Professional Documents
Culture Documents
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
ISBN: 0-8247-4302-4
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10 9 8 7 6 5 4 3 2 1
Founding Editor
HEINZ HEINEMANN
The book you are about to read will introduce you to modern ways of re-
engineering the chemical processing plant by means of Process Intensification (PI).
The story behind this book had begun with the paper Process Intensification:
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 Intensification is a very broad discipline and
includes many diverse expertise fields. So, instead of writing all chapters on our
own, we have invited a number of prominent experts in various areas of Process
Intensification, both from industry and from academia, to contribute to what now
has become the world’s first 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
Intensification. 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
Andrzej Stankiewicz
Jacob A. Moulijn
Preface
Contributors
1. INTRODUCTION
Process intensification (PI) is currently one of the most significant 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-Webster’s 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 first 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
intensification–oriented thinking can be found. One example is shown in Figure 1,
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.
process intensification was the highest-rated activity of DSM within the known
“Triple-P” (profit–planet–people) triangle, as shown in Table 1.
From this general philosophy of process intensification 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.
Triple P
3.1. Costs
Process intensification 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 efficiency
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 intensification 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 intensification would have prevented
all those tragedies. Yet a study done at AIChE showed that methyl isocyanate (MIC),
the poisonous intermediate that was released at Bhopal, could be generated and
immediately converted to final products in continuous reactors that contained a
total inventory of less than 10 kg of MIC (34)! But process intensification offers
not only smaller equipment but also much better possibilities for keeping processes
under control, for instance, via extremely efficient heat removal from exothermic
reactions (one speaks about heat transfer coefficients exceeding 20,000 W/m2K)
or via fully controlled gas–liquid flow in structured catalysts that prevents liquid
maldistribution and hot-spot formation. Furthermore, intensification 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”).
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-m3 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-m3 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, 130–300 injured
1989 hexene, hydrogen
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 1997–2002
(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
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 company’s 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 intensification is
all about.
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 efficient mixing has to be coupled with a solid-catalyzed
reaction a whole family of open-crossflow-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® is shown in Figure 10. It has good mixing
properties and can simultaneously be used as the support for catalytic material.
High geometrical areas per reactor volume, typically 1.5– 4 times higher
than in the reactors with particulate catalysts
Very high catalytic efficiency, practically 100%, due to very short diffusion
paths in thin washcoat layer
Stankiewicz (40) gives a spectacular example of reactor size reduction by a fac-
tor of ca. 100, as a result of replacement of the conventional system with a mono-
lithic reactor operated horizontally in a pipeline.
For highly exothermic reactions the so-called HEX reactors present a very
promising option. The basic common feature of all HEX reactors is much more
favorable heat transfer conditions in comparison with conventional reactors (heat
transfer coefficients typically 3500–7500 W/m2K, heat transfer areas up to
2200 m2/m3). A HEX reactor developed by BHR Group Ltd. (Figure 14) was able
to decrease the by-product formation in one of ICI Acrylics’ processes by 75%
(41) and to decrease the processing time in a Hickson & Welch fine chemical
process from 18 hours to 15 minutes, saving 98.6% of batch time (42).
Even higher values of heat transfer coefficients than those in the HEX reac-
tors can be achieved in microreactors. Here, values up to 20,000 W/m2K are rep-
orted (43). Microreactors (Figure 15) are chemical reactors of extremely small
dimensions that usually have a sandwich-like structure, consisting of a number of
slices (layers) with micromachined channels (10–100 µm in diameter). The layers
perform various functions, from mixing to catalytic reaction, heat exchange, or sep-
aration. Integration of these various functions within a single unit is one of the most
important advantages of microreactors. The very high heat transfer rates achievable
in microreactors allow for isothermal operation of highly exothermic processes (also
important in carrying out kinetic studies). The very low reaction-volume-to-surface-
area ratios make microreactors potentially attractive for carrying out reactions
involving poisonous or explosive reactants (think about partial oxidation reactions).
Also, microchannel heat exchangers have channel sizes around or lower than
1 mm and are fabricated via silicon micromachining, deep X-ray lithography, or
nonlithographic micromachining. The reported values of heat transfer coefficients
in the microchannel heat exchangers range from ca. 10,000 to ca. 35,000 W/m2K
(21,44).
High heat transfer coefficients, though not as high as in the previous case,
are also achievable in spinning disk reactors (Figure 16). This type of reactor has
been developed by Ramshaw’s group at Newcastle University and is primarily
applied to fast and very fast liquid–liquid reactions with large heat effect, such
as nitrations, sulphonations, and polymerizations. At very short residence times
(typically 0.1 s), heat is efficiently removed from the reacting liquid at heat trans-
fer rates reaching 10,000 W/m2K. The spinning disk reactor investigated in one
of SmithKline Beecham’s processes offered a 99.9% reduction in reaction time,
99% reduction in inventory, and 93% reduction in impurity level (45).
Rotational movement and centrifugal forces are used not only in spinning
disk reactors. The earlier-mentioned high-gravity (HiGee) technology, started at
ICI’s New Science Group in the late 1970s as a spinoff of a NASA research proj-
ect in deep space (microgravity environment), has developed into one of the most
promising branches of process intensification. It consists of intensifying the mass
applied for a controlled distributed feed of some of the reacting species, either to
increase the overall yield/selectivity of the process or to facilitate the mass trans-
fer (e.g., direct bubble-free oxygen supply/dissolution in the liquid phase via
hollow-fiber membranes (69)). The membrane can also be used for the in situ
separation of catalyst particles and even homogeneous catalysts from the reaction
products (70). Finally, the membrane can incorporate catalytic material, thus
becoming itself a highly selective reaction-separation system. Membranes are
more and more frequently employed in the life sciences sector, in manufacturing
of pharmaceuticals, in combination with a bioreactor in which enzymatic reaction
takes place (71).
Multifunctional reactors may also combine reaction and phase transition. A
well-known example of such a combination is reactive extrusion. Reactive extrud-
ers have been used increasingly in polymer industries. They enable reactive pro-
cessing of highly viscous materials without a need for using large amounts of
solvents, as is the case in stirred-tank reactors. Most of the reactions carried out
in extruders are single- or two-phase reactions. Recently, however, new types of
extruders have been investigated with catalyst immobilized on the surface of the
screws, which enables carrying out three-phase catalytic reactions (72).
REFERENCES
1. Agricola G. De Re Metallica Libri XII. Basel: J. Froben & N. Episopius, 1556.
2. Taber RE, Hawkinson DR. Fluid Mixing Device. US Pat. 2,894,732, Shell Develop-
ment Company, 1959.
David L. Trent
The Dow Chemical Company, Freeport, Texas, U.S.A.
1. INTRODUCTION
The use of high-gravity, or centrifugal, fields for chemical processing has generated
much interest in recent years. Fluid acceleration creates an environment in which
mass transfer rates are two to three orders of magnitude higher than rates
achieved in more conventional equipment, such as packed towers and stirred
tanks. Heat transfer is also enhanced. Short contact time and fast transfer rates
allow a reduction in equipment size and in-process inventory. Many chemical
processes could benefit from these unique properties by reducing the cost of con-
struction, reducing working capital, improving safety, producing less waste, etc.
In addition, the use of high-gravity fields may provide solutions to processing
problems more effectively and more economically than conventional equipment.
Before exploring the wide range of applications, a brief review of the his-
tory of development, a discussion of the process fundamentals, and an introduc-
tion to mechanical design issues will help to set the boundaries for use of
high-gravity fields in chemical processing.
2. HISTORICAL DEVELOPMENT
The use of centrifugal fields in chemical processing dates to the beginning of the
industry with such physical transport operations as pumping, compression, and
solid/liquid separations. Extending this use into mass and heat transport operations
3. PROCESS FUNDAMENTALS
In order to fully appreciate the application opportunities available from use of
high-gravity fields, an understanding of what happens within the rotor would be
helpful. Since many of the models used to describe chemical processes in more
conventional equipment do not apply to high gravity, much of the information
available is empirical. However, where possible the traditional models are being
modified to match the observed behavior. The process fundamentals of interest
here are mass transfer, heat transfer, fluid distribution and holdup, flooding, pres-
sure drop, power requirements, and rotor internals. Although this last item could
be considered with the mechanical design discussion, it is included here because
the rotor internals can have a significant impact on the other process variables.
3.1. Hydrodynamics
Understanding the flow of liquid and gas through a rotating packed bed is import-
ant to understand the performance results achieved. Liquid flow involves two
components, liquid introduction to the packing and flow through the packing. Flow
through the packing occurs in the radial direction with very little tangential or axial
spreading (see Figure 3). A slight curvature in the radial flow results from the
direction of rotation. The degree of curvature and spreading is primarily a function
of rotor speed and liquid viscosity and less a function of packing type and liquid
flow rate (12,13). Gas flow does not impact liquid flow through the rotor (14).
The flow pattern described results in incomplete wetting of the packing at
the outer diameter of the rotor (13). Thus, not all of the packing surface area is
utilized for mass transfer operations. For maximum use of the packing surface
area, the ratio of the outside diameter to the inside diameter should be minimized.
Scale-up from small-diameter to large-diameter rotors typically provides more
efficient use of the packing. In spite of this incomplete wetting of the packing,
very high mass transfer rates are achieved.
Enhanced mass transfer performance results from the initial contact of the liq-
uid feed with the rotor. Studies at the Higravitec Center of Beijing University of
Chemical Technology (HCBUCT), using a video camera attached to the rotor,
revealed a breakup of the liquid feed into smaller droplets that filled the void spaces
porosity decreases, due to the increased drag of the rotor on the gas (Figure 4b).
This behavior significantly impacts gas-side mass transfer performance (16).
The thickness of the liquid film on the rotor packing helps determine mass
transfer rates. Film thickness can be shown to be inversely proportional to rotor
speed to the 0.8 power (17). Visual measurements using a video camera attached
to the rotor show a water film thickness of 20–80 microns on foam metal packing
and 10 microns on wire gauze packing (15). Theoretical models estimate similar
film thickness values (13,18,19). Film flow is expected to be laminar. In addition
to rotor speed, liquid flow rate and fluid properties affect the film thickness (14).
3.2. Flooding
Rotating packed-bed devices handle high volumes of fluids in a small equipment
volume, compared to packed towers, due to the acceleration of gravity. The
Sherwood flooding correlation for packed towers (25) is expressed as a plot of
0.5
UG2 a p G 0.2 L G
L versus
gε 3 L G L
Early RPB researchers discovered that this flooding correlation for packed tow-
ers applied equally well to RPBs when the gravity term (g) was replaced by cen-
trifugal acceleration (r2). As acceleration increases, the gas flooding velocity
(UG) increases in order to maintain the same value of the first term. Since the ratio
of liquid (L) to gas (G) flow remains constant, liquid flow increases commensur-
ately with gas flow. Most researchers observed higher gas velocities before the
onset of flooding than predicted by the Sherwood correlation (17,26,27).
Measurement of flooding by traditional means of observing a sharp pres-
sure increase as gas rates increase is not effective with the RPB (28). Flooding
can be determined experimentally by adjusting rotor speed and holding gas and
liquid rates constant. Flooding will occur at the point of maximum pressure drop
over a range of rotor speeds (28) or by observing the increased pressure drop
change (inflection point) as a function of decreased rotor speed (27,29).
In liquid–liquid contact, two types of flooding can occur. The design of the
centrifugal contactor defines the throughput capability before flooding occurs.
The second type of flooding relates to the principal interface moving into either
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 defined by the design of the rotor,
bearings, and seals.
4. MECHANICAL DESIGN
Since the development of high-gravity fields 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.
4.3. Seals
Two types of seals are needed to prevent fluid 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 fluids
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.
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.
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 flows (9).
An example of industrial relevance is the removal of sulfur dioxide (SO2)
from vent gases by absorption into water or a lime slurry (48). In the water
absorption process, both gas-film and liquid-film resistance to mass transfer
occurs. As a result the overall mass transfer rate is proportional to gas-flow rate
and acceleration but inversely proportional to liquid-flow rate. Due to the fast
reaction of SO2 with lime, this system is only gas-film diffusion limited. The
overall mass transfer rate is largely unaffected by gas- or liquid-flow 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 transfer–limited absorption involving
SO2 absorption into a sodium hydroxide solution using a wire screen packing, the
overall mass transfer coefficient was found to be lower than reported data for
packed towers (16). Replacing the wire screen packing with two parallel rotating
plates significantly 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-flow rate. Heat of absorption removal was identified 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 field recovery and boiler
water feed (7). The oil field application demonstrated oxygen removal from 6–14
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-m2/m3 volumetric surface area
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 reflux. The pilot plant consisted of two RPBs, one for
stripping and one for rectification, along with external reboiler and condenser,
respectively (51). Retrofit 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 reflux. The system provided up to 6 transfer units
(NTU) of separation in a 21-cm packing depth. The primary variable affecting
5.5. Adsorption
Centrifugal adsorption technology (CAT) allows the use of very small adsorbent
particles (microns) to increase the mass transfer efficiency. Application to ion
5.7. Crystallization
In the reactive precipitation process of reacting CO2 with Ca(OH)2 slurry to pro-
duce nanoparticles of CaCO3, the controlling steps of the process are absorption
of CO2 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 CaCO3 particles of size 15–30 nm with
a narrow size distribution. Reaction time reduces 4- to 10-fold, compared to
stirred-tank reactors. Rotor speed, gas–liquid ratio, and initial calcium hydroxide
concentration influence 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 (NaAlO2), water,
and carbon dioxide and are formed in diameters of 1–10 nm and lengths of
50–300 nm. Rotor speed, gas- and liquid-flow 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 liquid–liquid
reaction of strontium nitrate and sodium carbonate.
