5

Process Intensification Through

Microreaction Technology

Wolfgang Ehrfeld
Ehrfeld Mikrotechnik AG, Wendelsheim, Germany

1. MICROTECHNOLOGY AS A KEY FOR THE

ADVANCED DESIGN OF CHEMICAL PLANTS
Since the middle of the 20th century, general technological progress has been
dominated essentially by a unique strategy of success, which constantly aims at
comprehensive miniaturization and integration of functional elements in
technical systems. The most outstanding development took place in
microelectronics, where integrated circuits with hundreds of millions or even
billions of transistors have become products of our daily lives. More recently,
micromechanical, microoptical, microfluidic, and many other microdevices have
become the basis for a multibillion dollar business, the market for
microtechnology (1–3). The products of microtech- nology have achieved a key
position in information, communication, entertain- ment, automotive, and
medical technologies.
In the chemical and pharmaceutical industries, biochemists were the first
or, at least, the fastest to make an interdisciplinary move into the promising field
of microtechnology. Terms like lab on a chip, microarrays, microfluidics, and
micro total analysis systems have become familiar to all working in the life
sciences and at the front line of genomics, proteomics, glycomics, metabolomics,
and all the other “omics” in this area. They regard biomolecules to some extent
like a source of data and, consequently, have no problems applying information-
based technologies to
innovations in their own field. In the same way, large information technology
(IT) companies have started to enter the area of life sciences, utilizing their
traditional strengths in combination with the concepts of microreaction
technology.
Researchers in chemical engineering are also intensively analyzing the
pos- sibilities potentially offered by the general strategy of miniaturization and
inte- gration to realize a radical change in design philosophy for modern
chemical plants. This research and development work started at ICI in the late
1970s, and the term process intensification was used to characterize the novel
concept. The main intention was to achieve much lower investment, operating,
and maintenance costs for chemical plants, without decreasing their production
capacity, by means of a dramatic reduction in plant size; they aimed at a
reduction factor of 100 or even 1000 (4,5).
This intention may look more like a dream than a serious concept.
However, the technological progress even in standard plant items has proven,
beyond doubt, that this concept has a realistic basis. One may just consider, on
the one hand, a standard stirred-tank reactor with a cooling jacket having a
volume of about 10 m3 and, on the other hand, a potentially equivalent reactor
for the same production capacity consisting of a static mixer and a compact heat
exchanger having a volume of about 0.1 m3 (6). This simple comparison
demonstrates the superior- ity of continuous operation over batch processing
with regard to specific plant volume and its importance in process
intensification. Many other potential exam- ples exist, such as spinning disk
reactors, vortex scrubbers, reactor-mixing sys- tems, and, of course,
multifunctional reactors, which integrate reactions and unit operations.
There is no doubt that the ultimate development of process intensification
leads to the novel field of microreaction technology (Figure 1) (7–9). Because of
the small characteristic dimensions of microreaction devices, mass and heat
trans- fer processes can be strongly enhanced, and, consequently, initial and
boundary con- ditions as well as residence times can be precisely adjusted for
optimizing yield and selectivity. Microreaction devices are evidently superior, due
to their short response time, which simplifies the control of operation. In
connection with the extremely small material holdup, nearly inherently safe plant
concepts can be realized. More- over, microreaction technology offers access to
advanced approaches in plant design, like the concept of numbering-up instead of
scale-up and, in particular, the pos- sibility to utilize novel process routes not
accessible with macroscopic devices.
As a matter of fact, microfabrication methods have to be introduced into
chemical engineering in order to profit from the potential advantages of micro-
reaction technology. Although this is a difficult hurdle, a few chemical
companies have successfully started to utilize microreaction technology for
commercial syn- theses of fine and special chemicals. Nevertheless, much effort
must still be spent to transfer further promising research results into commercial
application and to
FIGURE 1 Evolutionary development through process intensification.

get away from traditional strategies in chemical engineering. In the following,

a comprehensive analysis covering these aspects will be given.

