Chemistry in Microstructured Reactors

Reviews K. Jhnisch, V. Hessel et al.
Chemistry in Microreactors
Chemistry in Microstructured Reactors

Klaus Jhnisch,* Volker Hessel,* Holger Lwe, and Manfred Baerns
Keywords:
gas-phase reactions heterogeneous
catalysis high-throughput-
screening microstructured
reactors process
optimization
Angewandte
Chemie
406 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/anie.200300577 Angew. Chem. Int. Ed. 2004, 43, 406 446
Angewandte
Chemical Microprocess Engineering Chemie
The application of microstructured reactors in the chemical From the Contents

process industry has gained significant importance in recent
1. Introduction 407
years. Companies that offer not only microstructured reactors,
but also entire chemical process plants and services relating to 2. Properties of Microstructured
them, are already in existence. In addition, many institutes and Reactors 407
universities are active within this field, and process-engineering-
oriented reviews and a specialized book are available. Micro- 3. Liquid-Phase Reactions 411
structured systems can be applied with particular success in the 4. GasLiquid Reactions 417
investigation of highly exothermic and fast reactions. Often the
presence of temperature-induced side reactions can be signifi- 5. Photochemical and Electrochemical
cantly reduced through isothermal operations. Although Reactions 420
microstructured reaction techniques have been shown to opti-
6. Gas-Phase Reactions 422
mize many synthetic procedures, they have not yet received the
attention they deserve in organic chemistry. For this reason, this 7. Industrial Applications of
Review aims to address this by providing an overview of the Microstructured Reactors 437
chemistry in microstructured reactors, grouped into liquid-
8. Market Prognoses 439
phase, gas-phase, and gasliquid reactions.
9. Summary and Outlook 439
1. Introduction Thus, the knowledge of chemistry in a small but active area,

especially regarding possible applications, is exhibited on a
Microtechnology is currently an area of rapid growth in broader base. Meanwhile a wide range of microstructured,
many areas of application, and the last seven years have seen and even complete chemical process plants (especially for
the development of microstructured devices for chemical organic synthesis) are commercially available.[4, 1214] Compa-
reactions, the advantages of which have been demonstrated nies with microstructured devices and services are in the
most impressively.[17] market.[4, 13, 14] Many institutes devote themselves to this area,
An original patent from the former East Germany in 1986 universities offer lectures and practical classes,[15] and some
contained all of the essential features for how a microprocess-engineering-orientated reviews,[17, 1618] as well as a
structured system for chemistry should be built.[8] It is specialized book[3] are available.
noteworthy that the patent presented manufacturing proc-
esses for microstructured reactors; under the economic
circumstances, however, this knowledge could not be imple- 2. Properties of Microstructured Reactors
mented. By 1989, the Forschungszentrum Karlsruhe (Ger-
many) had already built the first micro-heat exchanger, and at 2.1. Definition of Microstructured Reactors
an early stage had identified and published its potential for
microchemical engineering.[9] Similar pioneering work also Microstructured reactors are (generally, but not exclu-
began in 1993 at the Pacific Northwest National Laboratory sively) reactors with three-dimensional structures, the inner
(PNNL, USA), although their work had a particular focus on dimensions of which are under a millimeter in size, and more
the energy sector.[10] specifically between ten and a hundred micrometers.[2, 3, 10] It
The application of microsystems for chemical and bio- therefore follows that the main feature of these reactors, in
logical reactions was discussed at a workshop in 1995 in Mainz comparison to conventional chemical reactors, is the high
(Germany), which can be seen as the starting point for surface-area-to-volume ratio. Specific surface areas of micro-
worldwide development.[11] In 1997, the first International
Conference for Microtechnology (IMRET 1) took place,
which has since been held annually in Europe and the USA, [*] Dr. K. Jhnisch, Prof. Dr. M. Baerns
and in 2001 the Industrial Platform of Modular Micro Institut f#r Angewandte Chemie Berlin-Adlershof e. V.
Chemical Technology (MicroChemTec), highlighting the Richard-Willsttter-Strasse 12, 12489 Berlin (Germany)
Fax: (+ 49) 30-6392-4350
industrial applications of microprocess engineering, was
E-mail: [email protected]
founded in partnership with DECHEMA.
Dr. V. Hessel, Prof. Dr. H. L@we
As a consequence of these initiatives, increasing industrial
Institut f#r Mikrotechnik Mainz GmbH
interest, in addition to nationally initiated funding, has led to Carl-Zeiss-Strasse 1820, 55129 Mainz (Germany)
the publication of approximately 1000 studies on microproc- Fax: (+ 49) 6131-990-305
ess engineering, albeit mostly in conference proceedings. E-mail: [email protected]
Angew. Chem. Int. Ed. 2004, 43, 406 446 DOI: 10.1002/anie.200300577 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 407
structures lie between 10 000 and 50 000 m2 m 3, while those of and model systems to develop microprocess engineering
traditional reactors are generally about 100 m2 m 3 and in rare apparatus by rational design. In many cases, basic physical
cases reach 1000 m2 m 3.[19] Since the heat-transfer coefficient mechanisms[2731] or intrinsic kinetics can be directly applied.
is inversely proportional to the channel diameter, a value on The prediction and confirmation of residence time distribu-
the order of 10 kW m 2 K 1 is obtained,[6, 20] which is signifi- tions are of great value to this procedure. Furthermore,
cantly higher than for traditional heat exchangers. This high controlled multiphase flow is due to the dominance of
heat-exchanging efficiency allows for fast heating and cooling surface and interface forces, as well as tailor-made active
in reaction mixtures within the microstructures whereby areas. Numerous publications are dedicated to conditions
reactions under isothermal conditions with exactly defined such as capillary flow,[32] slug flow,[3337] segmented flow,[38] or
residence times can be carried out.[2022] The development of hexagon-flow,[27] to name but a few.
hot spots or the accumulation of reaction heat within Process parameters such as pressure, temperature, resi-
microstructures is suppressed so that undesirable side reac- dence time, and flow rate are more easily controlled in
tions and fragmentations are hindered. The outcome in many reactions that take place in small volumes. The hazard
cases is higher selectivity, yield, and product quality. Thus, potential of strongly exothermic or explosive reactions can
microstructured reactors can be used to great effect for fast also be drastically reduced.[39, 40] Higher safety is also achieved
and/or strongly exothermic or endothermic chemical reac- in reactions with toxic substances or higher operating
tions.[23] pressures.[24, 41] The miniaturization has an immediate effect
In addition to heat transport, mass transport is also on the mechanism of explosions, in that radical chains or
considerably improved in microstructured reactors. Mixing thermal hold-up are suppressed.[39, 40] This allows a drastic
times in micromixers (down to several milliseconds) are broadening of the safe operating range in previous explosive
generally smaller than in conventional systems and due to the regimes. Indeed, reactions with toxic substances, or at high
small dimensions the diffusion times are very short, thus the pressures, have been carried out more safely.[24, 41] Veser[40]
influence of mass transport on the speed of a reaction can be explains that a relatively fault-tolerant safety level is achieved
considerably reduced.[24] because of the intrinsic conditions that are available, rather
A third aspect of microstructured reactors is the hydro- than through safety precautions.
dynamic flow in the microchannels, which is an important Due to the properties mentioned above, microstructured
feature of microfluidics.[25] The flows are mostly laminar, reactors can be advantageously used as process engineering
directed, and highly symmetric.[25, 26] In addition, the multi- tools for acquiring information, which allows, in a short time
phase flows often exhibit high order[2731] between the phases. and with greater safety, a process to be transferred to the pilot
These features are shown to allow the possibility to simulate and production scale. Information from microstructured
Klaus Jhnisch studied chemistry at TH Holger L>we studied at the University of