Crystallization that occurs during evaporation can potentially be intensified
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 fluid (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 (1–15 microns) and narrow particle size distribution (59).
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
7. FUTURE
Extension of the use of centrifugal fields into chemical processing, beyond the
physical movement of fluids, has shown limited niche application in the past, in
spite of considerable research activity. Specialty application of centrifugal fields
to liquid–liquid 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 efficiencies as compared to other liquid–liquid
extractors.
The commercial use of rotating equipment for the broader field of gas–
liquid operations has only a five-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 fields 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 gas–liquid loadings. Process performance in both cases
met or exceeded design criteria, with good operating reliability.
Further application will likely require significant cost or performance
advantages over more conventional process technology. Considerable commer-
cial experience will be needed before centrifugal fields 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 define the fun-
damental performance characterizations is needed. A number of empirical corre-
lations have been developed for pressure drop, residence time, power, flooding,
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
beneficial to confidently scale-up the technology.
C. Ramshaw
University of Newcastle upon Tyne, Newcastle upon Tyne,
England
1. INTRODUCTION
When considering the options for intensifying reactions that involve multiple
fluids, 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 fitted 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 baffles, as
shown. If a gas–liquid 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 superficially 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 difficult 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
could influence 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 fine 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 signifi-
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 significantly erodes the time available under
patent cover to recoup a company’s R&D expenditure and make a profit from a
potential “blockbuster” drug.
shown schematically in Figure 2. The equivalent stage height within the toroidal
packing is about 1.5 cm for a gas film—limited system, compared with about
60 cm in a conventional packed column. Equivalent flooding velocities may
be estimated from the Sherwood plot and can be very high, even for packing with
a specific surface area exceeding 1000 m1. Since the Higee duty was origi-
nally envisioned as being purely orientated to mass transfer, no specific 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
gas–liquid reactor (when fitted 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 film generated on its surface, and between the film and the
adjacent gas. The performance and applications of the SDR are considered in
detail later.
As might be expected, the enhanced acceleration field is established on a
permanent basis within a rotor that receives and discharges the working fluid. The
alternative approach, which relies upon a permanent vortex field, i.e., a cyclone,
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 O in 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 particle’s kinetic energy. Conversely, if the string were lengthened, the par-
ticle’s 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 dr兾dt, v, respectively, giving a resultant VR that is a tangent to the
spiral trajectory.
Noting that dr兾dt << v, the angle between v and VR is , where
tan (dr兾dt)兾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:
dv v 2 dr 1
m T sin m ⋅ ⋅ (as → 0)
dt r dt v
or
dv dr v
⋅ (1)
dt dt r
This confirms that v increases for an inward spiral trajectory (i.e., when
dr兾dt is negative). From Eq. (1) we have
dv dr
v r
and integration from v1r1 to v2r2 gives
2
dr
⋅
dt
Note that since the fluid is forced to rotate at the disc speed, is constant.
The change in angular momentum given by Eq. (3) is brought about by the torque
generated by a tangential force F exerted on the fluid at the radius r by the radial
channel and acting for a time dt. Since dM Fr dt, the tangential acceleration
imposed by the channel on the fluid as it moves radially is
F 1 dM dr
2 (4)
m r dt dt
This is the Coriolis acceleration, which is imposed on particles moving in a rotat-
ing reference frame—e.g., liquids on a rotating surface or winds in the earth’s
atmosphere. The resultant acceleration experienced by a particle is a combina-
tion of the radial and tangential components, making an angle to the radius,
where
dr 2 dr
tan 2 2 r
dt v dt
In general
dr
<< v
dt
and the unconstrained flow will be largely radial. This can be readily confirmed
during the operation of a spinning disc reactor or a rotating packed bed, because
any deposits from the fluid flow lie close to the radius vector.
on the schematic representation given in Figure 7. Part b represents the local film
at a radius r. The shear stress on the annular plane at a distance y from the disc
provides the radial acceleration for the fluid lying between y y and y s. Thus a
force balance on the film lying between r r and r r dr, with zero shear
stress at the gas–liquid interface, gives
du
2 r ( s y) (5)
dy
1 s w 2 rs 2
Uav
s ∫0 u dy
3
Referring to Figure 7a, the liquid is supplied to the disc at a radius ri and a
mass flow 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 flow rate is given by
M Uav s2r (8)
Hence the average time required for the liquid to travel from ri to ro is
1/ 3
dr 3 12 2
(ro )
R0
t ∫ ri4 / 3
4/3
(11)
Ri Uo 4 M 2 2
If we consider a typical example of water flowing over a disc under the fol-
lowing conditions:
then from Eq. (11) the average liquid transit time on the disc is 0.25 s, and from
Eq. (9) the film thickness at the disc edge (provided that the film does not break
up into rivulets) is 28 microns. A more viscous liquid, such as a polymer (say,
10 N-s/m2), would have a thickness at the disc periphery of 600 microns and
a transit time of about 5 seconds.
As already noted, the foregoing calculations must be regarded as a guide
only, since the films are intrinsically unstable, with waves being amplified as the
liquid proceeds to the edge of the disc. It will be appreciated that this process pro-
ceeds more rapidly with relatively inviscid liquids.
2.1.1. Mass Transfer
A conservative estimate of the disc’s mass transfer performance may be obtained
from the Nusselt model, assuming that there is no film mixing as it proceeds to
the edge of the disc. For unsteady diffusion into a finite stagnant slab, the plot
shown in Figure 8 from (8) gives the relative concentration distribution within the
slab at various times, with a zero initial concentration and a surface concentration
C0 imposed at time t 0. The parameter on the curves is the Fourier number, Fo,
where
Dte
Fo (12)
s2
and
D solute diffusivity within the film
te exposure time of the film surface
s film thickness
As can be seen from Figure 8, if Fo 0.02, the concentration changes
within the film are confined largely to the surface layer and the local mass trans-
fer coefficient is given by the Higbie penetration theory (9) as
1/ 2
D
kL (13)
te
For the previous example of a polymer flowing over the disc, a typical
Fourier number may be calculated from:
D ⬇ 109 m 2 /s
te ⬇ 5 s
s ⬇ 6 104 m
Thus Fo 0.014.
Equation (7) shows that the film surface velocity is given by
1/ 3
9 M 2 2
Umax 1.5 Uav ⋅ 2 r −1/ 3
32
However, it must be noted that as the film flows over the disc, the film thick-
ness progressively decreases, provided the liquid fully wets the disc. As this
occurs, the concentration profiles 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 kL can be corrected to
account approximately for the steepened concentration gradients by multiplying
by a factor s1兾s, where s1 is the film thickness at a radius r1 as given by Eq. (9).
The corrected local value of kL is then
1/ 6 2/3
1/ 2
2 M 2 2 r
kL
D 1
(16)
3
(r )
2 1/ 2
r1 4/3
r14 / 3
At the point of film formation, where r r1, Eq. (16) shows that kL .
However, the average value of kL over the disc surface is given by
r2
)∫
1
k Lav 2
k L r dr
(
(17)
r2 r12
2
r1
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 film by ripples has been neglected. This will reduce the exposure time sig-
nificantly, 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 gas–liquid interface and subsequently conducted through the draining con-
densate film, the conduction path length being the local film thickness. When a
liquid film 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 film. Since the thermal diffusivity of most
liquids is typically of the order of 107 m2/s, compared with a mass diffusivity of
around 109 m2/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 film rather than merely
T A By Cy 2 (18)
For our earlier example with water on a 0.5-m-diameter disc, Eq. (21)
implies that the heat transfer film coefficient at the periphery is 43 kW/m2k, with
the predicted film thickness of 28 microns. For this estimate to be realistic it is
essential that the film 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 film stagnation point the film momentum is potentially destroyed by the action
of the component of the surface forces parallel to the disc. Thus for an average film
velocity Uav we must satisfy the following condition for rivulet maintenance:
T (1 cos ) Uav
2
s
where T is the surface tension per unit length, is the contact angle, is the liq-
uid density, and s is the local film thickness.
Coherent films are less likely as they become thinner and their velocity
decreases. An inspection of Eqs. (9) and (10) reveals that U 2av s is proportional to
2/3M5/3. Hence the tendency to form rivulets is less at higher disc speeds and liq-
uid flow rates and increases with large T and small .
2.1.3. Film-Flow Instability
The existence of the wave structure within the film is of major practical interest, as
was highlighted by some elegant experimental work conducted by Brauner
and Maron (7). They monitored the instantaneous local film thickness of a
liquid flowing down a stationary inclined plane using a capacitance technique.
The only single-phase item involved is the solution heat exchanger, which
is intensified by the use of laminar flow in a matrix of fine 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 fulfills the four functions listed.
The working fluid 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 fluid 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 efficient 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 fluid 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 coefficient of performance of 1.0 at a tem-
perature lift of 35C using lithium bromide solution. This unit is about to enter
field trials. Its high performance is entirely due to the intensity of the heat and
mass transfer environment generated on the liquid film flowing 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
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 film 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 (kL 4 → 10 m/s 104) and
the Higbie predictions (approx 1 m/s 104) based upon total exposure time of
liquid on the disc. Clearly, liquid mixing within the film generates exposure times
that are much shorter than the liquid residence time on the disc.
Another study, by Jachuck and Ramshaw (17), explored the influence of
surface profile 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 significantly improved performance—presumably due
to the better film 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 film radial velocity was such that liquid was
projected off the disc, thereby compromising the heat transfer process.
any process, the SDR can radically improve the economics and efficiency of
many key processes, both in the commodity and in the fine chemical area.
In order to exert full control over the progress of a chemical reaction or phys-
ical transformation, the fluid dynamic environment must be sufficiently 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 A B → C, with the
reactants A, B traveling in plug flow 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 A兾B separation. This represents a total loss of control on two
counts:
1. The A兾B 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.
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 benefits 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 5–10 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.
TABLE 1 Comparison of the Best SDR Runs with Batch Results for
Conversion of -Pinene Oxide to Campholenic Aldehyde
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 0.18–0.32 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 0.1–1 microns, compared with 1–10 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
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 significant 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 significantly impairing the disc’s heat transfer performance.
fabricated in 316 stainless steel, complete with computer control and a service
unit delivering a disc temperature in the range 20C–150C. The cost of such a
reactor is estimated to be £250,000 with a range of £200–£400K.
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/Specification
The SDR system is available as a “desktop” or a “floor-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 floor 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 significant 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
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 7 mL/s;
fast down, with index and control system
c. Stirrers for the injectors £1,000
d. Cooled deflector ring system £1,400
e. Receivers, for operation up to 10 bar
1L £980
2L £1,400
4L £1,960
f. Additional instrumentation
Measurement of heat transfer fluid flow rate £1,400
Measurement of temperature difference across disc £400
Added temperature measurements (per channel) £100
Added pressure measurement (per channel) £400
3. CONCLUSION
It will be apparent from the examples cited that centrifugal fields in general, and
rotating surfaces in particular, can exert a profound influence 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 insufficiently persuasive for the acceptance and adoption of SDR tech-
nology. However, it has now been demonstrated that in addition to yielding
REFERENCES
1. Mallinson R, Ramshaw C. European Patent No. 2568B, 1969.
2. Woods WP. The hydrodynamics of thin liquid films flowing over a rotating disc.
Ph.D. dissertation, Newcastle University, Newcastle, U.K., 1995.
3. Thomas S, Faghri A, Hankey W. Experimental analysis and flow visualization of a
thin liquid on a stationary and rotating disc. Trans Asme—J Fluids Eng 1991; 113
(March):73–80.
4. Wasden FK, Dukler AE. A numerical study of mass transfer in free-falling wavy
films. AIChE 1990; 36(9):1379–1390.
5. Oron A, Davies SH, Bankoff SG. Long-scale evolution of thin liquid films. Rev
Modern Physics 1997; 69(3):931–980.
6. Brauner N, Maron DM, Dukler AE. Modeling of wavy flow in inclined thin films in
the presence of interfacial shear. Chem Eng Sci 1985; 40(6):923–937.
7. Brauner N, Maron DM. Characteristics of inclined thin films, waviness and the asso-
ciated mass transfer. Int J Heat Mass Trans 1982; 25(1):99–110.
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 Office of Saline
Water, 1959:40.
11. Saline Water Conversion Report for 1957. U.S. Dept. of Interior Office of Saline
Water, 1957:7.
12. Ramshaw C. The opportunities for exploiting centrifugal fields. Heat Recovery
Systems CHP 1993; 13(6):493–513.
13. Ramshaw C, Winnington TL. An intensified absorption heat pump. Proc Inst Refrig
1988; 85:26–39.
14. Gilchrist K, Lorton R, Green RJ. Process intensification applied to aqueous Li
B rotating absorption chiller with dry heat rejection. 7th UK National Conference
on Heat Transfer, Nottingham, U.K., Sept. 10–12, 2001.
15. Koerfer M. Hydrodynamics and mass transfer of thin liquid films flowing on rotat-
ing perforated discs. Departmental Report, Chemical Engineering Department,
Newcastle University, Newcastle, UK, 1986.
1. INTRODUCTION
In the first 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 fluid flow 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 m2/m3, and it is generally admitted that values
greater than 700 m2/m3 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 plate–fin 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
to Shah and Mueller (1) for further details. In the follo1wing sections, only non-
tubular heat exchangers will be described.
different streams and more in one single heat exchanger) and high efficiency under
close temperature approach (1–2C) in a large variety of geometric configurations.