2. EFFECT OF MINIATURIZATION ON UNIT OPERATIONS

AND REACTIONS
2.1. Enhancement of Heat
Transfer and Mass Transfer
Processes
Diffusion, thermal conductivity, and viscosity are physically similar phenomena
that involve the transport of a physical quantity through a gas or liquid. The driv-
ing forces for the corresponding transport fluxes of mass, energy, and
momentum are the gradients in concentration, temperature, and velocity,
respectively, where in all three cases the fluxes are in the same direction as the
gradients. For given differences in these properties, a decrease in the
characteristic dimensions results in an increase in these gradients and,
correspondingly, in higher mass and heat transfer rates as well as in higher
viscous losses. Accordingly, mixing and heat exchange systems with extremely
high transfer rates per unit volume can be real- ized by miniaturization; on the
other hand, however, the effect of viscous losses has to be taken into account.
Besides the effect of decreasing linear dimensions on the corresponding
gradients, the effective surface area for exchange processes has to be considered.
With decreasing characteristic dimensions, the surface-area-to-volume ratio of
the system increases. This results in a corresponding enlargement of the specific
interface area, i.e., of the area per unit mass or unit volume, for transfer
processes, so, in connection with the enhancement of the gradients, i.e., the
driving forces for heat and mass transfer, extremely efficient mixers and heat
exchangers can be realized by miniaturization. Furthermore, the amount of
material in a system is reduced with the reciprocal third power of the
characteristic dimensions, and, consequently, the response time of the
microdevice is extremely reduced so that in most cases large differences
concerning temperatures and concentrations are diminished immediately.
It was demonstrated in many cases that highly exothermal reactions can be
performed under isothermal conditions using the channels of micro heat exchan-
gers as reaction volumes (Figure 2) (10). Pioneering work on this subject started
in the late 1980s, when micro heat exchangers with extremely high transfer rates
per unit volume were produced by means of advanced mechanical micromachin-
ing methods (Figure 3) (11). Meanwhile, specific heat transfer rates of more than
20 kW per cm3 have been achieved, and a broad spectrum of materials has been
successfully applied.
A wide variety of micromixers are also available that allow mixing times
in the submillisecond range (8,12). They utilize mainly the concept of
multilamination, where two streams of fluids are split into a large number of small
substreams and fed alternately into an interdigital flow system, where they merge
into a joint stream (Figure 4). Other concepts are based on the principle of
splitting, side-to-side arrangement, and further splitting to generate an increasing
number of substreams with different compositions, as known from large-scale
static mixers. Vortex-type micromixers have also abeen applied.
A wide range of applications for micromixers exists in the fields of gas–
liquid suspensions and liquid–liquid emulsions, with extremely small bubble and
droplet sizes, respectively. A high uniformity concerning size distribution is
achievable; in particular, the specific power consumption for generating
suspensions and emulsions is much lower than in the stirring devices or high-
pressure jets usually applied in the macroscopic range (8,13). Accordingly,
micromixers are prom- ising tools to improve the performance of phase transfer
and other exchange processes.

2.2. Inherent Process Restrictions in Miniaturized

Devices and Their Potential Solutions
As a matter of fact, miniaturization inevitably results in a number of process
restrictions, and completely new problems arise, too. There are, above all, the
problems of blockage of microstructures by solid particles and fouling effects.
Moreover, corrosion might be much more dangerous for microscopic than for
macroscopic devices.
 FIGURE 2 Microreactor for parallel screening of catalysts for partial oxidation of methane.
(Source: D. Hönicke, TU Chemnitz.)

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 FIGURE 3 Micro heat exchanger produced by means of mechanical
micromachining. (a) Platelet with grooves of 30-µm depth and 70-µm width.
(b) Assembly of crossflow heat exchanger. (c) Final devices. (Source:
Forschungszentrum Karlsruhe.)

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

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 surface forces might far exceed those of mass or bulk forces. This problem is
immediately evident when regarding the reflux in a miniaturized distillation col-
umn or the settler in a micromixer/microsettler system. To some extent, rotating
devices can be applied and centrifugal forces can be utilized for material
transport. This approach has been demonstrated successfully in microfluidic
systems, but it is not a general solution. Consequently, other methods for phase
separation are required for miniaturized process devices, such as microfiltration to
break emulsions and the utilization of hydrophobic and hydrophilic surfaces or
capillary effects. Finally, surface effects will become more and more dominant
in chemical reac- tions when the characteristic dimensions are reduced, which
may produce advan- tages or disadvantages, depending on the respective type of
reaction.

