001; 192:243247.
258. Tennikova TB, Svec F. J Chromatography 1993; 646:279288.
259. Giovannini R, Freitag R, Tennikova TB. Anal Chem 1998; 70:33483354.
260. Podgornik A, Barut M, Jancar J, S
1
1
, . . . ,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
where d
i
is the generalized driving force:
(2)
Similar equations can be also written for the gas/vapor phase.
Thus the gas/vapor/liquidliquid mass transfer is modeled as a combination
of the two-lm model and the MaxwellStefan diffusion description. In this stage
model, the equilibrium state exists only at the interface.
The lm thickness represents a model parameter that can be estimated
using mass transfer coefcient correlations. These correlations reect the mass
transport dependence on physical properties and process hydrodynamics and are
available from the literature (see, e.g., Refs. 57, 68 and 90).
The two-lm model representation can serve as a basis for more compli-
cated models used to describe heterogeneously catalyzed RSPs or systems con-
taining suspended solids. In these processes a third solid phase is present, and
thus the two-lm model is combined with the description of this third phase. This
can be done using different levels of model complexity, from quasi-homogeneous
description up to the four-lm presentations that provide a very detailed descrip-
tion of both vapor/gas/liquidliquid and solid/liquid interfaces (see, e.g., Refs. 62,
68 and 91). A comparative study of the modeling complexity is given in Ref. 64
for fuel ether synthesis of MTBE and TAME by CD.
2.4. Computational Fluid Dynamics
Every separation unit operation is governed by the continuum conservation laws,
and thus, in principle, everything meaningful to know in the continuum for any
process can be determined with computational uid dynamics (CFD) (92). In
recent years there have been signicant academic and industrial efforts to enable
d
x
T
d
dz
i n
i
i i
1, . . . ,
FIGURE 13 Two-lm model.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the use of CFD for the design, scale-up, and optimal operation of a variety of
chemical process equipment.
Special attention has been given to the CFD modeling of two-phase ows. The
most frequently encountered computational techniques for calculating multiphase
ows are EulerLagrange and EulerEuler methods. EulerLagrange models are
applicable to dispersed ows (93). In these models the ow of the so-called carrier
phase is simulated by solving continuum-ow equations. The motion of individual
particles (or group of particles) of the dispersed phase is tracked through the ow
domain using the calculated carrier-phase ow eld as input; afterwards, mass,
momentum, and energy transfer between the two phases are computed and applied to
the carrier-phase ow eld prediction. This procedure requires several iterations (94).
EulerEuler models assume interpenetrating continua to derive averaged
continuum equations for both phases. The probability that a phase exists at a cer-
tain position at a certain time is given by a phase indicator function, which, for
steady-state processes, is equivalent to the volume of fraction of the correspond-
ent phase (volume-of-uid technique). The phase-averaging process introduces
further unknowns into the basic conservation equations; their description requires
empirical and problem-dependent input (94). In principal, EulerEuler models
are applicable to all multiphase ows. Advantages and disadvantages of both
methods are compared, e.g., in Refs. 95 and 96.
The volume-of-uid technique can be used for a priori determination of the
morphology and rise characteristics of single bubbles rising in a liquid (97,98).
Considerable progress has been made in CFD modeling of bubbling gassolid
uidized beds by adoption of the Eulerian framework for both the dilute (bubbles)
and dense (emulsion) phases (99102). The use of CFD models for gasliquid
bubble columns has also aroused signicant interest in recent years, and both
EulerEuler and EulerLagrange methods have been employed for the description
of the gas and liquid phases (9496,103113).
There are also some attempts available in the literature to model tray hydro-
dynamics using CFD (114119).
Despite considerable success in some elds of application, the CFD simu-
lations are still not fully mastered, especially where the considered processes
reveal clearly nonhomogeneous, segregated uid ow patterns. The latter are usu-
ally the basic phenomenon in packed or lmlike units used in reactive and non-
reactive separations.
One of the important issues with RSPs is the development of efcient col-
umn internals. Such internals have to enhance both separation and reaction and
maintain a sound balance between them. This is valid for both homogeneously
and heterogeneously catalyzed processes, being especially important for CD. An
understanding of the complex, multiphase ow on the internals interrelated with the
mass transport and chemical reaction constitutes a very important challenge for the
future. Some rst steps in this respect have been done concerning the performance
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
of SULZER packings KATAPAK-S
H
H
H
H
R
R
R
R
.
.
.
.
2NO O NO kJ/mol (R1)
NO NO N O kJ/mol (R2)
2NO N O kJ/mol (R3)
3NO H O 2HNO NO kJ/mol (R4)
2
2 2 4
2 2 3
2 2
0
2 3
0
0
0
2 114
39 9
57 2
35 4
H
H
H
H
R
R
R
R
.
.
.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The liquid feeds entering columns 7 and 8 are low-concentration nitric
acids. The liquid product has a HNO
3
concentration of about 35 wt %. The gas
feed has a concentration of NO
x
of about 60,000 vppm. A quarter of NO
x
is NO;
the rest is NO
2
.
3.1.3. Results and Discussion
The sensitivity analysis performed in Ref. 129 shows that the suggested model
provides concentration proles that are qualitatively correct. For the simulation of
the industrial absorption process shown in Figure 14, the following correlations
ensuring the most reliable results are selected:
The rate constant of Reaction (R1) (the slowest and hence the most import-
ant reaction in the system) according to Ref. 132
The liquid-side mass transfer coefcient according to Ref. 133
The gas-side mass transfer coefcient according to Wehmeier (see Ref. 134)
Figures 15 and 16 give an illustration of the model quality. Figure 15 shows
a comparison of the simulated and measured gas-phase concentrations of NO and
NO
2
throughout the whole absorption plant, whereas in Figure 16, experimental
and simulated liquid-phase concentrations of HNO
3
and HNO
2
are demonstrated.
FIGURE 14 Absorption plant consisting of four units (eight columns).
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The zigzag form of the simulated concentration proles results from switching
different sections of each single column (see Ref. 135). Good agreement between
experimental and simulation results can be readily observed, except for the rst
two columns. Here the larger deviations between experiments and simulated
results can be attributed to the fact that at high concentration of HNO
3
Reactions
(R5) to (R7), assumed to be irreversible reactions, convert to reversible ones; the
data on their rate constants are lacking.
3.2. Coke Gas Purication
3.2.1. Chemical System
Coke oven gas consists mainly of a mixture of carbon monoxide, hydrogen,
methane, and carbon dioxide. It is contaminated with a variety of organic and
inorganic compounds that have to be separated in absorption columns before its
further use as a synthesis gas. The selective absorption of coke plant gas contam-
ination results from a complex system of parallel liquid-phase reactions.
Instantaneous reversible reactions:
NH H O NH OH R9)
H S H O HS H O R10)
2
2 2 3
3 4
(
(
FIGURE 15 Experimental and simulated gas-phase concentrations of NO and
NO
2
throughout the absorption plant.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Finite-rate reversible reactions:
The reactions including CO
2
obey rst- and second-order kinetics, where-
as the other reversible reactions are based on simple proton transfers and are
therefore regarded as instantaneous by the corresponding mass action law equa-
tions. The formation of bicarbonate ions (HCO
3
(
(
(
HCN H O CN H O R11)
HCO H O CO H O R12)
H O OH H O R13)
2 3
2
3 2
3 3
2
3
2
(
(
(
FIGURE 16 Experimental and simulated liquid-phase concentrations of HNO
3
and HNO
2
throughout the absorption plant.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
mechanisms. The rate of the direct reaction between carbon dioxide and hydroxyl
ions (the most important step) is taken from Ref. 28.
Usually the reaction between CO
2
and water is very slow and hardly con-
tributes to the total rate of reaction of carbon dioxide. Nevertheless, in this work
it was considered of the rst order with respect to CO
2
, since the reaction kine-
tics depends on the carbonation ratio (136).
The absorption rate of carbon dioxide increases in the presence of amines
or ammonia. Therefore, the reaction kinetics of NH
3
and CO
2
has been consid-
ered in the model equations, too. The rate constant as a function of the temperature
has been determined according to Ref. 136. The coefcients for the calculation of
the chemical equilibrium constants in this system of volatile weak electrolytes are
taken from Ref. 137.
The CO
2
absorption is hindered by a slow chemical reaction by which the
dissolved carbon dioxide molecules are converted into the more reactive ionic
species. Therefore, when gases containing H
2
S, NH
3
, and CO
2
contact water, the
H
2
S and ammonia are absorbed much more rapidly than CO
2
, and this selectivity
can be accentuated by optimizing the operating conditions (23). Nevertheless, all
chemical reactions are coupled by hydronium ions, and additional CO
2
absorption
leads to the desorption of hydrogen sulde and decreases the scrubber efciency.
3.2.2. Process Setup
Todays coke plant gas purication processes are mostly carried out under atmos-
pheric pressure, employing a circulated ammonia-based absorbent. The con-
sumption of the external solvent is reduced via the use of ammonia available in
the coke gas (138). An example of innovative purication processes is the ammo-
nia hydrogen sulde circulation scrubbing (ASCS) (Figure 17), in which the
ammonia contained in the raw gas dissolves in the NH
3
absorber and then the
absorbent saturated with the ammonia passes through the H
2
S absorber to selec-
tively absorb the H
2
S and HCN components from the coke gas. The next step is the
thermal regeneration of the absorbent with the steam in a two-step desorption plant,
whereas a part of the deacidied water is fed back into the H
2
S absorber (25).
Pilot-plant experiments have been carried out at real process conditions in
the coke plant August Thyssen (Duisburg, Germany). The DN 100 pilot column
(Figure 17) was made of stainless steel and equipped with about 4 m of structured
packing (Sulzer MELLAPAK
and
carbamate decreases whereas the relative fraction of HS
H
R
0
4 2 .