The brazed plate–fin exchanger consists of stacked corrugated sheets (fins)
separated by flat plates, forming passages that are closed by bars, with openings
for the fluid inlet and outlet (Figures 12 and 13).
FIGURE 9 Spiral heat exchanger for the process industry. (Courtesy of Kapp.)
In its simplest form, a heat exchanger may consist of two passages, with the
cooling fluid in one passage and the warming fluid in the other. The flow direc-
tion of each of the fluids relative to one another may be countercurrent, cocurrent,
or crossflow.
The fins 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
contact are bonded by capillary action (Figure 14). Once the brazing alloy has
solidified, the assembly becomes one single block. All passages for flow 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 fitted, 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 fin corrugations have been developed, each with its own special
characteristics (Figure 15). Straight fins and straight perforated fins act like par-
allel tubes with a rectangular cross section. Convective heat exchange occurs due
to the friction of the fluid in contact with the surface of the fin. The channels of
serrated fins are discontinuous, and the walls of the fins are offset. For air flows,
louver fins are extensively used; for process applications (single- and two-phase),
continuous or offset strip fins 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
plate–fin 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 fluids and is suitable for marine applications.
a flat plate. The plates are stacked together and diffusion bonded. These heat
exchangers can support pressures up to 500–1000 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 flexible as for plate–fin heat exchangers, and crossflow
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.
3. SINGLE-PHASE FLOW
3.1. Flow Pattern
For corrugated heat exchangers, the flow is almost three-dimensional, and the
velocity field is difficult to measure. Flow visualization (33–34), 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 flow (Figure 24), which occurs at
Re 200, reduces the size of these areas. Local information (35–38) on the heat
transfer and velocity fields indicates that the heat transfer coefficients are linked
to the flow 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 quasi–plug
flow can be obtained. This indicates that corrugated heat exchangers could be suit-
able for chemical reactions. The angle of corrugation has some influence on the
global flow pattern. If we consider the entire channel as a two-dimensional medium,
the flow behavior can be studied. At this scale the flow can be considered homogen-
eous if there is the same flow rate through the channel width. Thonon et al. (37)
have shown that for low aspect ratio and low corrugation angle ( 30), there is
flow inhomogeneity, up to 15% of the flow rate distribution. But at high corruga-
tion angle or for higher aspect ratio (Ar 2), the flow is almost homogeneous.
In plate–fin heat exchangers, the flow structure depends on the fin geometry.
Continuous fins can be assimilated to rectangular channels and the flow is almost
identical to pipe flows. For offset strip fins or louvered fins, there is a high degree
of mixing (40), and the flow becomes turbulent even at low Reynolds number
(Figure 25).
0.5 mm, there is no significant 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 fluid flow 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
inefficiencies, 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 26 View of the deposit (30 corrugation angle at a velocity of 0.5 m/s).
While sizing plate heat exchangers, the great sensitivity of fouling to the
fluid 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
efficiency. It is often recommended that the fouling margin not exceed 25% of the
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 plate–fin 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
flow and the fluid 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 configuration 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-
nificant improvement in thermal performance can be achieved. For large compact
heat exchangers operating under two-phase flow 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 coefficients, and it is generally admitted that the
basic mechanisms occurring during flow boiling are similar to those encountered
in plain tubes (55–57), 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
coefficients are significantly 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 coefficients; hence
the vapor phase will be well mixed, and no major degradation of the heat trans-
fer coefficient should be observed.
Concerning plate–fin heat exchangers, the design of such units is much more
complicated because up to 12 different fluids can flow in the heat exchangers.
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 sufficiently accurate and general to be
applied for compact heat exchangers. In the convective regime, the heat transfer
coefficient is reported to the single-phase liquid heat transfer coefficient, and an
enhancement factor is introduced to take into account the liquid–gas interactions.
The main questions are to evaluate the single-phase heat transfer coefficient 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 fluids.
The fluids encountered are mixtures, and noncondensable gases are often present;
this makes the condensation process very complex.
In compact geometries the heat transfer coefficient depends on the two-phase
flow pattern (51–67). For low condensation rates, the heat transfer is gravity
controlled, and the heat transfer coefficient depends on the liquid film thickness.
For higher condensation rates, the heat transfer coefficient depends on the vapor
shear effect, and for small passages the liquid–vapor interaction leads to high heat
transfer coefficients.
These heat exchangers have a flexible 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 flow structures,
but it only gives access to qualitative information or time-average measurements.
Using advanced numerical methods allows simulating single-phase flow 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 fluid 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 flow is almost three-dimensional.
Analyzing the stream function inside the 60 heat exchanger (Figure 33), we can
see that flow is mainly in the direction of the flow inlet, which is a characteristic
of subchannel flow. However, a small part of the fluid is deviated by the channels:
furrow flow. So for this angle, quasi–plug flow can be obtained, which is in
accord with the work of Amblard (39) and Hugonnot (34). The flow can be con-
sidered homogeneous since there is the same flow 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 flow fea-
ture is equally in the direction of the flow inlet (subchannel flow) and inside the
furrow (furrow flow). 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 efficiency of corrugated channels is excel-
lent because one corrugation is nearly sufficient to have perfect mixing (Figure 35).
For finned passages, all the described phenomena (Figure 36) are in good
accord with the regime predicted by the literature (70). Indeed, the flow 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 flows upstream, creating a
recirculating and high-shear area; the other is convected downward by the mean
flow. 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
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 fin.
In plate–fin heat exchangers, the flow structure depends on the fin geometry.
For offset strip fins, there is a high degree of mixing (25), and the flow becomes
turbulent even at low Reynolds numbers (Figure 37). Indeed, after six rows of fins
(e.g., about 20 mm), the flow is homogeneous, so the macromixing in the plate–fin
heat exchanger is very efficient.
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.
where is given by
pu
L
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 fluid. The higher the
mixing efficiency, 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 (5–7) (Table 2). The lower the angle, the lower the mixing effi-
ciency. Indeed, while lowering the angle, the flow pattern moves from subchannel
flow (helicoidal motion) to furrow flow (duct flow), which reduces the mixing.
The mixing efficiency is very low (below 10%), so corrugated heat exchangers,
which are able to produce high heat flux, e.g., high macromixing, are not able to
produce micromixing.
For plate–fin 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
PHE
regime is not achieved (one must increase the velocity or the plate width by a fac-
tor of 2), but this geometry is efficient for heat transfer and mixing. It could be a
good concept in the area of temperature-controlled reactions.
6. APPLICATIONS
6.1. Feed/Effluent Heat Exchangers
Feed/effluent heat exchangers are used in many industrial processes to warm up
the fluid 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.
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) flash
evaporation through a discharge valve, (2) horizontal tubular or plate reboilers
(submerged or falling film), (3) vertical tubular or plate evaporators (climbing or
falling film), (4) specific evaporators (direct contact, scraped surface, etc.). Compact
heat exchangers are mostly used as vertical evaporators with either falling film
(Morgenroth et al. (73)) or climbing film (Brotherton (12), Patel and Thomson (11)).
A special high-capacity compact falling-film evaporator has been developed for
sugar plants. The use of falling-film evaporators allows one to reach higher heat
transfer coefficients than with climbing-film evaporators, especially for low tem-
perature differences. Compared to conventional systems, the overall heat transfer
performance can be up to two to five times higher, as a function of the fluid
REFERENCES
1. Shah RK, Mueller AC. Heat exchange. In: Ullmann’s Encyclopedia of Industrial
Chemistry, Unit Operations II. Vol. B3. Weinheim, Germany: VCH, 1988:Chapter 2.
2. Ohara T. The latest heat exchanger technology for vehicle’s. In: Shah RK et al., eds.
Compact Heat Exchangers and Enhancement Technology for the Process Industry.
Begell House, 1999:9–16.
Wolfgang Ehrfeld
Ehrfeld Mikrotechnik AG, Wendelsheim, Germany
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 efficient 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 efficiently
utilized to transport fluids at small characteristic dimensions, since the effects of
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 sufficiently 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-film 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 sufficiently 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 specifications 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
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
microfluidic devices have been manufactured by means of this method, such as
micropumps, microvalves, and flow-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
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 profit 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,
6. CONCLUSIONS
Future progress in chemical engineering will be strongly determined by process
intensification 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 efficient
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 sufficiently broad
scientific basis, to implement reliable and cost-effective fabrication of chemical
microdevices on an industrial basis, to gain experience in the design, construction,
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.
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,
profiles)
Ease of catalyst separation and handling
Heat supply and removal
Hydrodynamics (regimes, controllability, predictability)
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 first
application of a structured reactor.
multiphase reactors. Later it will be seen that combinations of static mixers and
monolithic catalysts have a high potential in process intensification.
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
system: Plugging does not occur. A disadvantage is the relatively low trapping
efficiency. In combustion foams result in stable combustion behavior.
The disadvantage, of course, is the high cost, due to the difficult, 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
configuration: 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.
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 NOx 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.
whereas sequential oxidation giving CO2 and H2O is not desired. This calls for
short residence times (ms), short diffusion length (as small as possible a diameter
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 profile 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.
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 efficient 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
the flow rate has to be above a specified 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 flow characteristics.
So the flow rates have to be sufficiently 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 upflow of gas and liquid is not to be preferred, because
lower flow rates might be applied. This appeared not to be the case. Again, high
flow rates are needed to establish a good gas–liquid flow distribution. It might be
worthwhile to investigate whether systems can be developed or conditions estab-
lished that allow low flow 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 flow rates.
Moreover, they might lead to flexibility, allowing more compact reactor systems.
The first 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 gas–liquid transfer (51–53), while in reactive studies the overall gas–solid or
liquid–solid 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
efficiently 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 kla, the
mass transfer coefficient times the exposed surface area per unit volume a. Values
of kla depend strongly on the gas and liquid properties, but for many systems val-
ues of 0.5 s1 are found, and values even much larger than 1 s1 possibly apply.
This is one order of magnitude higher than in conventional reactor types (1),
which underlines the process intensification potential of monolithic reactors.
In Table 3 the three common reactor types are compared. Obviously, the
monolithic reactor in the Taylor-flow regime leads to a high degree of process
intensification. When these numbers are recalculated into production rates, values
of 40 mol/m3reactor-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 gas–liquid–solid 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 flooding occurs (55,56). The reason is that in the small inter-
stitial space, extended momentum transfer takes place between the liquid flowing
down and the gas flowing upward. At velocities used in industry this would imply
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 flexibility 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 intensification. In the short term,
catalytic monoliths will be applied to replace trickle-bed reactor and slurry-phase
REFERENCES
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Hydrodynamic aspects of the monolithic loop reactor. Chem Eng Sci 2001; 56:
805–812.
2. Dautzenberg FM. Novel reactor concepts in hydrotreating. Cattech 1999; 3:54–63.
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):179–270.
5. Kapteijn F, Heiszwolf JJ, Nijhuis TA, Moulijn JA. Monoliths in multiphase catalytic
processes—aspects and prospects. Cattech 1999; 3:24–41.
6. Cybulski A, Moulijn JA. Monoliths in heterogeneous catalysis. Catal Rev Sci Eng
1994; 36:179–270.
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; 21:213–226.
8. Gulati ST. Ceramic catalyst supports for gasoline fuel. In: Cybulski, A Moulijn JA,
eds. Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:15–58.
9. Twigg MV, Webster DE. Metal and coated-metal catalysts. In: Cybulski A, Moulijn JA,
eds. Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:59–90.
10. Twigg MV, Wilkins AJJ. Autocatalysts—past, present and future. In: Cybulski A,
Moulijn JA, eds. Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:
91–120.
11. Heck RM, Farrauto RJ. The automobile catalyst. Cattech 1997; 1:117–124.
12. Marin GB, Hoebink JHBJ. Kinetic modeling of automotive exhaust catalysis.
Cattech 1997; 2:137–148.
13. Misono M. Catalytic reduction of nitrogen oxides by bifunctional catalysts. Cattech
1998; 2:53–69.
14. Beretta A, Orsenigo C, Tronconi E, Forzatti P, Berti F. Analysis of plate-type mono-
lith SCR-DeNO(x) catalysts. Kinet Catal 1998; 39:646–648.
15. Beretta A, Tronconi E, Groppi G, Forzatti P. Monolithic catalysts for the selective
reduction of NOx with NH3 from stationary sources. In: Cybulski A, Moulijn JA, eds.
Structured Catalysts and Reactors. New York: Marcel Dekker, 1998:121–148.
Andrew Green
BHR Group Limited, Cranfield, England
1. INTRODUCTION
High-intensity inline devices are often used to mix fluids in the process industries.
Such devices include simple pipes, baffled 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 intensification 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, gas–liquid, and liquid–liquid
applications, (b) evaluate manufacturers bids, and (c) identify opportunities for
intensifying processes, as either a retrofit for existing plant or as a new process.
AB → R
RB → S
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 first, there should not be too much
S formed. However if mixing is slow, the first reaction can be artificially slowed
down, which will then tend to favor production of S—and yield will reduce. The
flow pattern in the reactor will also influence the production of S. For “back-
mixed” flow, 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 flow” 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 flow.
The reactor is the nucleus of the process. Getting the fluid dynamics right
in the reactor means improved safety, productivity, and selectivity, which in turn
influences upstream (reduced raw material costs) and downstream (reduced sep-
aration and waste treatment costs); see Figure 1.