Mersburg, and received his doctorate from Leipzig and then worked from 1977 to 1984
the Institut f#r Organische Chemie, Berlin- as a research-group leader at the film-manu-
Adlerhof, in 1972 with E. Schmitz on the facturing company Wolfen. After graduating
amination of olefins and ketones. From at TH Merseburg (1984) he moved to TH
1980 to 1983, he worked as a group leader Ilmenau, specializing in electrochemistry and
at the Cuban Academy of Sciences in galvanotechnics. In 1991 he became group
Havana. He habilitated in 1991 at TH leader and departmental manager at IMM,
Mersburg, and since 1994 has been based at and in 1999 he became a R&ampD director
the Institut f#r Angewandte Chemie Berlin- responsible for chemical microprocess tech-
Adlerhof, where his work includes the asym- nology, biofluidic simulations, microoptics,
metric synthesis of amino acid derivatives, LIGA technology, and precision engineering.
and the functionalization of arenes in micro- He is the co-author of more than 250 publi-
structured reactors. cations, 30 patents, and a book about
microprocess engineering.
Volker Hessel studied chemistry at the Uni- Manfred Baerns studied chemistry in
versity of Mainz. He gained his doctorate Braunschweig and Hannover, and received
with H. Ringsdorf in 1993 on supermolecu- his doctorate in 1961 on mixing procedures
lar structures, micelles, and lyotropic liquid in fluidized-bed reactors. He then worked for
crystals. Since 1994, he has worked for the two years as a postdoctoral student at the
Institut f#r Mikrotechnik, Mainz GmbH Argonne National Laboratory, USA. After
(IMM), becoming a group leader in 1996 his habilitation at the University of Hann-
and a departmental manager for microreac- over (1970), he moved to the Krupp chemi-
tor technology and chemical processes in cal plant in Essen. From 1974 to 1995 he
1999. Since 2002, he has been the deputy was Professor of Technical Chemistry at the
R&ampD director of IMM. He is the co- Ruhr-Universitt Bochum, and since then
author of some 70 publications, a chapter in has been a scientific director of the ACA. He
the Ullmann's Encyclopedia of Industrial is also an honorary Professor at the Hum-
Chemistry, and a book about microprocess boldt-Universitt Berlin and the TU Berlin. He received the titanium
engineering. DECHEMA medal in 1999.
408 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org Angew. Chem. Int. Ed. 2004, 43, 406 446
Angewandte
reactors can also be used for optimizing process plants already