2.3. Consequences for the Selection of Reaction Routes

and Plant Design
The extreme enhancement in mass and heat transfer rates through
miniaturization of process devices results in fundamentally novel design
possibilities with respect to selecting alternative reaction routes and plant design.
In contrast to macro devices like large stirring tanks, the starting conditions for a
chemical reaction can be set precisely with respect to time and concentration
because of the much faster mixing of educts in a micromixer. The reaction starts
at precisely defined time and position with a spatially uniform composition. Thus,
unfavorable reaction conditions

FIGURE 4 Micromixers. (a) Interdigital structure of a multilamination micro-

mixer. (b) Principle of split-and-recombine static micromixers. (Source:
IMM.)

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 due to incomplete mixing are minimized that eventually result in undesired side
and secondary reactions and, consequently, losses in yield and selectivity.
The high heat transfer rates achievable in micro heat exchangers and
reactors avoid unfavorable reaction conditions resulting from hot spots or thermal
runaway effects. An optimum temperature or temperature profile for the reaction
can be chosen with respect to spatial distribution and time. Thus, a fast-flowing
fluid ele- ment can be cooled down or heated up very rapidly, in fractions of a
millisecond. Because of the small thermal mass of microdevices, a periodic
change of tempera- ture of the reactor can be realized, with a typical time
constant of some seconds. All these examples offer possibilities to improve
yield and selectivity.
Since micro reactors—except for high-throughput screening in combinatorial
materials research—are usually operated under continuous conditions, it seems
simple to adjust the optimum residence time by means of a suitable delay loop or
channel that is also favorable with respect to yield and selectivity (Figure 5).
How- ever, the flow conditions in microdevices are generally characterized by a
low Reynolds number; consequently, a parabolic Hagen–Poiseuille profile will
exist in long channels and ducts. This flow profile results in an unfavorable
broadening of the distribution of residence time. Special channel configurations
allow one to reduce this effect.

2.4. Process Control and Safety

The inherent advantage of precise adjustment of the starting and boundary con-
ditions for chemical reactions and unit operations in microdevices provides a
novel basis for process control. Taking into account, in addition, the small
holdup,

FIGURE 5 Process intensification by setting the optimum residence time.

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 FIGURE 6 Explosion-proof continuous synthesis in the explosive range. The
reaction system consists completely of flame-retarding microchannels.

it is evident that an extremely short response time is a further inherent advantage

of microreaction devices with respect to process control.
As a result, there is a unique chance to utilize alternative reaction routes
for chemical synthesis that so far have not been applied commercially, for
reasons of safety or difficulties in process control or because it is fundamentally
impos- sible to realize such reaction routes using macroscopic devices. This is
the case, in particular, for controlled reactions in the explosive regime (Figure 6)
(15). This is accessible by means of microreaction devices, since, due to their
small characteris- tic dimensions, they act like flame retention baffles. Moreover,
the small dimen- sions allow reactions to be performed at extremely high
pressure, which is of importance for chemical processes using supercritical
solvents.

2.5. Sustainable Development by Numbering-Up

and Distributed Production
The safety problems connected with the storage of large quantities of educts and
products remain, of course, unchanged when a conventional plant is replaced by
a microreaction plant with the same production capacity. Nevertheless, this
problem may be reduced by replacing a large plant by several small plants for
distributed production. In contrast to conventional plants with macroscopic
process devices, where scale-up usually results in a considerable reduction of
specific investment costs, microreaction plants may instead profit from the mass
production of micro- devices in reducing specific investment costs. Scale-up for
achieving the desired production capacity can be done only at one site, while a
plant comprising a large

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 number of identical chemical microdevices according to the numbering-up
concept can be split up for production at several sites. As a result, microreaction
technology may contribute to the strategy of sustainable development by saving
resources due to a higher yield and, in particular, by flexible production on site
and on demand.
There are a number of further advantages to the numbering-up concept.
Research results can be transferred into production faster, plants can be
constructed in a shorter time, and the production capacity can be adjusted more
flexibly to variations in demand. Since mass production of microdevices may
result in rela- tively a low cost per piece, novel cost-saving maintenance and
repair concepts based on disposable elements might be introduced.