2. MIXING CONCEPTS
2.1. Reynolds Number
The Reynolds number is the ratio of inertial to viscous forces in a flow. For a pipe:
u p d p
Re p (1)
The value of Re indicates the flow regime for a specific system. A particular
regime is a property of the flow field, not the fluid, which is why the Reynolds
number is useful. Re is an important parameter for mixing considerations because
the flow regime determines the mixing mechanisms of the flow field. At high Re,
inertial forces dominate. Energy input is required to sustain turbulent eddies, which
are active at different length scales; a degree of “self-mixing” exists. At low Re,
viscous forces dominate. External energy input is required to stretch, chop, and
fold fluid and accelerate molecular diffusion. Ultimately, all energy input is dis-
sipated to heat.
The mixer velocity is the superficial velocity divided by the mixer voidage (),
giving
u p d H
Re H (3)
For a motionless mixer, ReH Rep, and values of dH /dp vary significantly from
mixer to mixer, as shown in Table 1. T1
For fully turbulent flow (generally ReH 10,000), fM is roughly constant. For
laminar flow (ReH 1000), the product fM Re is a constant. Between these val-
ues (transitional flow), fM is a function of Re.
Approximate fully turbulent friction factors for motionless mixers are given
in Table 2. (Note: These figures 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
Fanning’s friction factor. The relationship between the three is:
fM 2 Ne 4 fF
(5)
Moody’s Newton number Fanning’s
This can then be used to determine the total energy dissipation rate in the mixer
(in W/kg):
Qp f u3
M (7)
Vm 2d
Sulzer/Koch SMV 6
SMXL 2.5
Chemineer Kenics (KMS) 2
HEV 0.4
Empty pipe 0.001–0.03
For fast reactions, the mixing rate can limit the product rate of formation
and, as described in the next section, product quality/yield.
With very fast mixing (t1/ 2 m << t1/ 2), 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, Xs will tend toward zero. However, slow mix-
ing compared to the fastest reaction (i.e., t1/ 2 m >> t1/ 2 ) slows down the desired
reaction, leading to high waste selectivities, Xs → 1. It should be noted that in this
analysis, t1/ 2 m 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.
For example, for q/Q 104, Rep 105, fD 0.02, and CoV 0.05, L/d for cen-
terline injection is 78, whereas for wall injection it is 234.
It should be noted that when additive flow has significant momentum, much
more rapid blending is possible (so-called T mixer). An optimum value of momen-
tum ratio between main flow and additive can be found (see Ref. 2 for details).
4.2.2. Turbulent and Transitional Flow Mixing
in Motionless Mixers
Motionless-mixer manufacturers usually have experimentally based correlations
to predict macromixing performance in turbulent flow. These often use slightly
different bases, so care has to be taken when comparing performance.
For the Koch/Sulzer SMV in turbulent flow (Rep 2000), significant mix-
ing continues to be achieved for several diameters downstream of the mixer.
Equations (16) and (17) are for measurements three pipe diameters downstream
of the mixer and are valid for viscosity ratios µB/µA 100.
The macromixing length (say, to give CoV 0.05) is insensitive to Re
under fully turbulent conditions. So for a higher velocity, though the mixer length
remains constant, the time for mixing will be shorter. Put another way, macromix-
ing time is inversely proportional to pipe velocity.
For transitional flow, precise correlations are not available; but for both
SMV and Chemineer Kenics mixers, extra elements are required to achieve a cer-
tain degree of mixing. The SMV does not achieve significant mixing downstream
of the mixer as in turbulent flow, so elements are not spaced out. The HEV is not
recommended for transitional flow.
4.2.3. Mixer Rankings for Turbulent-Flow
Blending Applications
The ranking of mixers for a blending application will depend on what the user is
trying to achieve. If blending efficiency is most critical (i.e., achieving the
required mixing for minimum pressure drop/energy use), the most efficient mixer
is, in fact, an empty pipe. After that the ranking is:
Empty pipe HEV Kenics or SMV SMX
1
1/ 2
1
micro (21)
E 0.058 ε
Numerical models for mesomixing control with reactions are being devel-
oped, although they are more complex than micromixing models and require the
input of empirically determined length scales. Mesomixing limitations give rise
to worse process performance than if micromixing alone were limiting, so if pos-
sible mesomixing time should be reduced (e.g., by increasing the number of addi-
tive feeds or reducing the additive flow rate) to the point that micromixing controls.
However, in practice this is often not possible.
If residence time is kept constant, fewer elements will be required at the larger
scale, and
1/ 3
d
lnew new lold (26)
dold
5. GAS–LIQUID MIXING
5.1. Introduction
Gas–liquid reactions form an integral part of the production of many bulk and
specialty chemicals, such as the dissolution of gases for oxidations, chlorin-
ations, sulfonations, nitrations, and hydrogenations. When the gaseous reactant
must be transferred to the liquid phase, mass transfer can become the rate-limiting
step. In this case, the use of high-intensity mixers (motionless mixers or ejectors)
can increase the reaction rate. Conversely, for slow reactions a coarse dispersion
of gas, as produced by a bubble column, will suffice. Because a large variety of
equipment is available (bubble columns, sieve trays, stirred tanks, motionless
mixers, ejectors, loop reactors, etc.), a criterion for equipment selection can
be established and is dictated by the required rate of mass transfer between
the phases.
Solids present
Slow reaction
Fast reaction
Energy
efficiency
important
Low gas
Pressure
Mixer type
p constraint
Space constraint
Solids present
Energy efficiency important
Need for heat removal
0.5
t
Ha MT (28)
tR
low liquid-flow rates and high gas-flow rates; stratified flow develops in low gas-
and liquid-flow rates.
Bubble flow is generally more desirable for liquid-film controlled mass
transfer processes because of the high turbulence level in the liquid phase, while an
annular flow is more desirable for gas-film controlled processes, where the
turbulence level in the gas phase is high. However, in reactive systems, stoichio-
metry will often define the gas- and liquid-flow rates, leaving no choice for the flow
pattern. Having said this, motionless mixers and ejectors can maintain the bubble
flow regime even at high gas-to-liquid flow ratios, where flooding of the impeller
would occur in a stirred tank or annular flow develop in empty pipes (Figure 7 (8)).
5.6.2. Pressure drop
Pressure drop is a critical parameter, in that it determines pumping requirements
and enables the power input to the mixer to be calculated.
Motionless Mixers. Major mixer manufacturers agree that the Lockhart
and Martinelli parameters for two-phase flow in pipes (9) can also be applied to
motionless mixers. To estimate the pressure drop, the single-phase liquid and gas
pressure drops are first calculated. The Lockhart and Martinelli para-meter X is
found from
pL
X (30)
pG
Gas chamber pressure, ps, 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.
1 D 4
p1 ps L u 2j 1 n (35)
2 D1
The majority of reported correlations for ejectors are for loop-type config-
urations, e.g., (13):
0.76
k L a 0.044
P
(40)
V
with very little reported on the stand-alone configuration.
0.6
We ′crit 0.6
dmax ε 0.4
2 ( ) (41)
0.2
c2 d
ni di3
d32 (42)
ni di2
0.6 0.6
We′c 0.4
d32 Cn 2 2 ε
2 (
L G )
(43)
a6 (44)
d32
6. LIQUID–LIQUID DISPERSIONS
6.1. Introduction
Motionless mixers are highly effective for producing dispersions of immis-
cible liquids. Applications can be physical (e.g., for liquid–liquid extraction)
or chemical (e.g., many nitration reactions). As with gas–liquid mixing, the
most relevant parameter to measure for such applications is the Sauter mean
diameter.
We c u 2p d p / (45)
Most correlations show that d32 is proportional to the Weber number raised
to the power of 0.6, which is consistent with the theory of drop breakup by tur-
bulent shear forces. Strictly, these correlations should be applied only where the
drop size is in the inertial subrange of turbulence, i.e.,
k d32 dp /4 (46)
where C 0.45 for the former and 0.49 for the latter. These are valid for fully tur-
bulent flow in a pipe (Rep 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 flow, Berkman and
Calabrese (16) developed the correlation further to give
0.6
d32 d32
1/ 3
0.6
0.49 We 1 1.38Vi
dp d p (49)
where
1/ 2
d u p c
Vi
d
(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)
d32
0.21We ′0.5 Re 0H.15 (51)
dH
where We is the Weber number based on hydraulic diameter, i.e.,
c u 2p d H
We ′ (52)
The correlation was developed for five 50-mm SMV elements (dH 8 mm) and
covered Reynolds numbers (ReH) in the range 200–20,000 and dispersed-phase
volume fraction up to 0.25.
0.6 0.1
(1 BVi)We c
0.6
c 0.4
d32 0.65(1 kd ) ε (53)
2 c d
6.4. Scale-Up/Scale-Down
When scaling up or scaling down a liquid–liquid process in turbulent flow, the
energy dissipation rate needs to be kept constant, giving
However, checks should be made that flow 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.,
1/ 3
d
lnew new lold (55)
dold
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.
NOMENCLATURE
Symbol Explanation Units
a Interfacial area m1
ci Concentration of species i mol-m3
c Mean concentration mol-m3
CoV Coefficient of variation —
Cn Constant ⬃ 0.6 —
C*AL Equilibrium concentration of A mol-m3
CBL Bulk liquid concentration of B mol-m3
D Stirred-tank impeller or rotor diameter m
DAL Diffusion coefficient of A in liquid m2-s1
Dm Molecular diffusivity m2-s1
Dta, Dax Axial turbulent dispersion coefficient m2-s1
Dtr Radial turbulent dispersion coefficient m2-s1
d Droplet diameter m
dB Feed pipe diameter m
dH Hydraulic diameter of motionless mixer m
dmax Maximum stable drop size m
dn nozzle diameter m
dp Internal pipe diameter m
d32 Sauter mean diameter m
E Engulfment rate coefficient s1
EB Ratio of viscous to interfacial forces —
Ep Rate of direct energy dissipation W-kg1
fM Moody’s friction factor —
g Acceleration due to gravity ms2
KL Overall mass transfer coefficient ms1
k Second-order reaction rate constant m3-mol1-s1
kL Liquid-side mass transfer coefficient ms1
Greek Symbols
Flow rate ratio (QA,C /QB) —
Shear rate s1
Turbulent energy dissipation rate W-kg1
Efficiency of turbulence generation —
Voidage of a motionless mixer —
Turbulence-generating length scale m
k Kolmogorov microscale m
Dynamic viscosity mPa-s
Kinematic viscosity m2-s1
Fluid density kg-m3
Standard deviation —
Interfacial tension N-m1
Characteristic time scale s
Total energy dissipation rate W-kg1
Dispersed phase volume fraction —
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; 52:659–661.
2. Hesketh RP, Russel T, Etchells AW. R&D notes. AIChE J 1987; 33(4):663–667.
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.
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 intensification of (bio)chemical processes.
Written from an industrial point of view, it focuses on the application aspects of
those integrative technologies. Potential application fields 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.
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 first 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 first 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 significant savings on energy.
Hydrolysis of methyl acetate presents an industrial example of such energy savings.
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
Esterification 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 esterification
88 Batch and fixed-bed adsorptive
reactors
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 CO2-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 effluents, regeneration of catalysts and adsorption materials,
and soil decontamination.
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
Selected
System refs. Remarks
seawater and brackish water. This so-called Memstill® technology (Figure 11a)
combines multistage flash and multieffect distillation modes into one membrane
module. Since the Memstill® module houses a continuum of evaporation stages
in an almost ideal countercurrent flow configuration, a very high recovery of the
evaporation heat is possible. The economic advantage of the 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 efficiency 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, flooding, foam-
ing, or channeling (due to indirect gas–liquid 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,
System/process Selected
investigated refs. Remarks/effects
System/process Selected
investigated refs. Remarks/effects
Selected
System/process investigated refs. Remarks/effects
R
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-fiber
naproxen thioesters membrane
Separation of D,L-alanine and D,L-phenylalanine 266,267 Hollow-fiber zeolite membrane
racemic mixtures
Removal of sulfanilic acid from wastewater 268 Hollow-fiber modules
Lactic acid purification 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-fiber membranes
Hydrogen separation from methane steam 274 Palladium alloy membranes
conversion products
Separation of liquid olefin/paraffin 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)
REFERENCES
1. A low-cost design for urea. Nitrogen 1996; (222):29–31.
2. Taylor R, Krishna R. Chem Eng Sci 2000; 55:5183–5529.
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, 1998:103–113.
4. Siirola JJ. AIChE Symp Ser 1995; 91(304):222–233.
5. Stein E, Kienle A, Sundmacher K. Chem Eng 2000; 107(13):68–72.
6. Podrebarac GG, Ng FTT, Rempel GL. CHEMTECH 1997; 27(5):37–45.
7. Schwarzer S, Hoffmann U. Chem Eng Technol 2002; 25:975–980.
8. Steinigeweg S, Gmehling J. Ind Eng Chem Res 2002; 41:5483–5490.
9. Georgiadis MC, Schenk M, Gani R, Pistikopoulos RN. Computer-Aided Chem Eng
2001; 9:997–1002.
10. Kenig EY, Bader H, Górak A, Bessling B, Adrian T, Schoenmakers H. Chem Eng Sci
2001; 56:6185–6193.
11. Siirola JJ. AIChE Symp Ser 1995; 91(304):222–233.
12. Moritz P, Blagov S, Hasse H. Chem Ing Tech 2002; 74:1207–1218.
13. von Scala C, Gotze L, Moritz P. Sulzer Tech Rev 2001; 83(3):12–15.