FIGURE 21 Dynamic change of the H
2
S gas-phase concentration along the
column after a sudden increase in the gas ow and its H
2
S load.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
guaranteed by segmentation of the catalyst bags and numerous contact spots with
the wire gauze sheets. The packing was equipped with the acid ion exchange resin
known as an effective catalyst for esterication processes (34,148).
A batch distillation column with a diameter of 100 mm and a reactive pack-
ing height of 2 m (MULTIPAK I
) )
.
2 3
0
37 7
H
R
FIGURE 26 Reactive distillation column, steady-state operation.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
presented (155). The column (used as an example here) has a catalytic section in the
middle part. This catalytic section may consist either of a packed bed of catalytical-
ly active rings (91) or of structured catalytic packing (147). The rectifying and strip-
ping sections are lled with Intalox Metal Tower Packing. The methanol feed is
introduced just above the catalyst section of the column and the hydrocarbon feed
just below.
3.5.3. Results and Discussion
Figure 28 demonstrates the simulated and measured concentration proles for the
pilot test made in the column, with the reactive section lled with catalytically
FIGURE 27 Liquid-phase composition proles along the 50-mm-diameter
catalytic distillation column for methyl acetate synthesis at reux ratio of 2.0
and different reboiler duties: (a) 295W (b) 873W (c) 1161W.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
active rings. In the simulations four componentsmethanol, isobutene, MTBE,
and 1-butenewere chosen to describe the system under consideration. Here,
segment 1 corresponds to the reboiler. A satisfactory agreement between calcu-
lated and measured values can be clearly observed. In Figure 29, the simulation
results for the column with different reactive internals, catalytic packing
MULTIPAK
b
b
2 2
2
a b
a a b a
Zn R H Zn R (RH) H
2
2 2 2
2 2
2
R H ,
2 2
RH,
FIGURE 28 Calculated and experimental liquid compositions for experiments
with catalytically active rings.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
FIGURE 29 Calculated and experimental liquid compositions for experiments with catalytic
structured packing.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The mass action law on the basis of concentrations then yields
(3)
where D
Zn
denotes the partition coefcient of zinc between the organic and the
aqueous phase (bar indicates organic species). In logarithmic form, the stoichio-
metry of the complex, b, is determined by slope analysis:
(4)
As can be seen, the partition increases with increasing ion exchanger concentra-
tion, and with pH. The determination of the equilibrium constant, K
eq
, is
discussed, e.g., in Ref. 158.
3.6.2. Process Setup
Apart from the nuclear industry, the most frequently installed pieces of process
equipment are mixer-settler cascades. The advantage is the easy control of each
stage regarding the pH value, selection of the phase to be dispersed, etc. (12,15).
The disadvantages are the high investment costs and large solvent inventory.
Nowadays, modern designed extractants (with fast kinetics) allow a process
design with highly efcient extraction columns (159). Applications are found in
the chemical industry, e.g., with sulfonic acid extraction (160). The rst applica-
tion on a big scale in hydrometallurgy was reported in 1997 at WMC Olympic
Dam, Australia, where 10 pulsed Batman columns (0.5 to 3 m in diameter and
35 m tall) were used for uranium recovery. An increased recovery (from 90% to
97%) was found after replacing the formerly used mixer-settler units.
The RE of zinc is reported in detail when using an RDC, including the dis-
cussion of the stripping process to regenerate the ion exchanger for cyclic reuse
(161163).
3.6.3. Results and Discussion
A comparison of predicted and experimental mass transfer coefcients is given in
Figure 30. The simulated overall mass transfer coefcient originates from a
model that is a combination of the microkinetic reaction according to Eq. (B9)
and eddy diffusion according to Eq. (B11) (see Appendix B). Figure 30 shows
that the mass transfer coefcient at higher concentrations is generally underesti-
mated, thus including some safety value for the process design. As discussed in
detail in Ref. 56, combinations of microkinetics [Eq. (B9)] with other eddy dif-
fusion correlations instead of Eq. (B11) (e.g., Refs. 164 and 165) are also appro-
priate to describe the system. In contrast to this, the combination of microkinetics
with molecular diffusion concepts fails, and the same is true when the equilibrium
R H
2 2
,
log R H pH log
Zn 2 2
eq
D b K log([ ]) 2
K D
b
b b
eq 2 2
2
2 2
Zn
2 2
ZnR RH) H
Zn R H
H
R H
[ ( ][ ]
[ ][ ]
[ ]
[ ]
2
2 2
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
approach is used neglecting the kinetics rate law. The results of the column sim-
ulations are discussed in Refs. 162 and 163, and a special discussion on contam-
ination effects is given in Ref. 166.
4. SUMMARY AND OUTLOOK
This chapter concerns the most important reactive separation processes: reactive
absorption, reactive distillation, and reactive extraction. These operations combin-
ing the separation and reaction steps inside a single column are advantageous as
compared to traditional unit operations. The three considered processes are similar
and at the same time very different. Therefore, their common modeling basis is dis-
cussed and their peculiarities are illustrated with a number of industrially relevant
case studies. The theoretical description is supported by the results of laboratory-,
pilot-, and industrial-scale experimental investigations. Both steady-state and
dynamic issues are treated; in addition, the design of column internals is addressed.
Reactive absorption, reactive distillation, and reactive extraction occur in
multicomponent multiphase uid systems, and thus a single modeling framework
for these processes is desirable. In this respect, different possible ways to build such
a framework are discussed, and it is advocated that the rate-based approach pro-
vides the most rigorous and appropriate way. By this approach, direct consideration
FIGURE 30 Comparison of experimental and simulated overall mass transfer
coefcients at different initial zinc concentrations and droplet diameters
(1, 2, or 3 mm) .
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
of the diffusional and reaction kinetics is realized. Special attention is paid to the
application of CFD, which could become a powerful theoretical tool to predict the
ow behavior for different column units and internals geometries for engineering
applications. In particular, CFD can play an outstanding role in the development of
the column internals for reactive separations. Fundamental advances in the under-
standing of the underlying physicochemical phenomena when coupled with CFD
would go a long way toward support of reactive separation technology.
The modeling of RA is illustrated by the absorption of NO
x
and by the
coke gas purication process. The rst case is modeled by using an analytical treat-
ment of the lm phenomena, whereas the second one is solved by a purely numer-
ical technique. The simulation results are compared with the experimental data
obtained at an industrial absorption plant consisting of eight units with
pump around (NO
x
) and at a pilot column for the ammonia hydrogen sulde
circulation scrubbing process (coke gas purication). For the latter case, both
steady-state and dynamic conditions are considered. The comparison results, on the
one hand, demonstrate a good agreement between the rate-based simulations and
experimental data, and, on the other hand, warn of using the equilibrium approach,
which appears completely inappropriate in the case of complex nite-rate reactions.
The modeling of RD processes is illustrated with the heterogenously catalyzed
synthesis of methyl acetate and MTBE. The complex character of reactive distilla-
tion processes requires a detailed mathematical description of the interaction of
mass transfer and chemical reaction and the dynamic column behavior. The most
detailed model is based on a rigorous dynamic rate-based approach that takes into
account diffusional interactions via the MaxwellStefan equations and overall reac-
tion kinetics for the determination of the total conversion. All major inuences of the
column internals and the periphery can be considered by this approach.
As an application example, the dynamic model was used for the simulation
of the steady-state and semibatch production of methyl acetate, performed in a
packed column with a catalytic packing. For the model validation, several experi-
ments were carried out in a pilot-plant column. For the investigated operation
range, the simulation results are in good agreement with the experimental data.
The use of this model for model-based process control calls for suitable
model reductions without a signicant decrease in the predictivity. For the methyl
acetate process, a simplied description of the mass transfer using effective dif-
fusion coefcients and neglecting diffusional interactions seems to be sufcient.
On the other hand, a detailed description of the reaction, including the specic
phenomena of the heterogeneous catalysis by an adequate consideration of the solid
phase, is required for the predictive simulation of even more complex systems,
including side and consecutive reactions. Optimal functioning of reactive distil-
lation depends on careful process design, with appropriately selected column
internals, feed locations, and catalyst placement. Greater understanding of the
general and particular features of the process behavior is equally essential.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
The modeling of RE processes is strongly related to the knowledge of the
reaction equilibrium and kinetics and mass transfer regime. The latter is decisive for
column simulations, whereas eddy diffusivity concepts often have to be used. The
parameters can easily be obtained in small-scale laboratory devices, with a minimum
of substance involved. A real challenge is the correct hydrodynamic description of
the two-phase ow. The assumption of plug ow gives acceptable results with col-
umn diameters smaller than 0.1 m. The commonly applied axial dispersion model
or back-mixing model uses one parameter to account for nonideal ow in each
phase. Here the dispersed phase is considered to be pseudo-continuous and
monodisperse. Droplet population models taking into account the dynamic pro-
cesses of coalescence and breakup of droplets should give a more realistic picture
and thus a more rm design of a process. The use of CFD calculations in liquid
liquid dispersed-phase ow is limited to single-droplet ow or low column holdup.
The simulation of large industrial columns especially is not feasible nowadays.
Some important general aspects of rate-based modeling as well as further
peculiarities of the specic process applications and the different solution strat-
egies are given in Appendices A and B.
The key reactive separation topics to be addressed in the near future are a
proper hydrodynamic modeling for catalytic internals, including residence time
distribution account and scale-up methodology. Further studies on the hydrodynam-
ics of catalytic internals are essential for a better understanding of RSP behavior
and the availability of optimally designed catalytic column internals for them. In
this regard, the methods of computational uid dynamics appear very helpful.