3. FROM BASIC PROPERTIES TO TECHNICAL

DESIGN RULES
In contrast to microelectronics, where extremely powerful software tools and
detailed design rules exist for the development of ultralarge-scale integrated cir-
cuits, there are no corresponding comprehensive means in microreaction
technol- ogy available to date. Such design tools should comprise mathematical
modeling of flow and chemical reactions in miniaturized systems as well as
specifications for suitable materials and simulation of manufacturing processes
applicable to the respective microreaction devices.
Since it will take several years to realize such an integral software toolbox,
individual approaches with separate steps have to be applied to meet gradually
the requirements of microreactor design. Standard software for computational
fluid dynamics is directly applicable in this context, and there are also powerful
software tools for the simulation of special steps in microfabrication processes.
However, there has been rather little experience with materials for
microreactors, optimiza- tion of microreactor design, and, in particular, the
treatment of interdependent effects. Consequently, a profound knowledge of the
basic properties and phenom- ena of microreaction technology just described is
absolutely essential for the suc- cessful design of microreaction devices.
For instance, proper design rules must take into account that mixing and
heat exchange systems with extremely high transfer rates per unit volume can be
realized via miniaturization but that an increase in viscous losses may counter-
balance the positive effects. Accordingly, suitable figures of merit must be
defined for micromixers and micro heat exchangers that consider the ratio of
mass or heat fluxes to pressure losses. However, the value of such a figure of
merit should be always considered in context with further boundary conditions
of the process and the interdependence of several process properties. Decreasing
the characteristic dimensions of a system results, as already explained, in a
reduction in the material holdup and a simultaneous enlargement of the surface-
area-to-volume ratio of the system. These aspects also determine the speed of
mixing and heat transfer and,

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 consequently, the degree of miniaturization required in a specific case. Such
aspects have to be considered for a favorable design of a microreaction system;
in some cases, extremely small dimensions are not necessary to avoid
unfavorable re- action conditions resulting from hot spots or thermal runaway
effects.
If large amounts of materials have to be transported, a favorable design should
instead consider large pumps rather than arrangements with many micropumps,
which, in most cases, are commercially unattractive for cost reasons and technic-
ally less suitable because of their comparatively low efficiency.

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

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 soft aspects will be considered in more detail in the following analysis of micro-
fabrication methods for reaction devices.

4.2. LIGA Technology

The LIGA technology allows the production of ultraprecise micro structures
with an extreme aspect ratio from a wide variety of materials (16,17). It is based
on a combination of deep lithography, electroforming, and molding processes. In
the first step of the manufacturing sequence, a pattern from a mask or by means
of a serial beam-writing process is transferred into a thick resist layer on an
electri- cally conductive substrate. Ultraprecise microstructures with an extreme
aspect ratio can be generated by deep X-ray lithography. Using special epoxy
resists like SU 8, which utilizes intrinsic optical waveguide properties of
irradiated crosslinked regions, favorable results are also achievable by means of
UV litho- graphy.
In the second step, the three-dimensional relief-like structure of the resist
polymer generated by deep lithography is transferred into a complementary
metal- lic structure by means of electroforming, starting from the electrically
conductive substrate. Usually a nickel sulfamate electrolyte is applied, but there
are also proven electrolytes available for deposition of other metals and metal
alloys.
The metal structure generated by means of electrodeposition may be the
final product in some special cases. In general, however, it is used in a third step
as a master tool for a replication process, such as injection molding, casting, or
emboss- ing, for mass fabrication of microstructures. A wide variety of mold
materials can be applied for micromolding, e.g., organic polymers, preceramic
polymers, and ceramic and metallic powders with organic binders for subsequent
sintering, so that most material requirements for chemical microdevices can be
favorably met.
It should be emphasized that the development of the LIGA technology
orig- inated from a special requirement in nuclear process engineering. Curved
micro- nozzles with characteristic dimensions in the micrometer range were
needed as mass products for aerodynamic separation of the uranium isotopes in
the frame- work of a large technological development work at the Karlsruhe
Nuclear Research Center (Figure 7). Today there are a number of LIGA
products that evi- dently have promising markets in the fields of micro-optics
and integrated optics, molecular biotechnology, and microactuators. More
recently, LIGA components and systems have been successfully applied to
chemical engineering and microreaction technology, respectively. A number of
chemical companies and, of course, research institutes utilize devices such as
micromixers, micro heat exchangers, and micro bubble columns as well as
modular systems with integrated functional elements for reaction, heat transfer,
mixing, separation, and fluid distri- bution for process development. LIGA
devices are also seriously being consid- ered by the chemical industry for the
production of fine chemicals.