14. Smejkal Q, Hanika J, Kolena J. Chem Eng Sci 2001; 56:365–370.
15. Chiang S-F, Kuo C-L, Yu C-C, Wong DSH. Ind Eng Chem Res 2002; 41:3233–3246.
16. Bollyn M, Wright AR. Chem Eng World 1999; 34(6):103–108.
17. Omota F, Dimian AC, Bliek A. Computer-Aided Chem Eng 2001; 9:9463–468.
18. Masamo J, Matsuzaki K. J Chem Eng Japan 1994; 27:1–5.
19. Kolah AK, Mahajani SM, Sharma MM. Ind Eng Chem Res 1996; 35:3707–3720.
20. Ward DJ. Etherification of isoamylenes by catalytic distillation. U.S. Patent 5196612,
UOP Inc., 1993.
21. Baur R, Taylor R, Krishna R. Computer-Aided Chem Eng 2001; 9:93–98.
22. Baur R, Krishna R. Chem Eng Proc 2002; 41:445–462.
23. Yeh A-I, Berg L. Chem Eng Commun 1992; 113:147–153.
24. Preston KL. Use of reactive distillation in the manufacture of methyl tertiary-butyl
ether. U.S. Patent 5741953, Huntsman Specialty Chemicals Corp., 1998.
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H.-J. Bart
University of Kaiserslautern, Kaiserslautern, Germany
1. INTRODUCTION: AN OVERVIEW OF
REACTIVE SEPARATIONS
Chemical manufacturing companies produce materials based on chemical reactions
between selected feed stocks. In many cases the completion of the chemical reac-
tions is limited by the equilibrium between feed and product. The process must then
include the separation of this equilibrium mixture and recycling of the reactants.
The fundamental process steps of bringing material together, causing them to react,
and then separating products from reactants are common to many processes.
Conventionally, each unit operation—whether mixing or absorption, distil-
lation, evaporation, crystallization, in fact, any of the heat-, mass-, and momentum-
transfer operations so familiar to chemical engineers—is typically performed in
individual items of equipment, which, when arranged together in sequence, make
up the complete process plant. As reaction and separation stages are carried out
in discrete equipment units, equipment and energy costs are added up from these
major steps. However, this historical view of plant design is now being challenged
by the combination of two or more unit operations into one plant unit. The poten-
tial for capital cost savings is obvious, but there are often many other process
advantages that accrue from such combinations (1).
under a pressure lower than that in the absorber. Part of the gas absorbed by the
rich solvent is desorbed due to flashing and heating. The other part has to be de-
sorbed in the stripper via countercurrent contact of liquid with the inert gas or
steam. The lean solvent then flows through heat exchanger H1 to recover heat nec-
essary for heating the reach solvent, passes through heat exchanger H2 to cool
down to a desired temperature, and finally enters the absorber (3).
Usually a small amount of fresh solvent should be added to the column in
order to equalize the solvent loss due to evaporation in the desorber or to irre-
versible chemical reactions occurring in the whole system (3).
Reactive absorption represents a process in which a selective solution of
gaseous species by a liquid solvent phase is combined with chemical reactions.
As compared to purely physical absorption, RA does not necessarily require ele-
vated pressure and high solubility of absorbed components; because of the chem-
ical reaction, the equilibrium state can be shifted favorably, resulting in enhanced
solution capacity (17). Most RA processes involve reactions in the liquid phase
only; in some of them, both liquid and gas reactions occur (18,19).
Usually the effect of chemical reactions in RA processes is advantageous
only in the region of low gas-phase concentrations, due to limitations stemming
from the reaction stoichiometry or equilibrium (20). Further difficulties of RA
applications may be caused by the reaction heat through exothermic reactions and
by relatively difficult solvent regeneration (21,22). Most RA processes are
A usual solution in this case is a sequence of a reactor and several separation units
(Figure 5). Another way—an integrated RD process such as shown in Figure 6—
allows for simultaneous formation of methyl acetate in the reaction zone, extract-
ive distillation and product enrichment in the upper part of the column, and
methanol separation in the stripping zone. The production of esters such as
methyl acetate, ethyl acetate, and butyl acetate has for years been an interesting
RD application.
The most important application of RD today seems to be the production of
ethers such as methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether
(ETBE), and tertiary amyl methyl ether (TAME), which are widely used as mod-
ern gasoline components. Figure 7, upper part, shows a traditional process for
MTBE production, which is a strongly exothermic reaction. The disadvantages of
that process can be avoided if the reaction and separation take place within the
same zone of the reactor (Figure 7, lower part).
Table 2 gives a short overview of possible RD applications.
The design of RD is currently based on expensive and time-consuming
sequences of laboratory and pilot-plant experiments, since there is no commer-
cially available software adequately describing all relevant features of reactions
(catalyst, kinetics, holdup) and distillation (VLE, thermodynamics, plate and pack-
ing behavior) as well as their combination in RD. There is also a need to improve
catalysts and column internals for RD applications (1,51). Figures 8 and 9 show
some examples of catalytic internals, applied for reactive distillation.
FIGURE 9 (a) Catalytic structured packing Montz Multipak and (b) an exam-
ple of reactive trays. (Part b from Ref. 53.)
Monodispersed droplets can be produced and in the latter case captured by the
counterflowing continuous phase in the conus of the Venturi tube (see Figure 10b).
The RE process proceeds in three major types of equipment: mixer-settler
systems, column extractors, and centrifugal extractors. Countercurrent column
extractors can be further subdivided into nonagitated nonproprietary columns and
agitated proprietary extractors. Agitating the liquid–liquid system breaks up
droplets and increases the interfacial area to improve the mass transfer and
column efficiency. Various forms of energy input are used, e.g., rotation of pro-
pellers, impellers, and discs; pulsation, vibration, and ultrasonic devices; and cen-
trifugal devices.
Some examples of mechanically agitated contactors are the rotating-disk
contactor (RDC), Karr, Oldshue–Rushton, Scheibel, and Kühni columns shown
in Figure 11.
There are three types of nonproprietary nonagitated types of extraction
columns (see Figure 12). The spray columns are the simplest type of extractors,
containing only distributors for the feed (often through perforated pipes). This
makes them cheap; however, they are limited in use due to significant axial mix-
ing in the column and the fact that the phases are not coalesced and redistributed.
This often results in low efficiencies, which are comparable to one or two
theoretical equilibrium stages. Packed columns are much more efficient since the
packing reduces back-mixing and enhances drop reformation. The packing types
that can be used are the same as those for normal distillation operations (e.g.,
rings, saddles, or slightly modified structured packings of corrugated metal
sheets). Compared to packed beds, structured packings need a reduced cross-
sectional area for liquid flow, resulting in smaller column diameters. Sieve-tray
columns resemble the distillation column design, except that there is no weir. In
3. CASE STUDIES
3.1. Absorption of NOx
3.1.1. Chemical System
The reactive system considered is a basic one in the production of nitric acid as
well as in some other industrial processes (19). It consists of 10 components,
including air (N2, O2), water (H2O), oxyacids of nitrogen (HNO2, HNO3), and
nitrogen oxides (NO, NO2, N2O, N2O3, N2O4). The components are involved in
simultaneous, parallel, and consecutive reactions occurring in both phases. The
reactions are of high orders and most of them are exothermic.
Reaction kinetics is described by the scheme suggested in Ref. 128 and
modified in Ref. 129. This scheme involves eight reactions and can be regarded
The liquid-phase reactions are valid for nitric acid concentrations below
34 wt %. In the case of higher nitric acid concentrations, Reactions (R5) to (R7)
become reversible. The oxidation of NO (Reaction (R1)) is the slowest reaction in
this system. Therefore, the total gas-phase holdup in absorbers can be determined
using the kinetic data for this reaction (130). The other gas-phase reactions are
instantaneous equilibrium reactions.
3.1.2. Process Setup
Measurements of an industrial NOx absorption process, schematically shown in
Figure 14, were described in Ref. 131. The absorption plant constitutes a sequence
of four units used for the removal of nitrogen oxides from the waste gas of an adipin
acid factory. Each unit is separated by a metal plate into two sections. In fact there
are eight columns joined together as a countercurrent absorption plant. This plant
is operated at atmospheric pressure. Columns 1–7 have a pump around for cooling
of the liquid. The diameter of each column is 2.2 m; the height is 7 m. The packing
height is 3.2 m. The packing consists of 35 mm INTALOX ceramic saddles.
The zigzag form of the simulated concentration profiles 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 first
two columns. Here the larger deviations between experiments and simulated
results can be attributed to the fact that at high concentration of HNO3 Reactions
(R5) to (R7), assumed to be irreversible reactions, convert to reversible ones; the
data on their rate constants are lacking.
The reactions including CO2 obey first- 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 (HCO3) takes place via two different
the liquid bulk phase does not change the absorption rates significantly, which
indicates fast conversion. Therefore, neglecting the film reaction unrealistically
reduces the absorption rates. On the other hand, neglecting the reaction kinetics
within the film results in completely different orders of magnitude for the calcu-
lated absorption degree. As a consequence, the reactions of carbon dioxide should
not be regarded as instantaneous, although the corresponding Hatta number of
about 7 characterizes the reaction as very fast (3).
The model optimized with respect to the numerical parameters and physico-
chemical properties has been validated against experimental data, whereas the
axial concentration and temperature profiles for both phases demonstrated good
agreement (Figure 19). It has also been found that the simulations of the scrubber
based on the equilibrium-stage model extended by the chemical reaction kinetics
yield results completely inconsistent with the experimental studies; namely, the
selectivity toward H2S and HCN absorption cannot be reflected (Figure 19). In
this case, the film reaction represents an essential element of the rate-based
approach that has to be considered in the model. As a result, the only feasible sim-
plification is represented by a linearization of the film concentration profiles,
including the implementation of the average reaction kinetics in the liquid film
region (143).
The low equilibrium constant and the strongly nonideal behavior that causes the
forming of the binary azeotropes methyl acetate/methanol and methyl acetate/
water make this reaction system interesting as a possible RD application (33).
Therefore, methyl acetate synthesis has been chosen as a test system and investi-
gated in a semibatch RD column. Since the process is carried out under atmo-
spheric pressure, no side reactions in the liquid phase occur (146).
3.3.2. Process Setup and Operation
The catalytic packing MULTIPAK® (147) applied in this case study consists of
corrugated wire gauze sheets and catalyst bags of the same material assembled
in alternate sequence. Sufficient mass transfer between gas and liquid phase is
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 filled 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 profiles for the
pilot test made in the column, with the reactive section filled with catalytically
where DZn denotes the partition coefficient 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:
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.
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
NOMENCLATURE
aI specific gas–liquid interfacial area m2/m3
As column cross section m2
B liquid load m3/(m2s)
c molar concentration mol/m3
CIP adjustable parameter, Eq. (B10)
dC column diameter m
di generalized driving force for component i 1/m
dp droplet diameter m
D Maxwell–Stefan diffusion coefficient m2/s
Dax axial dispersion coefficient m2/s
Deff effective diffusion coefficient m2/s
DZn partition coefficient of zinc
E length-specific energy holdup J/m
E dimensionless residence time distribution
F Faraday’s constant 9.65 104 C/mol
FC gas capacity factor Pa0.5
G gas molar flow rate mol/s
h molar enthalpy J/mol
H R0 reaction enthalpy J/mol
ky overall mass transfer coefficients m/s
Ki distribution coefficient
Keq equilibrium constant
[K] reaction matrix [Eq. (B1)] 1/s
l axial coordinate m
L liquid molar flow rate mol/s
n number of components of mixture
Ni molar flux of component i mol/(m2s)
Q heat flux W/m2
R total component reaction rate mol/m3s
R column vector with elements Ri mol/m3s
gas constant 8.3144 J /(mol K)
Re Reynolds number
Sc Schmidt number
Sh Sherwood number
t time s
T temperature K
uL liquid velocity m/s
U length-specific molar holdup mol/m
Greek Letters
film thickness m
dimensionless film coordinate
forward-reaction constant m3/2/(mol1/2s)
r backward-reaction constant s1
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 m3/m3
electrical potential V
Subscripts
G gas or second fluid 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 flow model with axial
dispersion and mass exchange
RA reactive absorption
RD reactive distillation
RE reactive extraction
RH di(2-ethylhexyl) phosphoric acid
RSP reactive separation process
d
0 ( LxiB ) ( N LiB a I RLiB L ) As i 1, . . . , n (A1)
dl
d
0 (GyiB ) ( NGiB a I RGiB G ) As i 1, . . . , n (A2)
dl
If chemical reactions take place in the (first) liquid phase only (this is
valid for most of RD processes), the phase balances for the second fluid phase
simplify to
d
0 (GyiB ) NGiB a I As i 1, . . . , n (A3)
dl
The bulk-phase balances are completed by the summation equation for the
liquid and second fluid bulk mole fractions:
n
∑x
i1
i
B
1
(A4)
∑ y 1
i1
i
B
(A5)
The volumetric liquid holdup, L, depends on the gas/vapor and liquid
flows and is calculated via empirical correlations (e.g., Ref. 65). For the determi-
nation of axial temperature profiles, differential energy balances are formulated,
including the product of the liquid molar holdup and the specific enthalpy as
energy capacity. The energy balances written for continuous systems are as
follows:
d
0 ( LhLB ) (QLB a I RLB L H RL
0
) As (A6)
dl
d
0 (GhGB ) (QGB a I RGBG H RG
0
) As (A7)
dl
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 specific
molar component holdup and the total molar holdup are taken into account. For
the liquid phase, these equations are as follows:
∂ ∂
U Li ( LxiB ) ( N LiB a I RLiB L ) As i 1, . . . , n (A8)
∂t ∂l
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).
dNLi
RLi 0 i 1, . . . , n (A10)
dz
Equations (A10), which are generally valid for both liquid and second fluid
phases, represent nothing but differential mass balances for the film region, with the
FIGURE 31 Comparison between the experimental RTD curve for the cata-
lytic packing MULTIPAK® (dC 0.1 m), the ADM model, and the PDE model.
smaller than those for fixed-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 flow paths, whereas each cell is described by the two-film model (see
Section 2.3). Using different numbers of cells in both flow paths allows one to
describe various flow patterns. However, a consistent experimental determination
of necessary model parameters (e.g., cell film thickness) appears difficult, 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-
flow 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
∂ D ∂2 ∂
ULi ax 2 ( LxiB ) ( LxiB ) ( N LiB a I RLiB L ) As i 1, . . . , n (A12)
∂t u L ∂l ∂l
Mass transfer
Binary diffusion coefficient
Phase coefficient correlation
xi 1 ∂i F 1 d
di x i zi i 1, . . . , n (B2)
ℜT L ∂ ℜT L d
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:
n
∑x z 0
i1
i i (B4)
∑N h
Q L (TLB T I )
B
i 1, . . . , n
L
L Li Li
i1
where
EL hLB ( L c Lt As ) (B7)
Similar to the mass balance equation, the vapor-phase energy balance simplifies
to Eq. (A7).