The development of new methodologies enabling the creation of intelligent,
tailor-made column internals and consequent RSP optimization constitutes one
of the burning present-day challenges. Such a development is already in progress
in some European research projects.
Despite the recent rapid development of computer technology and numer-
ical methods, the rate-based approach in its current realization still often requires
a signicant computational effort, with related numerical difculties. This is one
of the reasons the application of rate-based models to industrial tasks is rather
limited. Therefore, further work is required in order to bridge this gap and pro-
vide chemical engineers with reliable, consistent, robust, and comfortable simu-
lation tools for reactive separation processes.
ACKNOWLEDGMENTS
We would like to thank our colleagues at the Chair of Fluid Separation Processes,
Dortmund University, and all other project partners who have been involved
in the research activities. We are also grateful to the German Research Founda-
tion (DFG, Grants No. Schm 808/5-1, Ba 1569/2-1 2-2, Ba 1569/6-1), the
Volkswagen Foundation (Project No. I/70 875, 876, 877), the European
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
Commission (BRITE-EURAM program, CEC Project No. BE95-1335), the
German Federal Ministry of Education and Research (BMBF, Project No.
03C0306), the Foundation Rheinland-Pfalz fr Innovation (836-386261/193),
as well as BASF AG, Bayer AG, Axiva GmbH, Degussa.
NOMENCLATURE
a
I
specic gasliquid interfacial area m
2
/m
3
A
s
column cross section m
2
B liquid load m
3
/(m
2
s)
c molar concentration mol/m
3
C
IP
adjustable parameter, Eq. (B10)
d
C
column diameter m
d
i
generalized driving force for component i 1/m
d
p
droplet diameter m
MaxwellStefan diffusion coefcient m
2
/s
D
ax
axial dispersion coefcient m
2
/s
D
eff
effective diffusion coefcient m
2
/s
D
Zn
partition coefcient of zinc
E length-specic energy holdup J/m
E
forward-reaction constant m
3/2
/(mol
1/2
s)
r
backward-reaction constant s
1
thermal conductivity W/(m K)
chemical potential J/mol
c
dynamic viscosity of continuous phase Pa s
d
dynamic viscosity of dispersed phase Pa s
volumetric holdup m
3
/m
3
electrical potential V
Subscripts
G gas or second uid phase
i, j component/reaction indices
L liquid phase
t mixture property
Superscripts
B bulk phase
I phase interface
Abbreviations
ADM axial dispersion model
CD catalytic distillation
PDE piston ow model with axial
dispersion and mass exchange
RA reactive absorption
RD reactive distillation
RE reactive extraction
di(2-ethylhexyl) phosphoric acid
RSP reactive separation process
RH
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
REFERENCES
1. Noble T. Multifunctional equipmentall for one, and one for all? Chem Eng Prog
2001; 97(11):1013.
2. Doherty MF, Buzad G. Reactive distillation by design. Trans IChemE 1992; 70:
448458.
3. Zarzycki R, Chacuk A. Absorption: Fundamentals and Applications. Oxford: Perga-
mon Press, 1993.
4. Agar DW. Multifunctional reactors: old preconceptions and new dimensions. Chem
Eng Sci 1999; 54:12991305.
5. Kelkar VV, Ng KM. Design of reactive crystallization systems incorporating kine-
tics and mass-transfer effects. AIChE J 1999; 45:6981.
6. Stankiewicz AI, Moulijn JA. Process intensication: transforming chemical engi-
neering. Chem Eng Prog 2000; 96(1):2234.
7. Fricke J, Schmidt-Traub H, Kawase M. Chromatographic reactors. In: Ullmanns
Encyclopedia of Industrial Chemistry. Weinheim, Germany: Wiley-VCH, 2001.
8. Bart HJ. Reactive Extraction. Berlin: Springer, 2001.
9. Noeres C, Kenig EY, Grak A. Modelling of reactive separation processes: reactive
absorption and reactive distillation. Chem Eng Process 2003; 42:157178.
10. Hatcher WJ. Reaction and mass transport in two-phase reactors. In: Cheremisinoff
NP, ed. Handbook of Heat and Mass Transfer. Vol. 2. Houston: Gulf, 1986:837868.
11. Ritcey GM, Ashbrook AW. Solvent Extraction Principles and Applications to
Process Metallurgy. Vols. I, II. New York: Elsevier, 1979.
12. Lo TC, Baird MHI, Hanson C, eds. Handbook of Solvent Extraction. New York:
Wiley, 1983.
13. Thornton JD, ed. Science and Practice of LiquidLiquid Extraction. Vols. I, II.
Oxford: Oxford University Press, 1992.
14. Marr R, Bart HJ. Metallsalzextraktion. Chem Ing Tech 1982; 54:119129.
15. Godfrey JC, Slater MJ, eds. LiquidLiquid Extraction Equipment. Chichester, UK:
Wiley, 1994.
16. Marcus Y, Sengupta AK, eds. Ion Exchange and Solvent Extraction. Vol. 15.
New York: Marcel Dekker, 2002.
17. Sherwood TK, Pigford RL, Wilke CR. Mass Transfer. New York: McGraw-Hill, 1975.
18. Sherwood TK, Pigford RL. Absorption and Extraction. New York: McGraw-Hill, 1952.
19. Counce RM, Perona JJ. Designing packed-tower wet scrubbers: emphasis on nitro-
gen oxides. In: Cheremisinoff NP, ed. Handbook of Heat and Mass Transfer. Vol. 2.
Houston: Gulf, 1986:953966.
20. Sattler K. Thermische Trennverfahren. Weinheim, Germany: VCH, 1988.
21. Strelzoff S. Choosing the optimum CO
2
-removal system. Chem Eng 1975; 82:
115120.
22. Falbe J. Chemierohstoffe aus Kohle. Stuttgart: Georg-Thieme-Verlag, 1977.
23. Kohl AL, Riesenfeld FC. Gas Purication. Houston: Gulf, 1985.
24. Yu WC, Astarita G. Selective absorption of hydrogen sulphide in tertiary amine
solutions. Chem Eng Sci 1987; 42:419424.
25. Thielert H. Simulation und Optimierung der Kokereigaswsche. Ph.D. dissertation,
Technical University Berlin, Berlin, 1997.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
26. Kobus A. Ein heuristisch-numerischer Ansatz zum systematischen Entwurf und
Design von Absorptionsverfahren. Dsseldorf: VDI, 1999.
27. Danckwerts PV. GasLiquid Reactions. New York: McGraw-Hill, 1970.
28. Astarita G, Savage DW, Bisio A. Gas Treating with Chemical Solvents. New York:
Wiley, 1983.
29. Pal SK, Sharma MM. Solvay-type process: absorption of CO
2
in ammoniated aque-
ous and nonaqueous solutions of NaNO
3
, Ca(NO
3
)
2
, and KCl. Ind Eng Chem Proc
Des Dev 1983; 22:7679.
30. Sauchel V. Chemistry and Technology of Fertilizers. New York: Reinhold, 1960.
31. Gandhidasan P. Heat and mass transfer in solar regenerators. In: Cheremisinoff
NP, ed. Handbook of Heat and Mass Transfer. Vol. 2. Houston: Gulf, 1986:
14751499.
32. Kenig EY, Kholpanov LP, Katysheva LI, Markish IH, Malyusov VA. Calculation of
two-phase nonisothermal absorption in a liquid lm in downward cocurrent ow.
Theor Found Chem Eng 1985; 19:97102.
33. Agreda VH, Partin LR, Heise WH. High-purity methyl acetate via reactive distilla-
tion. Chem Eng Prog 1990; 86(2):4046.
34. Kreul LU, Grak A, Dittrich C, Barton PI. Dynamic catalytic distillation: advanced
simulation and experimental validation. Computers Chem Eng 1998; 22:371378.
35. Grak A, Hoffmann A. Catalytic distillation in structured packings: methyl acetate
synthesis. AIChE J 2001; 47:10671076.
36. Komatsu H, Holland CD. A new method of convergence for solving reacting distil-
lation problems. J Chem Eng Japan 1977; 4:292297.
37. Hartig H, Regner H. Verfahrenstechnische Auslegung einer Veresterungskolonne.
Chem Ing Tech 1971; 43:10011007.
38. Davies B, Jeffreys GV. The continuous trans-esterication of ethyl alcohol and
butyl acetate in a sieve-plate column. Part III: trans-esterication in a six-plate
sieve-tray column. Trans IChemE 1973; 51:275280.
39. Luo HP, Xiao WD. A reactive distillation process for a cascade and azeotropic
reacting system: carbonylation of ethanol with dimethyl carbonate. Chem Eng Sci
2001; 56:403410.
40. Fuchigami Y. Hydrolysis of methyl acetate in distillation column packed with reac-
tive packing of ion exchange resin. J Chem Eng Japan 1990; 23:354358.
41. DeGarmo JL, Parulekar VN, Pinjala V. Consider reactive distillation. Chem Eng
Prog 1992; 88(3):4250.
42. Sundmacher K, Hoffmann U. Activity evaluation of a catalytic distillation packing
for MTBE production. Chem Eng Technol 1993; 16:279289.
43. Thiel C. Modellbildung, Simulation, Design und experimentelle Validierung von
heterogen katalysierten Reaktivdestillationsprozessen zur Synthese der Kraftstoffether
MTBE, ETBE und TAME. Ph.D. dissertation, Technical University of Clausthal,
Clausthal, Germany, 1997.