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 FIGURE 7 Double-deflecting micronozzle for aerodynamic separation of ur-
anium isotopes manufactured by LIGA technology from nickel. The smallest
characteristic dimensions achieved in such devices are below 10 µm.
(Source: Institute of Nuclear Process Engineering at the former Karlsruhe
Nuclear Research Center, now Forschungszentrum Karlsruhe, Siemens.)

4.3. Wet and Dry Etching Processes

Wet etching processes are widely used to produce microstructures by means of
transferring resist patterns into various materials. However, for most materials only
isotropic etching processes exist, so, because of lateral underetching of the resist
pattern, only shallow microchannels or other shallow structures can be generated at
the surface of a bulk material. Three-dimensional structures can be manufactured
when the pattern is etched completely through thin foils, which then have to be
stacked in order to realize deep microchannels with a high aspect ratio (Figure 8).
Isotropic etching has been applied several times for manufacturing micro-
reaction devices. The technological expenditure is relatively low, but there are
some restrictions concerning accuracy, surface roughness, and geometrical
design. The product spectrum comprises various types of heat exchangers, micro-
mixers, separators, reaction units, and even integrated devices with several func-
tional elements.
Wet chemical anisotropic etching of monocrystalline silicon has been
widely applied in microtechnology (18,20). This method is based on the
dependence of etching velocity on crystal orientation, so only a few basic
geometries can be

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 FIGURE 8 Microetched foil of stainless steel for manufacturing micro heat
exchangers by stacking and diffusion welding. (Source: Ehrfeld
Mikrotechnik, Ätztechnik Herz.)

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

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 wafer. Subsequently, silicon is etched by means of a fluorine-containing low-
pressure plasma that generates gaseous silicon compounds.
In order to generate microstructures with an extremely high aspect ratio,
the directed etching process is connected with a subsequent deposition process
from the plasma where the walls oriented in parallel to the etching direction are
covered with a plasma polymer resistant to the reactive plasma (21). By means
of multiple repetition of directed etching and side wall passivation, channels and
other structures with nearly vertical walls can be realized; accordingly, extremely
high aspect ratios are achievable for nearly any cross-sectional shape (Figure 9).

FIGURE 9 Channel structure of a phase separator generated by ASE deep

etching of silicon. (Source: IMM.)

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 This so-called advanced silicon etching (ASE) process achieves etching
velocities on the order of 0.2 mm per hour. The ASE dry etching method has, of
course, limitations concerning, e.g., material selection and surface smoothness or
the brittleness of silicon, which makes it nearly impossible to use it directly as a
mold insert in micromolding processes. Nevertheless, it is possible to transfer
ASE silicon structures into complementary metal structures by electroforming.
For a number of applications, ASE is evidently a favorable alternative to LIGA
in manufacturing devices for microreaction technology.

4.4. Mechanical Micromachining

In the past few years, impressive progress has been made in so-called
mechanical micromachining, utilizing technologies based on so-called
ultraprecision machining. Complex three-dimensional microstructures have been
generated with shape accur- acies in the submicrometer range by means of
milling, turning, and grinding (11,22). Three- and five-axis ultraprecision
micromilling machines are available as commercial products. Using diamond
tools, an extremely low surface rough- ness of a few nanometers is achievable
for nonferrous materials. Progress has also been made in machining stainless
steel by using ultrafine-grain hard metal tools and novel technologies like
vibration cutting. In addition, mechanical micro- machining has been
successfully applied with brittle materials. Micromixers, micro heat exchangers,
and reaction systems have been successfully produced by means of this
technology (Figure 3).
It is evident that there are hardly any limitations concerning the generation
of microstructures for chemical microdevices with complex geometries,
extremely high aspect ratio, and high precision from a wide variety of materials
by means of mechanical micromachining. Rather, restrictions may exist when
manufacturing closely packed channels or other structures, because of the finite
size of the tools. Also, manufacturing costs may become a problem in mass
fabrication; but in such a case, mechanical micromachining may be helpful for
manufacturing mold inserts for mass fabrication by means of micromolding.
Moreover, there are other mechanical methods for high-volume production, like
punching and embossing, that have been successfully applied in fabricating, e.g.,
micro heat exchangers.