Experimental studies were carried out to derive correlations for mass trans-
fer coefficients, reaction kinetics, liquid holdup, and pressure drop for the pack-
ing MULTIPAK® (35). Suitable correlations for ROMBOPAK 6M® are taken from
Refs. 90 and 196. The nonideal thermodynamic behavior of the investigated mul-
ticomponent system was described by the NRTL model for activity coefficients
concerning nonidealities caused by the dimerisation (see Ref. 72).
Binary diffusion coefficients for the vapor phase and for the liquid phase
were estimated via the method proposed by Fuller et al. and Tyn and Calus,
respectively (see Ref. 72). Physical properties such as densities, viscosities, and
thermal conductivities were calculated from the methods given in Ref. 72. Heat
losses through the column wall were measured at pilot scale.
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 final 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 Maxwell–Stefan (54) or
eddy diffusion (56). The rate law is as follows:
2
where C1, C2, , 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:
v
K eq (B10)
r
David W. Agar
University of Dortmund, Dortmund, Germany
1. INTRODUCTION
Reaction engineers devote a lot of time and ingenuity to enhancing reactor per-
formance by attempting to follow an optimal trajectory for the reaction system (1)
and by overcoming the limitations imposed by the accompanying heat and mass
transfer processes. These objectives are often interrelated: Achieving the concen-
tration and temperature profiles required to maximize conversion rates and mini-
mize by-product formation, for example, dictates the absence of gradients that
might lead to local deviations from these values.
Process intensification can be considered to be the use of measures to increase
the volume-specific rates of reaction, heat transfer, and mass transfer and thus to
enable the chemical system or catalyst to realize its full potential (2). Catalysis
itself is an example of process intensification in its broadest sense. The use of
special reaction media, such as ionic liquids or supercritical fluids, high-density
energy sources, such as microwaves or ultrasonics, the exploitation of centrifugal
fields, the use of microstructured reactors with very high specific surface areas,
and the periodic reactor operation all fall under this definition of process intensi-
fication, and the list given is by no means exhaustive.
Reactor performance is dictated by the inputs, by the contacting pattern,
i.e., how and when individual elements pass through the reactor and contact one
another and how long they retain their identity, and by the cumulative kinetics and
thermodynamics to which elements are exposed along their reaction trajectory (3).
Identifying the most suitable reactor configuration, e.g., an ideal plug flow, is a
well-established procedure in chemical reaction engineering. Less appreciated
are the full range of possibilities available in manipulating the local rates of reac-
tion by imposing favorable temperature, concentration, and activity profiles along
a catalytic reactor. While the first option has received extensive attention, the last
two have been somewhat neglected, although they often offer a more selective
intervention in the progress of the reaction and complement the more common
tailoring of the temperature profile.
In general, temperature and concentration profiles may be externally influ-
enced by convective or recuperative and, less commonly, regenerative or reactive
strategies (Figure 1). The “convective” addition or withdrawal of side streams
along the reactor represents a simple technique for temperature control or for
improving selectivity by restricting availability of one reactant. In a recuperative
process, examples of which are provided by the cooled tubular reactor and the
membrane reactor, heat or material is exchanged, in the latter case usually in a
Hot spots usually dictate the attainable reactor performance in terms of conver-
sion, selectivity, safety issues, operating lifetimes, and materials of construction,
since most of the critical processes are confined to the immediate vicinity of the
temperature maximum.
The use of proven catalyst recipes would greatly curtail development times,
and the absence of extraneous material avoids unwanted catalytic effects and
enhances thermal stability. The fixation of catalyst on ceramic substrates such as
washcoats is a well-known, reliable, and relatively straightforward procedure.
The fabrication of complex small-scale ceramic structures is, however, more awk-
ward than for metals or plastics, and they exhibit relatively poor mechanical
strength. Furthermore, the porous ceramic nanostructure must be sealed to pre-
vent contact between the reaction medium and coolant.
In the past, the principles described have been implicitly recognized in sev-
eral attempts to convert monolithic catalysts into catalytic heat exchangers. While
the use of millimeter dimensions and nanoporous ceramic supports meets the pri-
mary criteria already mentioned, the parallel channel structure of monoliths is not
ideally tailored for heat exchanger applications, and complex header structures
are required to uniformly distribute and collect reaction medium and coolant to
and from the individual channels (Figure 9). The unsatisfactory interface between
the “milli-” and “macroscale” has been a major weakness of such concepts.
FIGURE 11 Monolithic catalyst adapted for the thermal coupling of endo- and
exothermic reactions. (From Ref. 11.)
Regeneration ?
remain controversial and are probably of little significance for industrial purposes.
Questions of scale-up, capacity limits, and materials of construction still need to
be addressed before industrial applications of microwaves in combination with
chemical reactors become more widespread.
An interesting application, derived from the use of microwaves for selective
desorption processes, is the modification of catalyst performance by the imposi-
tion of a temperature profile on a catalyst pellet, which is usually dictated by the
interaction between the heat of reaction and the thermal conductivity of the
pellet. Microwave heating together with the use of carrier materials of various
permittivities and conductivities would permit one to regulate the temperature
conditions within the catalyst pellet independently. An extension of this principle
would be the selective thermal activation of one sort of catalyst in a mixed fixed-
bed system. The external “switching” of catalytic activity in this manner could be
employed expediently to realize multistep syntheses in a single reactor. To prevent
thermal short-circuiting it would be necessary to isolate the individual catalyst
particles from one another in an insulating matrix.
• Bifunctional Catalysts
e.g. propene oxidation, Pt-doped zeolites, spillover-oxygen
• Supported Catalysts
e.g. impregnated catalysts, SLPC, SAPC
• Mass Transport
e.g. zeolites, membrane encapsulation, Aerogel
• Heat Transport
e.g. graphite carriers, coated-wall reactors, full metal catalysts
• Mass Storage
e.g. active C-carriers, hydride-containing catalysts
• Heat Storage
e.g. metallic monoliths
• Mechanical Resistance
e.g. protective coat, “washcoat”, gauzes
• Thermal Resistance
e.g. non-oxide ceramics, doped Ba-hexaaluminate
• Chemical Resistance
e.g. non-oxide ceramic, silicon dioxide, Al-phosphate
• Electromagnetic Properties
e.g. dielectrically heated catalysts, magnetic fluidized beds
resistance, and electromagnetic behavior (Table 3). The use of such microstruc-
tured hybrid catalysts can make an important contribution to process intensifica-
tion measures in other areas as well.
8. SUMMARY
The reaction engineer has a variety of tools at his disposal when attempting to
intensify heat transfer in chemical reactors, ranging from well-established meth-
ods to innovative technologies. For recuperative heat transfer, the most dramatic
improvements can be achieved by using catalytic or catalytically coated heat
exchange surfaces and working at the millimeter scale to harmonize the physical
and chemical processes taking place and render the catalytic chemistry the
performance-limiting step. These two measures overcome the most serious bot-
tlenecks in the traditional multitubular reactor.
The operation of regenerative and reactive processes for the manipulation
of temperature profiles in chemical reactors is usually more complex than con-
vective and recuperative techniques, due to the inherent dynamics and high sen-
sitivities involved. Regenerative and reactive processes can, however, permit
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1. INTRODUCTION
Process synthesis, also referred to as process integration, deals with the systematic
development of process flowsheets. The process synthesis activity has been
described as “the automatic generation of design alternatives and the selection of
the better ones based on incomplete information” (1). Design technology is required
to help the engineer find novel, improved solutions to process design problems in
the context of the incomplete information available. The ultimate aim of chemi-
cal process design is to synthesize a process that enables the production of desired
chemicals in the most cost-effective and environmentally benign manner possible
and is flexible as well as easily operated. Ideally, process synthesis tools should
allow one, out of the set of all feasible alternative structural and operational
process design options, to systematically determine the most promising process
designs, those that approach the performance limits of the system closely and
meet the constraints.
An enormous variety of decisions need to be made in order to solve process
design problems. These range from the selection of the most promising process
chemistry (reaction paths and catalysts) to the optimal exploitation of reaction,
Connections between process units are created in a third step while consid-
ering in detail the following aspects:
From raw materials to reactor: purification and conditioning of feeds (purif-
ication, heating, pressure)
From separator to product: final purification (finishing)
Reactor–separator connections: stream reconditioning (e.g., reduction of
temperature and/or pressure)
Connections of separator outlets: reactor performance, excess components,
recovery
Recycles from separators: connections to, e.g., reactor system
Step 4 consists of defining and matching the mass flows, including, e.g., the
excess of one component required in the reactor. The activity starts with building
preliminary mass balances before other conservation laws, i.e., heat and impulse,
are considered. Other relevant factors that have to be evaluated early in process
design are controllability and safety. The outcome of Step 4 is an overview of
process functions needed to realize the transition of raw materials into products,
including alternative flowsheets and unit operations that could be applied. Step 5
considers the combination of unit operations or task integration to develop the
opportunities for process intensification, viz., leading to smaller, more efficient,
and cheaper processes. This step includes screening for options related to heat
integration and reactive separations, among others.
Step 6 consists of the setup of the mass and heat balances, and alternatives
for the reaction and separation functions are considered. The alternatives are doc-
umented in a structure such as the one shown in Figure 1 or the synthesis tree pro-
posed by Seider et al. (6). Proceeding with the steps, many process alternatives
are generated form which the most promising ones need to be selected taking
3. REACTION ENGINEERING
The reactor is undoubtedly the most important ingredient of a chemical process
flowsheet, for it is the part where the product value is generated. From a decision-
making perspective, the reactor design is more of a difficult process design task
than the separation and energy systems design tasks. This is because the reaction,
heat transfer, and mass transfer phenomena tend to occur simultaneously in this
unit. Most reaction models of commercially relevant systems are highly complex,
and the development of both graphical and computational design tools that enable
quick decisionmaking so as to obtain high-performance reactor designs is chal-
lenging. Such tools are required to provide performance targets and design sug-
gestions for mixing and operational policies to give maximum decision support
to the designer.
There is an increasing awareness that the commonly employed textbook
knowledge and heuristics (9) is insufficient for the systematic development of
high-performance reactor designs. The result is a lack of innovation, quality, and
efficiency in many industrial designs. Researchers from various perspectives are
1→ B,
2A 2→ C,
B 3→ D,
A 4→ E
2B
The data are from Ref. 31. The objective for optimization is the maximization of
the effluent concentration of component B. The performance limit of the system
is identified with each stochastic run requiring an average of only 120 CPU sec
on an HP 9000-C100 workstation. Numerous designs are obtained from the sto-
chastic search that perform close to the performance target, mostly variations of
series arrangements of PFRs and CSTRs. A detailed discussion of this and other
studies is given in Ref. 31.
recycles, and bypasses, or variations on the same structure. The stochastic search
produces a multitude of solutions with similar performance, and its function is
exploited as a major advantage. These designs can be improved further with the
application of deterministic methods and more accurate models. The solutions devel-
oped from the screening stage are functional models based on the shadow reactor
superstructure model. The analysis and validation stage requires the translation of
these layouts into practical schemes. In general there are several ways to develop
practical schemes from the functional models because one can opt for either phys-
ically distinct units or multicompartment reactors.
Consider the reactor design for the production chlorination of butanoic acid
as an example to illustrate the technology developments. A full study is given in
Ref. 34, and only a brief summary of the results is presented here. The chlorina-
tion of butanoic acid (BA) involves two reactions in the liquid phase:
where MBA and DBA are abbreviations for monochlorobutanoic acid and
dichlorobutanoic acid, respectively. The system involves two phases, a liquid
phase where the reactions occur, and a gas phase consisting of chlorine feed and
hydrogen chloride product. Solubilities are calculated using Henry’s law, and
mass transfer rates are modeled according to film theory. The reaction kinetics
and all model parameters and other problem data used in the study are given in
Ref. 34. The objective of the study was to find those reactor networks with the
4. COMPLEX DISTILLATION
Despite advances in other separation technologies, distillation is still the most
widely used operation in chemical processes. Effective screening of separation
systems constitutes a critical stage, for engineers need to review and understand
trade-offs ahead of detailed modeling and simulation. In the separation, it is often
desired to explore the use of complex rather than simple columns because the
complex units reduce mixing losses, use available vapor and liquid more effec-
tively, and improve the separation efficiency (37). Despite their recognized poten-
tial in energy savings, complex distillation applications are limited due to their
difficult and demanding design-and-synthesis assignment. Synthesis challenges
and operability issues that arise from a more complex dynamic behavior have dis-
couraged wider acceptance in industry. A prohibitive number of configurations
emerge from different allocations of side-rectifiers, side-strippers, prefractiona-
tors, and side-draw columns. Such options are difficult to enumerate and assess.