44. Oost C. Ein Beitrag zum Umweltschutz: Reaktionstechnische Untersuchungen zur
Flssigphasesynthese des Antiklopfmittels TAME. Ph.D. dissertation, Technical
University of Clausthal, Clausthal, Germany, 1995.
45. Shoemaker JD, Jones EM. Cumene by catalytic distillation. Hydroc Proc 1987;
66:5758.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
46. Podrebarac GG, Ng FTT, Rempel GL. The production of diacetone alcohol with
catalytic distillation. Part I: catalytic distillation experiments. Chem Eng Sci 1998;
53:10671075.
47. Ung S, Doherty MF. Vaporliquid equilibrium in systems with multiple chemical
reactions. Chem Eng Sci 1995; 50:2348.
48. Mller D, Schfer JP, Leimkhler HJ. The economic potential of reactive distillation
processes exemplied by silane production. Proceedings of VDI-GVC, DECHEMA
and EFCE Meeting, Section Thermal Separations, Bamberg, Germany, 2001.
49. Ciric AR, Miao P. Steady-state multiplicities in an ethylene glycol reactive distilla-
tion column. Ind Eng Chem Res 1994; 33:27382748.
50. Belson DJ. A distillation method of aromatic nitration using azeotropic nitric acid.
Ind Eng Chem Res 1990; 29:15621565.
51. Fair JR. Design aspects for reactive distillation. Chem Eng 1998; 105(11):158162.
52. Rock K, Gildert GR, McGuirk T. Catalytic distillation extends its reach. Chem Eng
1997; 104(7):7880.
53. Marion MC, Viltard JC, Travers P, Harter I, Forestiere A. U.S. Patent 5,776,320,
Institute Franais du Petrol, 1998.
54. Klocker H, Bart HJ, Marr R, Mller H. Mass transfer based on chemical potential
theory: ZnSO4/H2SO4/D2EHPA. AIChE J 1997; 43:24792487.
55. Bart HJ, Rousselle HP. Microkinetics and reaction equilibria in the system ZnSO4/
D2EHPA/isododecane. Hydrometallurgy 1999; 51:285298.
56. Mrters M, Bart HJ. Mass transfer into droplets in reactive extraction. Chem Eng
Process, 2003, in press.
57. Taylor R, Krishna R. Multicomponent Mass Transfer. New York: Wiley, 1993.
58. Kenig EY, Grak A. A lm model based approach for simulation of multicompo-
nent reactive separation. Chem Eng Process 1995; 34:97103.
59. Kenig EY. Modeling of Multicomponent Mass Transfer in Separation of Fluid
Mixtures. Dsseldorf: VDI, 2000.
60. Sundmacher K, Hoffmann U. Multicomponent mass and energy transport on dif-
ferent length scales in a packed reactive distillation column for heterogeneously cata-
lyzed fuel ether production. Chem Eng Sci 1994; 49:44434464.
61. Krishna R, Wesselingh JA. The MaxwellStefan approach to mass transfer. Chem
Eng Sci 1997; 52:861911.
62. Higler AP, Krishna R, Taylor R. Nonequilibrium modeling of reactive distillation:
a dusty uid model for heterogeneously catalyzed processes. Ind Eng Chem Res
2000; 39:15961607.
63. Yuxiang Z, Xien X. Study on catalytic distillation processes. Part II. Simulation of
catalytic distillation processesquasi-homogenous and rate-based model. Trans
IChemE 1992; 70:465470.
64. Sundmacher K, Uhde G, Hoffmann U. Multiple reactions in catalytic distillation
processes for the production of fuel oxygenates MTBE and TAME: analysis by rig-
orous model and experimental validation. Chem Eng Sci 1999; 54:28392847.
65. Mackowiak J. Fluiddynamik in Kolonnen mit modernen Fllkrperpackungen und
Packungen fr Gas/Flssigkeitssysteme. Frankfurt am Main: Sauerlnder, 2001.
66. Billet R. Packed Towers. Weinheim, Germany: VCH, 1995.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
67. Kenig EY, Klker M, Egorov Y, Menter F, Grak A. Towards improvement of reac-
tive separation performance using computational uid dynamics. Proceedings of
International Symposium on Multifunctional Reactors (ISMR-2), Nuremberg, 2001.
68. Doraiswamy LL, Sharma MM. Heterogeneous Reactions: Analysis, Examples and
Reactor Design. New York: Wiley, 1984.
69. Westerterp KR, van Swaaij WPM, Beenackers AACM. Chemical Reactor Design
and Operation. Chichester, UK: Wiley, 1984.
70. Chen CC, Evans LB. A local composition model for the excess Gibbs energy of
aqueous electrolyte systems. AIChE J 1986; 32:444459.
71. Mock B, Evans LB, Chen CC. Thermodynamic representation of phase equilibria
of mixed-solvent electrolyte systems. AIChE J 1986; 32:16551664.
72. Reid R, Prausnitz JM, Poling BE. The Properties of Gases and Liquids. New York:
McGraw-Hill, 1987.
73. Froment GF, Bischoff KB. Chemical Reactor Analysis and Design. New York:
Wiley, 1990.
74. Taylor R, Krishna R. Modeling reactive distillation. Chem Eng Sci 2000; 55:
51835229.
75. Sorel E. La rectication de lalcool. Paris: GauthiersVillais et Fils, 1893.
76. Henley EJ, Seader JD. Equilibrium-Stage Separation Operations in Chemical
Engineering. New York: Wiley, 1981.
77. van Krevelen DW, Hoftijzer PJ. Kinetics of gasliquid reactionsPart I: General
theory. Recl Trav Chim Pays-Bas 1948; 67:563586.
78. Holma H, Sohlo J. A mathematical model of an absorption tower of nitrogen oxides
in nitric aid production. Computers Chem Eng 1979; 3:135141.
79. Carta G. Scrubbing of nitrogen oxides with nitric acid solutions. Chem Eng
Commun 1986; 42:157170.
80. Suzuki I, Yagi H, Komatsu H, Hirata M. Calculation of multicomponent distillation
accompanied by a chemical reaction. J Chem Eng Japan 1971; 4:2633.
81. Chang YA, Seader JD. Simulation of continuous reactive distillation by homotopy
continuation method. Computers Chem Eng 1988; 12:12431255.
82. Stewart WE, Prober R. Matrix calculation of multicomponent mass transfer in
isothermal systems. Ind Eng Chem Fundam 1964; 3:224235.
83. Toor HL. Solution of the linearized equations of multicomponent mass transfer.
AIChE J 1964; 10:448455, 460465.
84. Grak A. Simulation thermischer Trennverfahren uider Vielkomponentengemische.
In: Schuler G, ed. Prozesssimulation. Weinheim, Germany: VCH, 1995:349408.
85. Seader JD. The rate-based approach for modeling staged separations. Chem Eng
Prog 1989; 85(10):4149.
86. Katti SS. Gasliquidsolid systems: an industrial perspective. Trans IChemE 1995;
73(part A):595607.
87. Lewis WK, Whitman WG. Principles of gas absorption. Ind Eng Chem 1924;
16:12151220.
88. Higbie R. The rate of absorption of a pure gas into a still liquid during short peri-
ods of exposure. Trans Am Inst Chem Engrs 1935; 31:365383.
89. Hirschfelder JO, Curtiss CF, Bird RB. Molecular Theory of Gases and Liquids.
New York: Wiley, 1964.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
90. Pelkonen S, Kaesemann R, Grak A. Distillation lines for multicomponent separa-
tion in packed columnstheory and comparison with experiment. Ind Eng Chem
Res 1997; 36:53925398.
91. Sundmacher K, Hoffmann U. Development of a new catalytic distillation process for
fuel ethers via a detailed nonequilibrium model. Chem Eng Sci 1996; 51:23592368.
92. Davidson DL. The enterprise-wide application of computational uid dynamics
in the chemicals industry. Proceedings of the 6th World Congress of Chemical
Engineering, Melbourne, 2001.
93. Sommerfeld M. Modellierung und numerische Berechnung von partikelbeladenen
turbulenten Strmungen mit Hilfe des Euler/Lagrange-Verfahrens. Aachen,
Germany: Shaker Verlag, 1996.
94. Scheuerer G. Solution algorithms and implementations strategies for Eulerian
Eulerian multiphase-ow models. Proceedings of ACFD 2000 International
Conference on Applied Computational Fluid Dynamics, Beijing, 2000.
95. Kuipers JAM, van Swaaij WPM. Application of computational uid dynamics to
chemical reactor engineering. Rev Chem Eng 1997; 13:1118.
96. Sokolichin A, Eigenberger G, Lapin A, Lbbert A. Direct numerical simulation of
gasliquid two-phase ows. Euler/Euler versus Euler/Lagrange. Chem Eng Sci
1997; 52:611626.
97. Krishna R, van Baten JM. Simulating the motion of gas bubbles in a liquid. Nature
1999; 398:208.
98. Krishna R, Urseanu MI, van Baten JM, Ellenberger J. Wall effects on the rise
of single gas bubbles in liquids. Int Commun Heat Mass Transfer 1999; 26:
781790.
99. Ding J, Gidaspow D. A bubbling uidization model using the kinetic theory of
granular ow. AIChE J 1990; 36:523538.
100. Fan LS, Zhu C. Principles of GasSolid Flows. Cambridge: Cambridge University
Press, 1998.
101. Marschall KJ, Mleczko L. CFD modeling of an internally circulating uidized-bed
reactor. Chem Eng Sci 1999; 54:20852093.
102. van Wachem BGM, Schouten JC, Krishna R, van den Bleek CM. Validation of the
Eulerian simulated dynamic behavior of gassolid uidized beds. Chem Eng Sci
1999; 54:21412149.