4.5. Microelectrodischarge Machining

An interesting alternative to standard mechanical micromilling, turning, drilling,
and grinding methods is microelectrodischarge machining (EDM), which is
virtu- ally unlimited with respect to the geometrical shape of the work piece (23).
Material is removed in a discharge between the electrically conductive work
piece and an electrode by small sparks in a dielectric fluid such as oil or
deionized water. An important advantage in micromachining is that the forces
acting on the work piece

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 in EDM are extremely low. The disadvantages of micro EDM are a relatively large
surface roughness, limitations in miniaturization because of the finite size of the
electrodes and the spark gap in the electrical discharge, and very long machining
times, so this method is essentially used to manufacture mold inserts or
prototypes. The methods of mechanical micromachining and micro EDM have
been extensively applied to the fabrication of components such as micro heat
exchangers, mixers, and reaction channels as well as chemical microsystems with
integrated
heat exchange, reaction, mixing, and distribution elements (Figure 10).

4.6. Micromachining by Means of Laser Radiation

Microfabrication by means of laser radiation covers a wide range of different
methods (24,25). On the one hand, these are processes where material is
removed in an intense electromagnetic field by melting, evaporation,
decomposition, photo- ablation, or a combination of these phenomena. On the
other hand, generating processes exist where structures are built up from liquid
resins, laminated layers, or powders using, e.g., photochemically induced
crosslinking of organic compounds

FIGURE 10 Micromixing element generated by microelectrodischarge machin-

ing. (Source: Ehrfeld Mikrotechnik, Zumtobel.)

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 FIGURE 11 Part of a static micromixer manufactured by laser ablation from
aluminum oxide. (Source: Ehrfeld Mikrotechnik, Heidelberg Instruments
Microtechnologies.)

in stereolithography or powder solidification by laser sintering. In addition, welding

by means of laser radiation is of major importance for the connection and assem-
bly of microdevices.
There are no restrictions worth mentioning concerning materials in micro-
machining by laser radiation, which is a real advantage for chemical
microdevices (Figure 11). However, limitations exist to achieving critical
dimensions below 10 µm and low surface roughness. Removal of material is also
often connected with the generation of debris, which reduces accuracy. Since laser-
based microfabrication
processes, except lithography, are essentially serial rather than parallel
machining methods, their productivity is comparatively low. Nevertheless, they
offer a huge potential in rapid prototyping.
Laser-based micromachining processes have been applied to date only on
a relatively small scale for manufacturing chemical microdevices (27). This will
probably change relatively soon, since rapid prototyping will become more and
more important for developing novel microreaction devices.

5. IMPLEMENTATION OF MICROREACTION TECHNOLOGY

Microreaction technology has created a novel basis for:
Accelerating screening in combinatorial material development
Realizing extremely powerful tools for the evaluation of new reaction
path- ways
Implementing comprehensively the concept of process intensification for
the production of fine and special chemicals (Figure 12)

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 Following the development route of miniaturization in the life sciences,
the implementation of microreaction technology in combinatorial material
develop- ment has been very successful. Companies like Symyx, located in
Silicon Valley, whose business is based on the highly effective synthesizing and
screening of a huge number of chemical compounds, have demonstrated that
faster development and cost savings are achievable by means of microreaction
devices. Not only can the amount of reactants, auxiliary substances, waste,
energy, and space be mini- mized, but all the other advantages of microreaction
devices mentioned earlier can also be favorably utilized (see, e.g., Ref. 27). The
research work of such companies is focused on more efficient catalysts, new
polymers, high-performance phosphors for illumination, and, of course, drug
development and many other substances. Promising work in this direction is also
being done at universities and govern- ment research centers (7,8,26,28).
Researchers at BASF have shown that microreactors can be utilized that
give access to operating conditions that cannot be realized by means of
macroscopic equipment. They succeeded in improving yield and selectivity in a
highly exother- mal two-phase reaction in connection with the synthesis of a
vitamin precursor. At Degussa company, a microreactor test facility for
proprietary reactions is under construction. The major focus in this context is the
implementation of microreaction devices as powerful tools for process
development and, in particu- lar, for the evaluation of new reaction pathways.
Companies like Clariant and Merck use microreactors for production, and
they are obviously convinced that the ultimate development of process intensifi-
cation leads to microreaction technology. In contrast to other companies,
Clariant

FIGURE 12 Microreaction technology aims at production of (a) information,

(b) tools for process development, and (c) chemicals.