The design alternatives increase rapidly, and the trade-offs are impossible to
assess with an exhaustive (implicit or explicit) enumeration of the options.
Previous efforts have focused on the development of shortcut methods
that had a purpose of evaluating fixed configurations and initializing simulation
models. Stupin and Lockhart (38) developed the equivalent arrangements of
simple columns to represent complex configurations. Several other researchers
(37, 39–47) extended knowledge from shortcut models as available for simple
columns to evaluate the performance of complex configurations. Tedder and
Rudd (48) performed a parametric analysis for complex designs and identified
optimality regions as functions of the feed composition and the relative volatili-
ties. Glinos and Malone (49) identified dimensionless parameters and proposed
guidelines for the selection of complex distillation schemes. With less emphasis
on fixed layouts, thermodynamic methods (50–53) produced procedures to assess
energy efficiency in the integrated separation.
Mathematical programming approaches promote process novelty with the
use of superstructure development. Sargent and Gaminibandara (54) pioneered a
progressive distillation train that Agrawal (55) later extended with additional con-
nections of vapor–liquid streams to include satellite columns. Christiansen et al.
(56) added more connections between component states to include structures with
triangular walls in a single shell. Several researchers (57–62) have proposed dif-
ferent superstructures and developed mixed-integer nonlinear programming
(MINLP) models for the synthesis of distillation systems. These superstructures
5.3. Optimization
In order to establish a basis for optimization, the reaction and separation super-
structure is formulated as a mathematical model that involves the component
material balances for the RMX units, the mixers prior to the separation task units,
and the product mixers, as well as the energy balances for the RMX units (for the
unit-based nonisothermal representation). The formulation incorporates models
for the reaction kinetics, physical property and mass transfer models, shortcut
models and regression expressions for equipment sizing and costing, and the
objective function. General relationship-modeling terms will introduce nonlinear-
ities into the superstructure network model. As for the reactor network synthesis
problems, the reaction and separation superstructures are optimized using sto-
chastic search techniques. Linke and Kokossis (77,78) have studied the perform-
ance of SA and tabu search (TS) for this type of problem. They found robust
performances for both algorithms and TS to be the more efficient search meta-
heuristic. A detailed description of the implementation of the stochastic search
algorithms is given in Ref. 79.
For illustration purposes, consider the Williams–Otto flowsheeting prob-
lem (80). In the conventional design, raw materials A and B are fed to a reactor,
where the following reactions occur:
(1) AB → C
(2) BC → PE
(3) PC → G
The reactor effluents are cooled and fed to a decanter for removal of heavy waste
G, which requires further treatment. From the remaining mixture, the desired
product P is removed via distillation. The unreacted raw materials as well as
unwanted byproduct E and a fraction of P are partly recycled back to the reactor.
As components E and P form an azeotrope, an amount of the desired product
equivalent to at least 10% weight fraction of E is lost through the purge, which is
used on site as a fuel. The volatilities i of components i in the system have the
following descending order: P > E > C > B > A > G. The reaction rates of
components A, B, C, P, E, and G respectively are functions of the weight fractions
X and given by the vector
The complete data are given in Ref. 79. The objective of the synthesis exercise is
to find the designs that maximize the annual profit of the process for a minimum
production rate of 400 kg/h of component P.
5.3.1. Screening Stage
The stochastic search of superstructures featuring three RMX and three uncon-
strained separation task units yields an absolute profit target of around $618 k/yr.
A variety of design alternatives exist that can achieve the targets, featuring one,
two, or three reactors and component distributors. The process design require-
ments as identified in the screening stage can be stated as follows:
Separation and removal of by-products E and G
Separation and removal of desired product P
Separation of components A, B, and C from the reacting mixture and dis-
tribution among the reactor units
Excess of component B in the reaction zones minimizes by-product forma-
tion (low concentration of product P)
Reaction zones exhibit plug-flow behavior
5.3.2. Design Stage
Based on the insights gained in the first design instance, appropriate separation
venues can be identified and included in the search. Distillation enables separa-
tion of mixtures according to the order of volatilities and hence allows separation
in support of the raw material and intermediate recovery. To avoid fouling, G
needs to be decanted prior to the operation, which can be achieved at a low cost
in a decanter. However, component P forms an azeotropic mixture with compo-
nent E, resulting in a loss of desired product to the low-value fuel. A solvent is
available that allows selective extraction of desired product P from the mixture.
The equilibrium relationship and maximum solvent loading are given in Ref. 79.
The design stage therefore considers a superstructure of RMX units and STUs to
capture the reaction–extraction–distillation–decanting system.
Stochastic optimization yields a target performance of around $433 k/yr for
the system. Designs with performances close to the target can be grouped into
two main categories according to their use of the solvent: reactive extraction
designs and reactor–hybrid separation designs, each achieving performances
close to the target. Two sample designs are illustrated in Figure 11. Designs uti-
lizing the distillation–extraction hybrid achieve higher selectivities in the con-
version of the raw materials to product P than do the reactive extraction designs,
Energy Pressure
Design cost Design Column (bar) Trays
I 6.57 1 4.9 30
2 1.8 4
3 1.8 82
II 6.60 1 3.5 4
2 3.5 90
3 4.9 29
2 4.9 29
3 1.8 54
a direct sequence (Design I). The lowest pressures are selected for all the tasks in
the designs. This results in the most favorable separation factors. The complex
column configurations require high pressures, and the benefits of thermal cou-
pling are counterbalanced by the requirement of higher reflux. Pressure effects
were found to dominate the results and to minimize the thermal coupling.
REFERENCES
1. Westerberg AW. Synthesis in engineering design. Comp Chem Eng 1989; 13:365.
2. Smith R. Chemical Process Design. New York: McGraw-Hill, 1995.
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6. Seider WD, Seader JD, Lewin DR. Process Design Principles, Synthesis, Analysis
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7. van den Berg H. Methods for process intensification projects. In: Proceedings of
the 4th International Process Intensification Conference. Bruges, Belgium: BHR,
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8. Green A. In Proceedings of the 4th International Conference on Process
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Chemical Reactors. New York: Wiley, 1962.
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mathematical programming. Ind Eng Chem Fundam 1986; 25:621.
11. Achenie LEK, Biegler LT. Developing targets for the performance index of a reactor
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operation. Chem Eng Sci 1990; 45:595.
Remko A. Bakker
DSM Fine Chemicals Austria, Linz, Austria
1. INTRODUCTION
In this chapter a method is explained for how process intensification can be intro-
duced in a commercial company. When one would like to introduce process inten-
sification, certain steps can be followed that increase the chances of success.
One very important aspect is the awareness of the drivers for introducing
process intensification for certain processes and companies: the why of process
intensification. This is explained in Section 3 in some detail, for without the
knowledge of these drivers, one risks introducing process intensification ineffec-
tively and inefficiently. After that, a short overview is given of the technologies
available for process intensification, serving as a basis for the real process inten-
sification study. The method of introducing process intensification is then
explained in Section 5, which is the main section: What steps should be incorpo-
rated in a process intensification study, what a good group of participants is, and
in what phase of a chemical process the study should be introduced. The chapter
concludes with two concrete examples of process intensification, one in a bulk
chemical process and one in a fine chemical process.
Process intensification can bring many benefits regarding business, legislative,
and environmental aspects and is therefore very worthwhile to be implemented.
Legislative
requirements
Business (environment
Aspect (costs) and safety) Environment Examples
Characteristics
Up to hundreds of kilotons Up to hundreds of tons Up to tens of tons Up to tens of tons
Continuous Mostly batch, some Mostly batch, some Mostly batch
parts continuous parts continuous
Total profits are 5–30% Total profits are 20–40% Total profits are 30–50% Total profits are 30–70%
turnover turnover turnover of turnover
Material and energy costs Material and energy costs Material and energy costs Material and energy costs
are 70–90%, labor costs are 70–90%, labor costs are 50–80%, labor costs are 10–30%,labor costs
10–30% of total costs 10–30% of total costs 20–50% of total costs 70–90% of total costs
Why PI?
Material and energy cost Higher efficiency, labor Higher efficiency, labor Labor cost reduction (also
reduction cost reduction cost reduction in cleaning procedures)
Higher efficiency, higher Higher production capacity, Higher production capacity, Higher production
production capacity material cost reduction material cost reduction capacity
Space and Energy cost reduction, Optimal price and time Optimal price and time of
waste reduction optimal price of delivery delivery
How?
Focus on materials and Focus on labor and Focus on labor and Focus on number of
energy (large impact efficiency (efficiency so efficiency (efficiency so steps (labor and
on costs) that all steps in the that all steps in the cleaning intensive)
process are well balanced) process are well balanced)
(Chapter 4), and many more. The last imperative covers technologies that use cen-
trifugal fields for contacting (Chapters 2 and 3), separations, and crystallization or
that involve extremes of pressure and temperature, ultrasound waves, microwaves
(for e.g., drying) and electric fields (for e.g., separation or dispersion).
Basically, using these technologies one would like to move forward to the
theoretical optimum of a chemical process, which is that there are no other limi-
tations than chemical kinetics. Normally a chemical process is influenced by
more than just kinetics: hydrodynamics (mixing), heat transfer, and mass transfer
determine the quality of the process. Process intensification focuses on removing
these three limitations to reaching the goal of kinetically limited processes. This
is schematically depicted in Figure 2.
These three basic imperatives can be used to begin thinking about when to
try to intensify a process in a chemical plant. They are also part of another area
of chemical engineering: safety aspects of plant designs. In the 1980s, effort was
put into developing strategies for designing so-called “intrinsically safe designs,”
which means that the process designs are such that dangers are intrinsically
minimized so that the safety of a process does not depend on safety devices.
1. Goal definition
Determine the scope The goal of the study
Unit and section of the plant or the
entire plant
All the people involved (also; the
internal customers)
2. Scouting of ideas
Identify the thermodynamics, For existing process: from known data
kinetics, and balances (mass, For new process from literature and
energy) plus the cost factors thermo databanks
Determine the theoretically optimal
process (no limitations)
Identify the breakthroughs In multidisciplinary teams
Make cost estimates of different options
3. Selection
Select the most feasible option All the people involved (also, the
internal customers)
4. Detailed design
Identify the detailed Databanks and new measurements
thermodynamics and kinetics Concluding the intensification project
Final design of the unit or plant
have new concepts ready for the future. In that case one can also use
technologies that are still in development at the present date. When the
goal is to achieve direct implementation, the time frame is short and one
should use the available data and available technologies to optimize a
process. The budget necessary for the latter study is then also different
from that for the former type.
What part of a process should be looked at? This can be one unit, one chemi-
cal conversion step, a total process, or even a combination of processes that
are interlinked through streams of intermediate products or energy streams.
Step 2. The second step is the actual study: the scouting of the ideas. This
phase consists of two subparts. The first part is data collection:
What are the kinetics and material properties in the process?
What are the mass and energy balances?
Keywords Example
6. EXAMPLES OF INTRODUCTIONS
6.1. S-Ibuprofen
The first example of process intensification at DSM is the pilot-scale test of the
enzymatic production of S-ibuprofen, a nonsteroidal, anti-inflammatory drug. The
molecular scheme is given in Figure 5. More details can be found in Refs. 3 and 4.
The conventional production consisted of many process steps, typical for a
fine chemical process. These process steps are given in Figure 6. The selectivity
of the enzyme is rather high. The downstream processing is rather laborious,
because it requires that the product be completely enzyme free. Furthermore, the
product, S-ibuprofen, causes enzyme deactivation. Altogether, many unit opera-
tions are required to obtain the product; due to the deactivation of the enzyme, a
maximum conversion of 21% can be reached.
Removing the product as fast as possible from the reaction mixture could
possibly prevent the enzyme from deactivating. This was experimentally tried on
pilot scale using an ultrafiltration unit, parallel to the reactor. In this filtration unit
the product is separated and the unreacted components and the enzyme are
returned to the reactor. An even better option, using a true membrane reactor in
which the catalyst (enzyme) would remain on one side and the product would
remain on the other side, was not tested. Both options are given schematically in
Figure 7.
FIGURE 9 Conversion of the S-ibuprofen process with and without the ultra-
filtration unit.
6.2. Urea
The second example of process intensification at DSM is the urea process (5). The
history of the urea process at DSM is rather long, as shown in Table 5. Urea is pro-
duced in a two-step process. The first step is the formation of carbamate from NH3
and CO2. This reaction is exothermic. The second step is the decomposition of car-
bamate into urea and water. This second reaction is slightly endothermic. Both
reactions are equilibrium reactions. The conversion to urea in equilibrium is about
60%. This means that substantial recycle flow is necessary to obtain sufficient
overall conversion. In the reaction section the main unit operations are:
The stripper, in which remaining CO2 and NH3 are being stripped with CO2
from the product flow
The scrubber, where the reactants in the reactor offgas are stripped
7. CONCLUSIONS
As shown in this chapter, the methodology for applying process intensification in
commercial industries requires a broad interest and cooperation within companies,
including a vision of the company management and individuals. Some boundary
conditions need to be met, such as a vision in place that offers the initial time and
money to set up the necessary infrastructure for applying these new technologies:
a basic knowledge of the possibilities and available technologies and of the
methodology. Process intensification can then bring substantial benefit in terms of
business, legislation, and environment, as is demonstrated in this chapter as well
as in the entire book, therefore making PI very worthwhile to be implemented.