103. Grienberger J, Hofmann H. Investigations and modelling of bubble columns. Chem
Eng Sci 1992; 47:22152220.
104. Lapin A, Lbbert A. Numerical simulation of the dynamics of two-phase gas
liquid ows in bubble columns. Chem Eng Sci 1994; 49:36613674.
105. Sokolichin A, Eigenberger G. Gasliquid ow in bubble columns and loop reactors.
Part I. Detailed modelling and numerical simulation. Chem Eng Sci 1994; 49:
57355746.
106. Grevskott S, Sannaes BH, Dudukovic MP, Hjarbo KW, Svendsen HF. Liquid circu-
lation, bubble-size distributions, and solids movement in two- and three-phase
columns. Chem Eng Sci 1996; 51:17031713.
107. Lin TJ, Reese J, Hong T, Fan LS. Quantitative analysis and computation of two-
dimensional bubble columns. AIChE J 1996; 42:301318.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
108. Delnoij E, Lammers FS, Kuipers JAM, van Swaaij WPM. Dynamic simulation of
dispersed gasliquid two-phase ow using a discrete bubble model. Chem Eng Sci
1997; 52:14291458.
109. Jakobsen HA, Sannaes BH, Grevskott S, Svendsen HF. Modeling of bubble-driven
vertical ows. Ind Eng Chem Res 1997; 36:40524074.
110. Sanyal J, Vasquez S, Roy S, Dudukovic MP. Numerical simulation of gasliquid
dynamics in cylindrical bubble-column reactors. Chem Eng Sci 1999; 54: 50715083.
111. Thakre SS, Joshi JB. CFD simulation of bubble-column reactors: importance of
drag-force formulation. Chem Eng Sci 1999; 54:50555060.
112. Krishna R, Urseanu MI, van Baten JM, Ellenberger J. Inuence of scale on the
hydrodynamics of bubble columns operating in the churn-turbulent regime: exper-
iments vs. Eulerian simulations. Chem Eng Sci 1999; 54:49034911.
113. Peger D, Becker S. Modelling and simulation of the dynamic ow behavior in a
bubble column. Chem Eng Sci 2001; 56:17371747.
114. Fischer CH, Quarini GL. Three-dimensional heterogeneous modeling of distillation
tray hydraulics. Proceedings of AIChE Annual Meeting, Miami Beach, 1998.
115. Metha B, Chuang KT, Nandakumar K. Model for liquid-phase ow on sieve trays.
Trans IChemE 1998; 76:843848.
116. Krishna R, van Baten JM, Ellenberger J, Higler AP, Taylor R. CFD simulations of
sieve-tray hydrodynamics. Trans IChemE 1999; 77:639646.
117. Lju CJ, Yuan XG, Yu KT, Zhu XJ. A uid-dynamic model for ow pattern on a dis-
tillation tray. Chem Eng Sci 55:22872294, 2000.
118. van Baten JM, Krishna R. Modelling sieve-tray hydraulics using computational
uid dynamics. Chem Eng J 2000; 77:143151.
119. van Baten JM, Ellenberger J, Krishna R. Hydrodynamics of reactive distillation tray
column with catalyst-containing envelopes: experiments vs. CFD simulations.
Catal Today 2001; 66:233240.
120. van Gulijk C. Using computational uid dynamics to calculate transversal disper-
sion in a structured packed bed. Computers Chem Eng 1998; 22:767770.
121. Higler AP, Krishna R, Ellenberger J, Taylor R. Countercurrent operation of a struc-
tured catalytically packed-bed reactor: liquid-phase mixing and mass transfer.
Chem Eng Sci 1999; 54:51455152.
122. van Baten JM, Ellenberger J, Krishna R. Radial and axial dispersion of the liquid
phase within KATAPAK-S structure: experiments vs. CFD simulations. Chem Eng
Sci 2001; 56:813821.
123. Rieger R, Weiss C, Wigley G, Bart HJ, Marr R. Investigating the process of liquid
liquid extraction by means of CFD. Computers Chem Eng 1996; 20:14671475.
124. Zahiarieva A, Masberat O, Aoun Nabli M, Giraud P, Gourdon C. Experimental and
numerical 2D turbulent eld in a pulsed extraction column. In: Shallcross DC
et al., eds. Value Adding Through Solvent Extraction. Vol. 2. Melbourne: University
of Melbourne, 1996:12331238.
125. Fei WY, Wang YD, Wan YK. Physical modelling and numerical simulation of
velocity elds in rotating-disc contactor via CFD simulation and LDV measure-
ment. Chem Eng J 2000; 78:131139.
126. Modes G, Bart HJ. CFD simulations of nonideal dispersed-phase ow in stirred
extraction columns. Chem Eng Technol 2002; 24:12421245.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
127. Bart HJ. From single droplet to column design. Keynote lecture at 6th World
Congress on Chemical Engineering, Melbourne, 2001.
128. Suchak NJ, Jethani KR, Joshi JB. Modeling and simulation of NO
x
absorption in
pilot-scale packed columns. AIChE J 1991; 37:323339.
129. Wiesner U, Wittig M, Grak A. Design and optimization of a nitric acid recovery
plant from nitrous waste gases. Computers Chem Eng 1996; 20:S1425S1430.
130. Ulrichs K, Laue W, Renovanz HD. Salpetersure und salpetrige Sure, Stickst-
offoxide, Nitrate, Nitrite. In: Ullmanns Encyclopdie der technischen Chemie.
Vol. 20. Weinheim, Germany: VCH, 1981:305362.
131. Wiesner U, Grak A, Kenig EY, Steude H, Brger GG. Modelling of absorption of
nitrous waste gases. IChemE Symp Ser 1997; 142(1):323333.
132. Kafarov VV, Shestopalov EA, Novikov EA, Belkov VP. Mathematical model of
absorption of NO
x
in production of weak nitric acid. Soviet Chem Ind 1975; 7:
12241226.
133. Kolev N. Wirkungsweise von Fllkrperschttungen. Chem Ing Tech 1976; 48:
11051112.
134. Brauer H. Stoffaustausch einschliesslich chemischer Reaktionen. Aarau: Sauerlnder,
1971.
135. Kenig EY, Wiesner U, Grak A. Modeling of reactive absorption using the
MaxwellStefan equations. Ind Eng Chem Res 1997; 36:44254434.
136. Danckwerts PV, Sharma MM. The absorption of carbon dioxide into solutions of
alkalis and amines (with some notes on hydrogen sulde and carbonyl sulde). The
Chemical Engineer 1966; (JulyAug):244280.
137. Maurer G. On the solubility of volatile weak electrolytes in aqueous solutions. ACS
Symp Ser 1980; 133:139172.
138. Tippmer K. Progress in the desulphurization of coke oven gas and utilization of
H
2
S-Still Ottos SOLOX process. Coke Making Int 1994; 6:3243.
139. Schneider R, Kenig EY, Grak A. Dynamic modelling of reactive absorption with
the MaxwellStefan approach. Trans IchemE 1999; 77(part A):633638.
140. Kenig EY, Schneider R, Grak A. Rigorous dynamic modelling of complex reactive
absorption processes. Chem Eng Sci 1999; 54:51955203.
141. Schneider R, Grak A. Model optimization for the dynamic simulation of reactive
absorption processes. Chem Eng Technol 2001; 24:979989.
142. Schneider R, Kenig EY, Grak A. Complex reactive absorption processes: model
optimization and dynamic column simulation. Proceedings of ESCAPE 11 European
Symposium on Computer-Aided Process Engineering, Kolding, Denmark, 2001.
143. Kenig EY, Schneider R, Grak A. Reactive absorption: optimal process design via
optimal modelling. Chem Eng Sci 2001; 56:343350.
144. Pantelides CC. The consistent initialization of differential-algebraic systems. SIAM
J Sci Stat Comp 1988; 9:213231.
145. Schneider R, Kenig EY, Grak A. Dynamische Simulation reaktiver Absorption-
sprozesse am Beispiel einer Sauergaswsche: Modellentwicklung, -analyse und
-optimierung. Chem Ing Tech 2000; 72:12241229.
146. Song W, Venimadhavan G, Manning JM, Malone MF, Doherty MF. Measurement
of residue curve maps and heterogeneous kinetics in methyl acetate synthesis. Ind
Eng Chem Res 1998; 37:19171928.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
147. Grak A, Kreul LU, Skowronski M. Strukturierte Mehrzweckpackung. German
patent 19701045 A1, 1998.
148. Schneider R, Noeres C, Kreul LU, Grak A. Dynamic modeling and simulation of
reactive batch distillation. Computers Chem Eng 1999; 23:S423S426.
149. Schneider R, Noeres C, Kreul LU, Grak A. Dynamic modeling and simulation of
reactive batch distillation. Computers Chem Eng 2001; 25:169176.
150. Krafczyk J, Gmehling J. Einsatz von Katalysatorpackungen fr die Herstellung von
Methylacetat durch reaktive Rektikation. Chem Ing Tech 1994; 66:13721375.
151. Hoffmann A, Grak A. Scale-up of reactive distillation columns with catalytic
packing. Chem Eng Process (submitted).
152. Gicquel A, Torck B. Synthesis of methyl tertiary butyl ether catalyzed by ion-
exchange resin. Inuence of methanol concentration and temperature. J Catal 1983;
83:918.
153. Rehnger A, Hoffmann U. Kinetics of methyl tertiary butyl ether liquid-phase syn-
thesis catalyzed by ion exchange resin. I. Intrinsic rate expression in liquid-phase
activities. Chem Eng Sci 1990; 45:16051617.
154. Parra D, Tejero J, Cunill F, Iborra M, Izquierdo JF. Kinetic study of MTBE liquid-
phase synthesis using C
4
olen cut. Chem Eng Sci 1994; 49:45634578.