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 FIGURE 13 Modular microreaction system consisting of functional elements
for reactions and unit operations arranged on a base plate. The cube-
shaped modules of stainless steel with built-in microstructures have a side
length of 25 mm and can be operated at pressures up to 100 bar. ( Source:
Ehrfeld Mikrotechnik.)

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,

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 measurement, and control. The modules can be arranged and connected in a
wide variety of configurations and serve as a toolbox for realizing development
platforms similar to microplants (Figure 13). By means of such platforms, the
optimum oper- ation conditions of chemical processes as well as favorable plant
configurations can be determined and novel reaction routes tested. There is also
a wide range of applications in combinatorial chemistry. Since the microplants
are usually set up for continuous operation, they have a comparatively high
productivity and can be utilized directly for small-scale production of special
chemicals.

6. CONCLUSIONS
Future progress in chemical engineering will be strongly determined by process
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,

FIGURE 14 Roadmap of microreaction technology for novel process routes

and efficient production.

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 and operation of microreaction plants, and finally to demonstrate real
commercial success. Meanwhile, a lot of effort has gone in this direction, but
there is still a multitude of tasks to solve until decisionmakers will be convinced
enough of the commercial prospects of microreaction technology to accept the
inevitable finan- cial risks of technological progress.

REFERENCES
A comprehensive overview of the international development work on microreaction tech-
nology can be found in the Proceedings of the International Conferences on
Microreaction Technology, which are listed in the following.
Ehrfeld W, ed. Proceedings of the 1st International Conference on Microreaction
Technol- ogy. Berlin: Springer, 1998.
Ehrfeld W, Rinard I, Wegeng R, eds. Process Miniaturization: 2nd International
Conference on Microreaction Technology, IMRET 2; Topical Conference Preprints.
AIChe, New Orleans, 1998.
Ehrfeld W, ed. Proceedings of the 3rd International Conference on Microreaction
Technol- ogy. Berlin: Springer, 2000.
Rinard I, ed. 4th International Conference on Microreaction Technology. Topical Confer-
ence Proceedings. AIChE Spring National Meeting, Atlanta, GA, March 5–9, 2000.
Matlosz M, Ehrfeld W, Baselt JP, eds. Proceedings of the 5th International Conference on
Microreaction Technology. Berlin: Springer, 2001.
Rinard I, ed. 6th International Conference on Microreaction Technology, Conference
Proceedings. AIChe Spring Meeting, New Orleans, March 10–14, 2002.
The literature cited in this contribution is listed here.
1. Ehrfeld W, Ehrfeld U, Kiesewalter S. Progress and profit through
microtechnologies. Proceedings VDE World Microtechnologies Congress,
MICRO.tec, Vol. 1, 2000: 9–17.
2. Market Analysis for Micro Systems II, 2000–2005. A NEXUS Task Force Report,
2002.
3. Bundesministerium für Bildung und Forschung. Förderkonzept Mikrosystemtechnik
2000+, Bonn, Germany, Jan 2000.
4. Stankiewicz AI, Moulijn JA. Process intensification: transforming chemical engin-
eering. Chem Eng Prog 2000; (Jan):22–33.
5. Green A, Johnson B, John A. Process intensification magnifies profits. Chem Eng
1999; (Dec):66–73.
6. Wood M, Green A. A methodological approach to process intensification. IchemE
Symposium Series No. 144, 1998:405–416.
7. Jensen KF, Hsing I-M, Srinivasan R, Schmidt MA, Harold MP, Lerou JJ, Ryley JF.
Reaction engineering for microreactor systems. Proceedings of the 1st International
Conference on Microreaction Technology. Berlin: Springer, 1998:2–9.
8. Ehrfeld W, Hessel V, Haverkamp V. Microreactors. In: Ullmann’s Encyclopedia of
Industrial Chemistry. 6th ed. Weinheim: Wiley-VCH, 1999.
9. Jäckel K-P. Microreaction Technology—Vision and Reality. Plenary Lecture,
ACHEMA 2000, Frankfurt.