8. APPENDICES
8.1. Appendix 1: Excerpt from U.S. Vision 2020
This excerpt is taken from Ref. 6.
U.S. chemical companies must innovate and change to keep competitive
in the global environment. Chemical Industry Vision 2020 Technology
* The term substantially means over 20–30% in the shorter term or over 10% per year in the longer
term.
REFERENCES
1. BHR Group. Process Intensification Conferences. http://www.bhrgroup.co.uk/confsite/
pi01home.html.
2. Elverding P. DSM’s Triple Bottom Line. DEFACTO 2001; 15(5):28–32.
3. Bakker RA, Stankiewicz AI, Schyns VJAJ. Process intensification within DSM, gen-
eral methodology and concrete examples. In: Proceedings of the 4th International
Conference on Process Intensification for the Chemical Industry. Cranfield, UK,
BHR Group, 2001.
4. Cauwenberg V, Vergossen P, Stankiewicz A, Kierkels H. Integration of reaction and
separation in manufacturing of pharmaceuticals: membrane-mediated production of
S-ibuprofen. Chem Eng Sci 1999; 54:1473–1477.
5. Technical information brochures on the Urea 2000plus™ process can be obtained
from Stamicarbon B.V., the licensing company of DSM.
6. U.S. Vision 2020, section of the Office of Industrial Technologies (OIT). http://www.
oit.doe.gov/chemicals/visions_new_chemistry.shtml.
7. European Union 5th Framework Research Program 1998–2002. Thematic program
GROWTH: http://europa.eu.int/comm/research/growth/index.html and http://
europa.eu.int/comm/research/growth/pdf/growth-workprog2000_en.pdf.
8. SUSTECH Technology program, part of the CEFIC organization. http://www.cefic.be.
Dennis C. Hendershot
Rohm and Haas Company, Bristol,
Pennsylvania, USA
1. INTRODUCTION
Process intensification is an important strategy in the development of inherently
safer chemical processes and plants. By reducing the inventory of hazardous mate-
rial or energy in the process, the potential consequence of failure to control that
hazardous material or energy is reduced. Rather than relying on add-on safety
features such as interlocks, procedures, and consequence mitigation systems, the
safety of the plant is based on reducing the magnitude of the possible damage.
While safety devices can be designed to be highly reliable, no safety device is per-
fect, and all will have a finite failure probability. If a chemical plant contains a
large amount of hazardous material or energy, the consequences of the failure of
the add-on safety devices may be large. A smaller plant is safer because we have
reduced its inherent capability to cause damage, rather than because we have con-
trolled that capability through additional safety devices.
2. INHERENT SAFETY
Inherent is defined as “existing in something as a permanent and inseparable ele-
ment, quality, or attribute” (1). A chemical process can be described as inherently
safer if it reduces or eliminates a hazard when compared to another process alter-
native. To understand this definition, it is necessary to understand what is meant
categories are generally considered to be more robust and reliable. They depend
on the physical and chemical properties of the system rather than on the success-
ful operation of instruments, safety devices, and procedures. Inherent and passive
strategies are often confused, but they are different. A truly inherent solution to a
safety issue will either completely eliminate the hazard or reduce the potential
magnitude of an incident associated with the hazard sufficiently that it cannot
cause significant damage. On the other hand, passive strategies do not eliminate
major impact on the distance over which hazardous concentrations of material can
occur in the atmosphere if the pipe is broken. Figure 5 shows the footprint of a toxic
phosgene cloud for a specific set of conditions, where the only difference is the size
of the phosgene pipe. The smaller pipe results in a much smaller toxic vapor cloud.
Inventory of hazardous material in pipes can also be minimized by using
the hazardous material as a gas rather than as a liquid. The Dow Chemical Exposure
Index (14) is a tool that can be used to measure inherent safety with regard to poten-
tial toxic exposure risk. Table 2 shows the reduction in the Chemical Exposure
Index that can be realized by handling a number of hazardous materials as a gas
rather than as a liquid, assuming that the same-size pipe can deliver the required
flow rate. Figure 6 shows the decrease in the hazard zone (toxic cloud footprint)
that resulted from relocating a chlorine vaporizer from a production building to
a storage area. Following the modification, the long chlorine transfer line contained
gaseous chlorine instead of liquid chlorine.
6.3.1. Nitration
Nitration reactions are highly exothermic, can generate high pressure in a closed
system from noncondensible by-products from undesired side reactions, and
often produce unstable reaction products, such as explosives. Many years ago,
products such as nitroglycerine were manufactured in large batch reactors. As
engineers began to understand the physical and chemical processes involved in
nitration chemistry, they recognized that the chemical reaction actually occurs
very rapidly once the reactants come into contact with each other. The large reactor
Inherent
Process route safety index
9. SUMMARY
Safety considerations are an inseparable part of the development of a chemical
process and the design and operation of a chemical plant. While risk manage-
ment and safety features can be added on to a plant design or to an operating
plant, safety is most reliably and robustly ensured by developing inherently safer
processes.
Safety strategies can be categorized as inherent, passive, active, and proce-
dural. Inherent and passive strategies generally relate to the basic process tech-
nology and plant design and are nearly always implemented early in the design
life cycle. They focus on elimination of hazards or minimizing the degree of haz-
ard rather than on management of hazards. Process intensification is an important
approach to the development of inherently safer chemical processes because it
reduces the quantity of hazardous material in the process, thereby reducing the
inherent risk.
Active and procedural strategies are usually also a part of a chemical process
risk management program—it is not often possible to eliminate all hazards.
Process intensification can also make active and procedural safety features more
effective and economical. Safety equipment can be made smaller and less costly.
It may be feasible to use safety devices to protect against the hazards from small
processing equipment that are impractical for use in a large plant. The faster
response time of small equipment may allow effective automatic or manual inter-
vention to detect an incipient problem and take action to prevent it from develop-
ing into a serious accident. Chemical process safety cannot be viewed in isolation
from other process and plant design criteria. The chemical plant must meet many
requirements for workers (safety, long-term health, employment and wages), own-
ers (operating costs, capital investment, profitability), customers (product quality,
reliability of supply, cost), neighbors (safety, health, environmental impact, eco-
nomic impact), and government (compliance with laws and regulations). All of
these are important, and they may be in conflict. The chemical process designer
must work to select the optimum design that considers all stakeholders. Process
intensification is an important approach to minimizing the hazards associated
with chemical handling and manufacture and will be an important factor in the
future for designing safe, environmentally friendly, and economically competitive
chemical plants.
Social/people
Provide for the needs of the poor: Prime goal
water, food, clothing, local
energy, etc
Fair distribution of wealth, power, Adaptable, nondisruptive to society
and knowledge
Social acceptance By stakeholder engagement
Safe Loss prevention at all conditions
Noise Below legal limits
Smell No obnoxious emissions
Occupational health Long-term effects of exposure to
chemicals should be known and
acceptable
Plot area impact Low; important in densely
populated areas
Skyline impact Low aesthetic and bird friendly
Ecological/planet
Sensitivity to world-scale nature No emission of components whose
and ecology ultimate environmental fate is
unknown
Depletion of abiotic resources Keep air, surface water, and soil
healthy
Depletion of biotic resources; Maintain biodiversity
biodiversity
Dehydration Maintain water reservoirs
Ozone depletion potential (ODP) No ODP gas emissions
Global warming potential Green house gas emissions reduced
by factor 4
Photochemical ozone pollutants Volatile organic component
emissions below expected future
legal limits
2.3.1. Social/People
A prime goal of sustainable development on a world scale is to provide for the
needs of the poor. Throughout one should keep in mind that developed
economies have different challenges than survival economies. For survival coun-
tries the main goal is to provide for the needs of the people in an affordable way
while not consuming natural capital (29). Hence this is an important item on the
n
Global - warming effect (kg) ∑ (Emissions to air)i (GWP)i
i1
Example: The GWP of a factory that per year emits 1 megaton of CO2, 10 kilo-
tons of CH4, and 1 kiloton of N2O is
3(1 1 megaton 0.01 62 0.001 290)
1.352 megatons CO2 equivalent per year
Other environmental impacts can be calculated similarly by using the
appropriate equivalency factor. Impacts of human toxicity and ecotoxicity are, for
example, determined by factors such as toxicity data (for humans, resp. various
nonhuman life forms), persistence, and bioaccumulation. Equivalency factors for
a wide range of substances can be found in the literature (32) and for industrial
chemicals (33).
4. Valuation. In the valuation step, all impacts are multiplied by norm fac-
tors. The resulting figures are added up to yield a single total figure. The norm
factors are subjective, for they express the relative importance one gives to totally
different environment effects. This subjectivity can be made more acceptable by
having the norm factors set by a panel with representatives of various worldviews
or political parties.
5. Improvement. One of the great uses of LCA is to pinpoint places in the
lifecycle that cause major environmental impacts and thus lead to highly efficient
improvement of the impact spectrum for a given product.
The LCA results can be used for a sustainability assessment of a new tech-
nology by comparing the outcome with the existing technology results. In the
conceptual phase of the new technology, a relative assessment can be used to
highlight where improvements should be made and where the problem areas are.
This is shown in Section 3 on process intensification assessment.
Detailed Information on the LCA method is provided by Hauschild (32).
2.3.3. Economy/Profit
It is obvious that if scarce nonrenewable resources such as fossil fuels and rich
metal ores are going to be depleted, prices will become extremely high. Which
means that the next generation will experience higher costs for the same goods,
which is not fair. If scarce resources are depleted, then developments should also
start to provide alternatives at a similar price, so-called “strong sustainability
economic development” (2). Obvious scarce resources—water and fossil fuels—
are explicitly put on the scorecard.
The future high resource cost and the external cost related to emissions
should also be taken into account in the total lifecycle cost.
Long-term profit is also placed on the scorecard. If a technology is not prof-
itable it will not be accepted by business. However, it is very important to think
Social/people
Provide for the needs of the poor:
water, food, clothing
Fair distribution of wealth, power,
and knowledge
Social acceptance
Safe: lower reactive, dangerous content Yes Yes
Noise
Smell
Occupational health —
Size (equipment volume reduction) 3 3
Smaller plot area impact 10 4 4–10
Smaller skyline impact
Ecological/planet
Sensitivity to world-scale nature
and ecology
Depletion of abiotic resources
(clean air, etc.)
Depletion of biotic resources;
biodiversity
Dehydration
Depletion of stratospheric ozone layer
Global warming 5 >1.4 1.4 1.2 1.2–5
Formation of photochemical 10 1.2 12–10
pollutants
Acidification 5 >1.4 1.4 1.2 1.2–5
Human toxicity
Ecotoxicity (terrestrial and aquatic)
Nutrification (eutrophication)
Radiation
Thermal pollution 5 16 1.4 1.2 1.2–16
Waste 3.5 3.5
Economy/profit
Scarce resource depletion
Drinking water resource depletion
Fossil fuel depletion 5 >1.4 1.2 1.2–5
External (future) cost low
Capital expenditure 5 0.8–1.6 1.6 0.8–5
Operational cost 5 1.4 1.6 1.4–5
Profitable over total lifecycle
Derived from process data, assuming other lifecycle steps are hardly affected.
Process intensification
Sustainable development item improvement potential
Social/people
Provide for the needs of the poor: water, Not identified yet
food, clothing
Fair distribution of wealth, power, and Not identified yet
knowledge
Social acceptance Probably yes
Safe: lower reactive, dangerous content Yes; factor > 10 possible
Noise Yes; fewer pumps and
pieces of equipment
Smell Yes; fewer flanges, less
diffusive emissions
Occupational health Yes; by less diffusive
emissions
Construction volume reduction Yes; factor > 4 possible
Plot area impact Yes; factor > 4 possible
Skyline impact Yes; factor > 4 possible
Ecological/planet
Sensitivity to world-scale nature To be assessed for each case
and ecology
Depletion of abiotic resources Yes; lower emissions
(clean air, etc.)
Depletion of biotic resources; biodiversity Not identified
Dehydration Not identified
Depletion of stratospheric ozone layer
Global warming Yes; far less energy required
Formation of photochemical pollutants Yes; less diffusive emissions
VOC
Acidification Yes; less energy required
Human toxicity
Ecotoxicity (terrestrial and aquatic)
Nutrification (eutrophication)
Radiation
Thermal pollution Yes; less energy required
Waste Yes
Economy/profit
Scarce resource depletion To be assessed for each case
Drinking water resource depletion Not identified yet
Fossil fuel depletion Yes; improvement factor > 4
External (future) cost low Yes
Lower capital expenditure Yes; factor > 4
Lower operational cost Yes; factor > 4
Profitable over total lifecycle Likely
4. EPILOGUE
It is clear from the foregoing that presently known PI methods can contribute con-
siderably to the process industry in meeting the social, ecological, and economic
constraints of sustainable development. For each new application it remains a
challenge to the engineers to identify ways to provide for the needs of people,
especially the poor, while meeting all SD constraints.