155. Kenig EY, Jakobsson K, Banik P, Aittamaa J, Grak A, Koskinen M, Wettmann P.
An integrated tool for synthesis and design of reactive distillation. Chem Eng Sci
1999; 54:13471352.
156. Kolarik Z. Critical evaluation of some equilibrium constants involving acidic
organophosphorous extractants. Pure Appl Chem 1982; 54:25932674.
157. Kolarik Z, Grimm R. Acidic organophosphorous extractants XXIV: the polymer-
ization behavior of Cu(II) Cd(II), Zn(II) and Co(II) complexes of D2EHPA in fully
loaded organic phases. J Inorg Nucl Chem 1976; 38:17211727.
158. Mrters M, Bart HJ. Extraction equilibria of zinc with bis(2-ethyl-hexyl) phos-
phoric acid. J Chem Eng Data 2000; 45:8285.
159. Bart HJ. Reactive extraction of acids and metalsthe state of the art in column
design. Chem Eng Sci 2002; 57:16331637.
160. Schfer JP, Sluyts D. Aufarbeitung eines Prozessabwassers mittels Reaktivextraktion.
In: VDI-Jahrbuch. Dsseldorf: VDI, 1996:285295.
161. Veglio F, Slater MJ. Design of liquidliquid extraction columns for the possible test
system Zn/D2EHPA in n-dodecane. Hydrometallurgy 1996; 42:177195.
162. Mansur MB, Slater MJ, Biscaia EC. Kinetic analysis of the reactive liquidliquid
test system ZnSO4/D2EHPA/n-heptane. Hydrometallurgy 2002; 63:107116.
163. Mansur MB, Slater MJ, Biscaia EC. Equilibrium analysis of the reactive liquid
liquid test system ZnSO4/D2EHPA/n-heptane. Hydrometallurgy 2002; 63:117126.
164. Steiner L. Mass-transfer rates from single drops and drop swarms. Chem Eng Sci
1986; 41:19791986.
165. Slater M. A combined model of mass transfer coefcient for contaminated drop
liquid liquid systems. Can J Chem Eng 1995; 73:462469.
166. Brodkorb M, Slater MJ. Multicomponent and contamination effects on mass trans-
fer in a liquidliquid extraction rotating disk contactor. Trans IChemE 2001;
79(part A):335346.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
167. Kenig EY, Butzmann F, Kucka L, Grak A. Comparison of numerical and analyti-
cal solutions of a multicomponent reactionmass transfer problem in terms of the
lm model. Chem Eng Sci 2000; 55:14831496.
168. Noeres C, Benvenuti C, Hoffmann A, Grak A. Reactive distillation: nonideal-ow
behavior of the liquid phase in structured catalytic packings. Proceedings of Inter-
national Symposium on Multifunctional Reactors (ISMR-2), Nuremberg, 2001.
169. Higler AP, Krishna R, Taylor R. Nonequilibrium-cell model for multicomponent
(reactive) separation processes. AIChE J 1999; 45:23572370.
170. Danckwerts PV. Continuous ow systemsdistribution of residence times. Chem
Eng Sci 1953; 2:113.
171. van Swaaij WPM, Harpentier JC, Villermaux J. Residence time distribution in the
liquid phase of trickle ow in packed columns. Chem Eng Sci 24:10831095, 1969.
172. Noeres C, Grak A. Zur dynamischen Modellierung der Reaktivrektikation unter
Bercksichtigung des Verweilzeitverhaltens katalytischer Packungen. Proceedings
of GVCFachausschuss Thermische Zerlegung, Bingen, Germany, 2002.
173. Rod V. Calculating mass transfer with longitudinal mixing. Br Chem Eng 1966;
6:483488.
174. Casamatta G. Compartment de la population des gouttes dans une colonne dex-
traction: transport, rupture, coalescence, transfer de matiere. Ph.D. dissertation,
Institute National Polytechnique de Toulouse, Toulouse, France, 1981.
175. Kronberger T, Ortner A, Zulehner W, Bart HJ. Numerical simulation of extraction
columns using a drop population model. Computers Chem Eng 1995; 19:639644.
176. Ortner A, Kronberger T, Zulehner W, Bart HJ. Tropfen-Populanz-Bilanzmodell am
Beispiel einer gerhrten Extraktionskolonne. Chem Ing Tech 1995; 67:984988.
177. Gerstlauer A. Herleitung und Reduktion populationsdynamischer Modelle am
Beispiel der FlssigFlssig Extraktion. Dsseldorf: VDI, 1999.
178. Modes G. Grundstzliche Studie zur Populationsdynamik einer Extraktionskolonne
auf Basis von Einzeltropfenuntersuchungen. Aachen, Germany: Shaker, 2000.
179. Attarakih M, Bart HJ, Faqir NM. An approximate optimal moving-grid technique
for the solution of discretized population balances in batch systems. Proceedings of
ESCAPE 12 European Symposium on Computer-Aided Process Engineering, The
Hague, 2002.
180. Simon M, Bart HJ. Experimental studies of coalescence in liquid/liquid systems.
Chem Eng Technol 2002; 25:481484.
181. Wei J, Prater CD. The structure and analysis of complex reaction systems. Adv
Catal 1962; 13:203392.
182. Hikita H, Asai S. Gas absorption with (m, n)-th order irreversible chemical reac-
tions. Int Chem Eng 1964; 4:332340.
183. Toor HL. Dual diffusion-reaction coupling in rst order multicomponent systems.
Chem Eng Sci 1965; 20:941951.
184. DeLancey GB. Multicomponent lm-penetration theory with linearized kinetics
I. Linearization theory and ux expression. Chem Eng Sci 1974; 29:23152323.
185. Astarita G, Sandler SI. Kinetic and Thermodynamic Lumping of Multicomponent
Mixtures. Amsterdam: Elsevier, 1991.
186. Kenig EY, Kholpanov LP. Analysis of formulation and solution of multicomponent
reaction-diffusion problems. Theor Found Chem Eng 1992; 26:510521.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
187. Onda K, Takeuchi H, Okumoto Y. Mass transfer coefcients between gas and liq-
uid phases in packed columns. J Chem Eng Japan 1968; 1:5662.
188. Fuller EN, Schettler PD, Giddings JC. A new method for prediction of binary gas-
phase diffusion coefcients. Ind Eng Chem 1966; 58:1927.
189. Siddiqi MA, Lucas K. Correlations for prediction of diffusion in liquids. Can J
Chem Eng 1986; 64:839843.
190. Mika V. Model of packed absorption column. I. Physical absorption. Coll Czech
Chem Commun 1967; 32:29332943.
191. Schwartz SE, White WH. Solubility equilibria of the nitrogen oxides and oxyacids in
dilute aqueous solutions. In: Pfafin JR, Zeigler EN, eds. Advances in Environmental
Science and Engineering. Vol. 4. New York: Gordon and Breach, 1981:145.
192. Engels H. Anwendung des Modells der lokalen Zusammensetzung auf Elektro-
lytlsungen. Ph.D. dissertation, RWTH Aachen, Aachen, Germany, 1985.
193. Horvath AL. Handbook of Aqueous Electrolyte Solutions. Chichester, UK: Ellis
Horwood, 1985.
194. Rocha JA, Bravo JL, Fair JR. Distillation columns containing structured packings
2. Mass transfer model. Ind Eng Chem Res 1996; 35:16601667.
195. Ranzi E, Rovaglio M, Faravelli T, Biardi G. Role of energy balances in dynamic
simulation of multicomponent distillation columns. Computers Chem Eng 1988;
12:783786.
196. Ronge G. berprfung unterschiedlicher Modelle fr den Stoffaustausch bei der
Rektikation in Packungskolonnen. Dsseldorf: VDI, 1995.
197. Xu ZP, Chuang KT. Kinetics of acetic acid esterication over ion exchange cata-
lysts. Can J Chem Eng 1996; 74:493500.
198. Powers MF, Vickery DJ, Arehole A, Taylor R. A nonequilibrium-stage model of
multicomponent separation processesV. Computational methods for solving the
model equations. Computers Chem Eng 1988; 12:12291241.
199. Ellenberger J, Krishna R. Countercurrent operation of structured catalytically
packed distillation columns: pressure drop, holdup, and mixing. Chem Eng Sci
1999; 54:13391345.
200. Moritz P, Hasse H. Fluid dynamics in reactive distillation packing Katapak-S.
Chem Eng Sci 1999; 54:13671374.
201. Stichlmair JG, Fair JR. Distillation: Principles and Practice. New York: Wiley-
VCH, 1998.
202. Sundmacher K, Hoffmann U. Macrokinetic analysis of MTBE synthesis in chemi-
cal potentials. Chem Eng Sci 1994; 49:30773089.
203. Mrters M, Bart HJ. Fluorescence-indicated mass transfer in reactive extraction.
Chem Eng Technol 2000; 23:17.
204. Mack C. Untersuchungen zum Stofftransport und Stoffaustauschverhalten bei der
Extraktion von Chrom (III) und Zink mittels D2EHPA. Ph.D. dissertation,
Technical University of Darmstadt, Darmstadt, Germany, 2000.
205. Marangoni CGM. ber die Ausbreitung der Tropfen einer Flssigkeit auf der
Oberche einer anderen. Ann Phys Chem (Poggendorf) 1871; 143:337354.
206. Thomson W (Lord Kelvin). The inuence of wind on waves in water supposed fric-
tionless. Phil Mag 1871; 10:330333.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
207. Pitzer KS. Theory: ion interaction approach. In: Pytkowicz RM, ed. Activity
Coefcients in Electrolyte Solutions. Vol. 1. Boca Raton, FL: CRC Press, 1979:
157208.