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 10. Mayer J, Fichtner M, Wolf D, Schubert K. A microstructured reactor for the
catalytic partial oxidation of methane to syngas. Proceedings of the 3rd International
Confer- ence on Microreaction Technology. Berlin: Springer, 2000:187–196.
11. Schubert K, Bier W, Linder G, Seidel D. Herstellung und Test von kompakten
Mikrowärmeübertragern. Chem Ing Tech 1969; 61:172–173.
12. Löwe H, Ehrfeld W, Hessel V, Richter T, Schiewe J. Micromixing technology. Pro-
ceedings of the 4th International Conference on Microreaction Technology. AIChE
Spring National Meeting, Atlanta, GA, March 2000.
13. Bayer T, Heinichen H, Natelberg T. Emulsification of silicon oil in water—
comparison between a micromixer and a conventional stirred tank. Proceedings of
the 4th Inter- national Conference on Microreaction Technology. Atlanta, GA,
AIChE Spring National Meeting, March 2000:167–173.
14. Wochner M. Mikroreaktoren—kleine Ergänzung für grosse Kessel, Clartext No. 3/
2002.
15. Hagendorf U, Jänicke M, Schüth F, Schubert K, Fichtner M. A Pt/Al 2O3 coated
microstructured reactor/heat exchanger for the controlled H2/O2 reaction in the
explosion regime. Proceedings of the 2nd International Conference on
Microreaction Technology, AIChE Spring Meeting, New Orleans, LA, March
1998, 81–87.
16. Ehrfeld W, Münchmeyer D. Three-dimensional microfabrication using synchrotron
radiation. Nucl Inst Meth Phys Res 1991; A303:523–531.
17. Ehrfeld W, Ehrfeld U. Microfabrication for process intensification. In: Matlosz M,
Ehrfeld W, Baselt JP, eds. Proceedings of the 5th International Conference on
Microreaction Technology. Berlin: Springer-Verlag, 2001:3–12.
18. Koehler M, Ätztechniken. In: Ehrfeld W, ed. Handbuch Mikrotechnik. München:
Carl Hanser Verlag, 2001:279–322.
19. Freitag A, Dietrich TR, Scholz R. Glass as a material for microreaction technology.
Proceedings of the 4th International Conference on Microreaction Technology. AIChE
Spring National Meeting, Atlanta, GA, March 2000:48–54.
20. Rangelow IW, Kassing R. Silicon microreactors made by reactive ion etching. Pro-
ceedings of the 1st International Conference on Microreaction Technology. Berlin:
Springer, 1998:169–174.
21. Laermer F, Schilp A (Robert Bosch GmbH). Method of Anisotropically Etching Silicon.
U.S. Patent No. 5501893, 1996.
22. Weck M. Ultraprecision machining of microcomponents. In: Weck M, ed. Proceed-
ings of the International Seminar on Precision Engineering and Microtechnology,
Aachen: European Society for Precision Engineering and Nanotechnology, July
2000.
23. Michel F, Ehrfeld W, Koch O, Gruber H-P. EDM for microfabrication—technology
and applications. In: Weck M, ed. Proceedings of the International Seminar on
Precision Engineering and Microtechnology, Aachen, July 2000.
24. Bremus E, Gillner A, Hellrung D, Höcker H, Legewie F, Poprawe R, Wehner M,
Wild M. Laser processing for manufacturing microfluidic devices. In: Proceedings
of the 3rd International Conference on Microreaction Technology. Berlin: Springer,
2000:187–196.
25. Gillner A, Klotzbücher T. Lasermikrobearbeitung. In: Ehrfeld W, ed. Handbuch
Mikrotechnik. München: Carl Hanser Verlag, 2001:105–143.

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.

 26. Wiessmeier G, Schubert K, Hönicke D. Monolithic microreactors possessing regular mesopore systems for the
successful performance of heterogeneously catalysed re- actions. In: Ehrfeld W, ed. Proceedings of the 1st
International Conference on Micro- reaction Technology., Berlin: Springer, 1998:20–26.
27. Jandeleit B, Schaefer DJ, Powers TS, Turner HW, Weinberg WH. Combinatorial materials science and
catalysis. Angew Chem Int Ed 1999; 38:2494–2532.
Claus P, Hönicke D, Zech T. Miniaturization of screening devices for the combina- torial development of heterogeneous
catalysts. Catal Today 2001; 67:319–339

Copyright © 2004 by Marcel Dekker, Inc. All Rights Reserved.