208. Hildebrand JM, Scott RL. The Solubility of Nonelectrolytes. New York: Reinhold,
1950.
209. Henschke M, Pfennig A. Mass transfer enhancement in single-drop extraction
experiments. AIChE J 1999; 45:20792086.
210. Handlos AE, Baron T. Mass and heat transfer from drops in liquidliquid extrac-
tion. AIChE J 1957; 3:127136.
APPENDIX A. A DETAILED DESCRIPTION OF
RATE-BASED MODELING
A.1. Balance Equations
The mass balance equations of the traditional multicomponent rate-based model
(see, e.g., Refs. 57 and 58) are written separately for each phase. In order to give
a common description to all three considered RSPs (where it is possible, of
course) we will use the notion of two contacting uid phases. The rst one is
always the liquid phase, whereas the second uid phase represents the gas phase
for RA, the vapor phase for RD and the liquid phase for RE. Considering homo-
geneous chemical reactions taking place in the uid phases, the steady-state bal-
ance equations should include the reaction source terms:
(A1)
(A2)
If chemical reactions take place in the (rst) liquid phase only (this is
valid for most of RD processes), the phase balances for the second uid phase
simplify to
(A3)
The bulk-phase balances are completed by the summation equation for the
liquid and second uid bulk mole fractions:
(A4)
x
i
B
i
n
1
1
0 1
d
dl
Gy N a A i n
i
B
Gi
B I
s
( ) , . . . ,
0 1
d
dl
Gy N a R A i n
i
B
Gi
B I
Gi
B
G s
( ) ( ) , . . . ,
0 1
d
dl
Lx N a R A i n
i
B
Li
B I
Li
B
L s
( ) ( ) , . . . ,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
(A5)
The volumetric liquid holdup,
L
, depends on the gas/vapor and liquid
ows and is calculated via empirical correlations (e.g., Ref. 65). For the determi-
nation of axial temperature proles, differential energy balances are formulated,
including the product of the liquid molar holdup and the specic enthalpy as
energy capacity. The energy balances written for continuous systems are as
follows:
(A6)
(A7)
In the dynamic rate-based stage model, molar holdup terms have to be con-
sidered in the mass balance equations, whereas the changes in both the specic
molar component holdup and the total molar holdup are taken into account. For
the liquid phase, these equations are as follows:
(A8)
(A9)
The gas/vapor holdup can often be neglected due to the low gas-phase
density, and the component balance equation reduces to Eq. (A2) (see also
Ref. 139).
A.2. Mass Transfer and Reaction Coupling in Fluid Films
The component uxes entering into Eqs. (A1)(A3) are determined based on
the mass transport in the lm region. Because the key assumptions of the lm
model result in the one-dimensional mass transport normal to the interface, the
differential component balance equations including simultaneous mass transfer
and reaction in the lm are as follows:
(A10)
Equations (A10), which are generally valid for both liquid and second uid
phases, represent nothing but differential mass balances for the lm region, with the
dN
dz
R i n
Li
Li
0 1, . . . ,
N
i
B
U x U x c A i n
Li i
B
Lt i
B
L Lt s
( ) , . . . , 1
t
U
l
Lx N a R A i n
Li i
B
Li
B I
Li
B
L s
( ) ( ) , . . . , 1
0
0
d
dl
Gh Q a R H A
G
B
G
B I
G
B
G RG s
( ) ( )
0
0
d
dl
Lh Q a R H A
L
B
L
B I
L
B
L RL s
( ) ( )
y
i
B
i
n
1
1
devi-
ates from plug-ow behavior (Figure 31). Calculated axial dispersion coefcients
are about 10
4
10
2
m
2
/s, which are several orders of magnitude larger than that
for molecular diffusion (Figure 32). Therefore, in the investigated operating
range, nonideal mixing effects are caused by hydrodynamic rather than molecu-
lar diffusion effects. Calculated Bodenstein numbers are one order of magnitude
FIGURE 31 Comparison between the experimental RTD curve for the cata-
lytic packing MULTIPAK
(d
C
0.1 m), the ADM model, and the PDE model.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
smaller than those for xed-bed reactors, which may be caused by two effects: the
occurrence of stagnant zones in the catalyst layer, and liquid bypassing due to the
hybrid structure of the catalytic packing (168).
The rate-based models suggested up to now do not take liquid back-mixing
into consideration. The only exception is the nonequilibrium-cell model for
multicomponent reactive distillation in tray columns presented in Ref. 169. In this
work a single distillation tray is treated by a series of cells along the vapor and
liquid ow paths, whereas each cell is described by the two-lm model (see
Section 2.3). Using different numbers of cells in both ow paths allows one to
describe various ow patterns. However, a consistent experimental determination
of necessary model parameters (e.g., cell lm thickness) appears difcult, where-
as the complex iterative character of the calculation procedure in the dynamic
case limits the applicability of the nonequilibrium cell model.
A far more promising approach is represented by the so-called differential
models, such as the axial dispersion model (ADM) (170) as well as the piston-
ow model with axial dispersion and mass exchange (PDE) (171). Experimental
studies (168) show that the ADM gives an appropriate description of the nonideal
flow behavior of the liquid phase in catalytic packings (see Figure 31). Considering
FIGURE 32 Axial dispersion coefcients for the catalytic packing MULTIPAK
(d
C
0.1 m) , calculated based on the ADM model.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the nonideal ow behavior via the ADM, the dynamic mass balances [cf. Eqs.
(A8)] take the following form:
(A12)
A thorough investigation of the inuence of the ow nonideality in catalytic
packings on the dynamic process behavior of specic CD processes is an objec-
tive of some current studies (172).
Equation (A12) is widely used in RE, but it does not account for the spe-
cic interactions of the dispersed phase. In this respect current research is focused
on drop population balance models, which account for the different rising velo-
cities of the different-size droplets and their interactions, such as droplet breakup
and coalescence (173180).
APPENDIX B. MODELING PECULIARITIES AND
MODEL PARAMETERS FOR THE CASE STUDIES
B.1. Absorption of NO
x
In terms of the concentration vector, Eq. (A10) is a nonlinear differential equa-
tion of the second order. The boundary-value problem [Eqs. (A10) and (A11)] is
usually solved numerically. However, it is also possible to linearize the reaction
term using the method suggested in Ref. 181:
(B1)
Equation (B1) provides a satisfactory representation for many processes over the
entire reaction range and is a good linear approximation for most systems in a suf-
ciently small range (see, e.g., Refs. 68 and 182184). Equation (B1) has gained
widespread acceptance in various chemical and reactor engineering areas (185) and
is recommended for use in the modeling of reactive separation operations (59,184).
The approximation of Eq. (B1) allows one to reduce Eqs. (A10) and (A11)
to a linearized boundary-value problem (183,184,186). The latter can then be
solved analytically and yields a compact matrix-form solution for the concentra-
tion proles in the lm region [58]. Such a solution gives simple analytical
expressions for the component uxes with regard to the homogeneous reaction in
the uid lms (see Ref. 135), which can be of particular value when large indus-
trial reactive separation units are considered and designed.
The methods of determination of the reaction matrix [K] are considered in
Refs. 167, 181, 183, 184 and 186. Another important matrix parameter entering
into the linearized lm mass transport equation is the multicomponent diffusion
matrix [D]. The latter results from the transformation of the MaxwellStefan Eqs. (1)
to the form of the generalized Ficks law (83). Matrix [D] is generally a function of
R x [ ] K
t
U
D
u
l
Lx
l
Lx N a R A i n
Li
L
i
B
i
B
Li
B I
Li
B
L s
ax
2
2
1 ( ) ( ) ( ) , . . . ,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
the mixture composition and it is assumed constant along the diffusion path (83).
The direct expressions for the elements of the diffusion matrix [D] can be found,
for example, in Ref. 57.
The linearization of the initial lm mass transport equation and its analytical
solution were applied to simulate the industrial NO
x
absorption process considered.
In order to calculate the multicomponent diffusion matrices [D], the binary
diffusivities in both phases should be known. The lm thickness representing an
important model parameter is estimated via the mass transfer coefcients (57,83).
The binary diffusivities and mass transfer coefcients were calculated from the
correlations summarized in Table 3.
The correlations of Billet (66) and Onda et al. (187) are valid for various
mixtures and packings and cover both absorption and distillation processes. The
correlation of Kolev (133) is obtained for RA and certain random packings. In
general, the mass transfer coefcient correlations need to be compared to one
another and validated using experimental data. This shows, in particular, the way
the mass transfer correlations inuence the concentration proles of the compo-
nents and other relevant process characteristics.
Nitric acid is a strong electrolyte. Therefore, the solubilities of nitrogen
oxides in water given in Ref. 191 and based on Henrys law are utilized and fur-
ther corrected by using the method of van Krevelen and Hoftijzer (77) for elec-
trolyte solutions. The chemical equilibrium is calculated in terms of liquid-phase
activities. The local composition model of Engels (192), based on the UNIQUAC
model, is used for the calculation of vapor pressures and activity coefcients of
water and nitric acid. Multicomponent diffusion coefcients in the liquid phase
are corrected for the nonideality, as suggested in Ref. 57.
TABLE 3 Binary Diffusion Coefcients and Mass Transfer
Coefcients
Mass transfer
Binary diffusion coefcient
Phase coefcient correlation
Gas Ref. 188 Ref. 187
Ref. 66
Wehmeier (see
Ref. 134)
Liquid Ref. 189 Ref. 187
Ref. 66
Ref. 133
Ref. 190
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
B.2. Coke Gas Purication
In Ref. 139 a purely numerical approach to the solution of the considered com-
plex RA problem was suggested. The liquid lm is treated as an additional bal-
ance region, in which reaction and mass transfer occur simultaneously. Therefore,
the reactions are considered both in the liquid-bulk-phase mass balances, Eq. (A1),
and in the differential balances for the liquid lm, Eq. (A10).
To be able to describe the presence of electrolytes in the system, the elec-
trical driving force also needs to be taken into account (57). Therefore, the gradi-
ent of the electrical potential is introduced into the generalized driving force
d
i
[cf. Eq. (2)]:
(B2)
In dilute electrolyte systems, the diffusional interactions can usually be
neglected, and the generalized MaxwellStefan equations are reduced to the
NernstPlanck equations (B3):
(B3)
where n is the solvent index. The consideration of the electrical potential requires
an additional condition, the electroneutrality, which has to be met in each point
of the liquid phase:
(B4)
Thermodynamic nonidealities are considered both in the transport equations
(A10) and in the equilibrium relationships at the phase interface. Because elec-
trolytes are present in the system, the liquid-phase diffusion coefcients should be
corrected to account for the specic transport properties of electrolyte solutions.
The thermodynamic equilibrium at the gasliquid interface is described as
follows:
(B5)
where the distribution coefcient K
i
comprises fugacities in both phases and
activity coefcients in the liquid phase. For the system considered, the values of
K
i
, Eq. (B5), are determined from the electrolyte NRTL method (70,71).
The liquid-phase diffusion coefcients are found with the NernstHartley
equation (193), which describes the transport properties in weak electrolyte
systems. The gas-phase diffusion coefcients are estimated according to the
y K x i n
i
I
i i
I
1, . . . ,
x z
i i
i
n
1
0
N
c D
dx
d
x z
F
T
d
d
x N i n
Li
Lt Li
L
i
i i i Ln
,
, . . . ,
eff
_
,
1 1
d
x
T
x z
F
T
d
d
i n
i
i
L
i
i i
L
1 1
1
, . . . ,
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
ChapmanEnskogWilkeLee model (72). The correlations for the mass transfer
coefcients are taken from Ref. 194.
B.3. Methyl Acetate System, Batch Distillation
The rate-based models usually use the two-lm theory and comprise the materi-
al and energy balances of a differential element of the two-phase volume in the
packing (148). The classical two-lm model shown in Figure 13 is extended here
to consider the catalyst phase (Figure 33). A pseudo-homogeneous approach is
chosen for the catalyzed reaction (see also Section 2.1), and the corresponding
overall reaction kinetics is determined by xed-bed experiments (34). This
macroscopic kinetics includes the inuence of the liquid distribution and mass
transfer resistances at the liquidsolid interface as well as diffusional transport
phenomena inside the porous catalyst.
For the determination of conversion corresponding to the average residence
time, the reaction kinetics is integrated into the mass balances, and the liquid
FIGURE 33 Film model for a differential packing segment with heteroge-
neous catalyst.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
holdup, as the accumulation term, is accounted for simultaneously, as in Eqs. (A8)
and (A9). Because of low vapor-phase density, the vapor holdup is neglected, and
the vapor-phase-component balance equation reduces to Eq. (A2).
Ranzi et al. [195] found that the full energy balances, including the accu-
mulation term, have to be considered in order to predict correct dynamic process
behavior. Therefore, the differential dynamic energy balance for the liquid phase
is applied as follows:
(B6)
where
(B7)
Similar to the mass balance equation, the vapor-phase energy balance simplies
to Eq. (A7).
Experimental studies were carried out to derive correlations for mass trans-
fer coefcients, reaction kinetics, liquid holdup, and pressure drop for the pack-
ing MULTIPAK
t
E
l
Lh Q a R H A
Q T T N h i n
L L
B
L
B I
L
B
L RL s
L
B L
L
L
B I
Li
i
Li
( ) ( )
( ) , . . . ,
0
1
2
1
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
In order to determine the model parameters, several experiments were per-
formed at laboratory scale. Pressure drop experiments were carried out in glass
columns, with a total packing height of 1 m at ambient pressure. Air/water was used
as a test system, with a circulating liquid phase set at a constant temperature of 20C.
The experimental data cover a wide range of possible column loads. The gas
load for the column with 100-mm diameter was restricted to 1.7 Pa
0.5
. Therefore,
the liquid load was increased to higher values to reach the ooding region of the
catalytic packing. Two different ow regimes similar to those of conventional
structured packings can be observed. Flooding of the packing can be observed at
a pressure drop above 10
3
Pa/m. The possible column loads for MULTIPAK
are
very similar to those reported in Refs. 199 and 200 for KATAPAK-S.
The number of theoretical stages per meter of the catalytic packing was
determined as a function of the gas capacity factor. For the whole range of column
loads, the separation efciency is at least four theoretical stages per meter. Moritz
and Hasse (200) determined an NTSM value of 3 for the laboratory-scale
KATAPAK-S. The separation efciency remains constant for a wide loading
range of the packing. For lower column loads, the NTSM value increases to 6, a
phenomenon already reported in Ref. 90 for the conventional structured packing
Montzpak A3-500. A simple transfer-unit concept assuming all mass transfer
resistance in the vapor phase was used to determine the vapor-side mass transfer
coefcients (201). The mass transfer correlation
(B8)
represents all experimental data with an accuracy of 13%. A comparison with
experimental data is shown in Figure 34.
B.5. Synthesis of Methyl Tertiary Butyl Ether
The mathematical description considered in Section 2.3 and Appendix A was
used as a modeling basis for the specially developed completely rate-based
simulator DESIGNER (155). This tool consists of several blocks, including
model libraries for physical properties, mass and heat transfer, reaction kinetics,
and equilibrium, as well as a specic hybrid solver and thermodynamic package.
DESIGNER also contains different hydrodynamic models (e.g., completely
mixed liquidcompletely mixed vapor, completely mixed liquidvapor plug ow,
mixed pool model, eddy diffusion model) and a model library of hydrodynamic
correlations for the mass transfer coefcients, interfacial area, pressure drop,
holdup, weeping, and entrainment that cover a number of different column inter-
nals and ow conditions.
In DESIGNER, different ways of taking account of heterogeneous reaction
kinetics are available, depending on the reaction rate and character. One further pos-
sibility is to use a detailed model for the heterogeneous catalyst mass transfer
Sh Re Sc
1/3
G G
0 009
0 92
.
.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
efciency based on the approach of Ref. 91. When applying this type of kinetic
model, the intrinsic kinetics data are needed. Another way is the pseudo-homoge-
neous approach, with effective kinetic expressions, by which the kinetics description
is introduced as source terms into the balance equations [cf. Eqs. (A1) and (A2)].
For the system considered here, the reaction is slow as compared to the
mass transfer rate. For this reason the pseudo-homogeneous approach is used, the
reaction being accounted for in the liquid bulk only.
Basically, DESIGNER can use different physical property packages that are
easy to interchange with commercial owsheet simulators. For the case consid-
ered, the vaporliquid equilibrium description is based on the UNIQUAC model.
The liquid-phase binary diffusivities are determined using the method of Tyn and
Calus (see Ref. 72) for the diluted mixtures, corrected by the Vignes equation
(57), to account for nite concentrations. The vapor-phase diffusion coefcients
are assumed constant. The reaction kinetics parameters taken from Ref. 202 are
implemented directly in the DESIGNER code.
B.6. Reactive Extraction of Zinc
In conventional RE processes, the diffusive resistance is concentrated mainly inside
the droplet, whereas the aqueous-side resistance can be neglected. This has been
proven in Ref. 203 using the laser-induced-uorescence (LIF) technique. Usually
the organic phase is more viscous and the diffusion coefcients of the organic com-
plexes are larger than those at the aqueous side, which supports this nding.
The mass transfer within a rigid droplet is determined by the Maxwell
Stefan diffusion. The appropriate diffusion coefcients experimentally determined
FIGURE 34 Sherwood number correlation for MULTIPAK
.
Copyright 2004 by Marcel Dekker, Inc. All Rights Reserved.
for this zinc extraction system in Ref. 204 are presented in Table 4. With nonrigid
droplets, a mass transfer enhancement by internal convection has to be consid-
ered. However, with industrial feed solutions there are always impurities present
that may dampen the mass transfer (8). In contrast, there also might be a mass
transfer increase due to Marangoni effects (205,206). Therefore, for a nal design
of a column, mass transfer measurements are recommended.
The macrokinetics of zinc extraction is discussed in detail in Ref. 8. It is a
combination of a reaction kinetics term (55) with the MaxwellStefan (54) or
eddy diffusion (56). The rate law is as follows:
(B9)
where C
1
, C
2
,
, and
r
, are the estimated kinetics parameter (see EFCE test
systems discussed earlier).
The rate constant for the backward reaction,
r
, can be replaced by the ther-
modynamic equilibrium constant:
(B10)
The species concentrations are formulated in activities using the Pitzer
model (207) for the aqueous phase and the HildebrandScott solubility parame-
ter (208) for the organic phase.
The effective diffusion coefcient is calculated according to the model of
Ref. 209, which accounts for interfacial instabilities. This model includes a
HandlosBaron-like correlation (210) and one adjustable parameter, C
IP
:
(B11) D
w d
C
p
IP
d
c
eff
2048 1
_
,
K
v
r
eq
d
dt
v
R H R RH
R H C
R H
C R H
r
[ ] [ ] [ ] [ ] [ ( )]
[ ] [ ]
[ ]
[ ]
.
.
Zn Zn H Zn
H
2 2
2 2
2
2
2 2
2
2 2
2 2 2
2
1 5
1 5
1
_
,
i
i
n
i
1