in operation. This approach has been successfully docu-
mented by WDrz et al. (BASF) in many examples from
chemical production.[23, 4244]
Microstructured reactors also give opportunities for new
production concepts. Depending on demand, more micro-
structured reactors or such subunits could be connected in
parallel (numbering-up) so that the required intermediate
products and end-products can be produced in their required
amounts.[45, 46] Dimensionalization and capacity utilization
problems, such as those witnessed with big plants, would be
eliminated. It should be mentioned that these concepts have
been, until now, insufficiently implemented from a technical
point of view. The reasons for this are partly due to the
significant distribution and fouling problems in the complex
connected microstructured reactors of the current technology,
which still need to be resolved, as well as the hesitation of
industry to use this potential. The latter factor, often based on
sound principles, results mainly from the complexity of the
chemical processes involved, and a reluctance to change from
known and reliable procedures (in this case, being batch
operation).
Nevertheless, it seems it is only a matter of time until these
technical hurdles are tackled. One example is the German,
publicly funded, DEMiS project, with partners in both
industry and academia. Within the framework of this project
a pilot plant for heterogeneously catalyzed gas-phase reac-
tions was founded in Degussa in Hanau. The core of the plant
(which is two storeys high) is a microstructured reactor. The
aim of this project is to answer key constructive, process, and
operational questions and thereby to demonstrate the feasi-
bility of this technology on the industrial scale (Figure 1).
Figure 1. Degussa's experimental reactor for the pilot operation of a
It is evident that multiscale approaches using micro-
gas-phase reaction (source: Degussa, Hanau).
structured reactors will be chosen more often in the future
(for example, for process-innovative equipment with different
optimum characteristic inner and outer dimensions), rather Mixing procedures are thus limited to diffusion and secondary
than monolithic constructions for pilot and production flows. Turbulence-induced mixing procedures, such as agita-
operation; this is in line with the motto: only as small as is tion, are in general not possible.[52] For this reason, the typical
necessary.[4] Another aspect of multiscaling is that the small sequence from macro- to micromixing is not observed.
is part of the big; that is, the ability to use hybrid substitutes Micromixing starts almost exclusively from regular periodical
of small reactors next to large reactors or larger process- concentration profiles, preferably with steep gradients. Due to
engineering components[4] (see also for example, the con- this, very short mixing times can be achieved in micro-
struction of Axiva reactors[3, 4749]). In this sense, in certain mixers;[10, 53] for liquids this is typically from a second down to
cases combined scale-up and numbering-up approaches a few milliseconds.[53]
would also be chosen to combine the best properties of Similarly it is true that very efficient heat transfer is
traditional and microprocess engineering operations.[50, 51] created.[6, 10, 54] The different contributions to heat conduction
All these approaches are thus generally appropriate in in the fluid and the reactor material, as compared to
assisting a continuous mode of operation. Discontinuous macroscopic apparatus, should be noted. At first sight, it
batch reactions could in certain cases be operated through the was calculated that glass is superior to copper as a material for
application of microreactors in an economically advantageous counterflow. In glass there is considerably reduced axial heat
continuous-process mode.[45, 46] conduction performance, which negatively affects the temper-
ature profile.[55] In addition to fluidfluid heat transfer, heat
conduction through the material of construction is also
2.2. Physical Principles for Chemical Processing in directly and advantageously used in microstructured reactors
Microstructured Reactors for setting the temperature in the reaction region or to
dissipate the heat of reaction.[56] This can, for example, be
Microstructured reactors are as a general rule character- done through electrical heating.[57] The high wall volume to
ized by laminar flow; typical Reynolds numbers lie between 1 reaction volume ratio is advantageous for control of the
and 1000 depending on velocity and channel dimensions.[25] reaction. Complex scenarios, for example, investigating the
Angew. Chem. Int. Ed. 2004, 43, 406 446 www.angewandte.org 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 409
effect of heat conduction of the housing of the microstructure, to the numbering-up concept.[76, 77] Here, mainly theoretical
have also been recently the subject of scientific investigations. gas-distribution studies for arrays with various compensation
Since the assemblies are made of materials with different arrangements were presented. Experimental findings for the
conductivities, heat management in narrow spaces and at verification of these predictions are still rare.
interfaces is rather complex, and requires special methods for
heat addition and removal, such as, for example, an asym-
metric introduction of cooling fluid flows.[5860]
The small reaction volume of microreactors is also 2.3. Geometrical Parameters and Process Sizes of
responsible for advantages in their technical safety.[61] The Microstructured Reactors
small inner dimensions not only serve to aid heat removal but
can also mechanistically control a reaction where, for In order to point out the differences between micro-
example, radical chains are terminated such that the non- structured reactors and conventional equipment, four geo-
explosive region is significantly broader as compared to metric parameters and three process sizes will be discussed
conventional reactors.[40, 62] This arises from the presence of a below.
surface-area reaction of radicals (quenching) on the walls of Reactor volume: The internal volume of microstructured
the microchannels. reactors can range from significantly below 1 mL up to several
The laminar flows cause velocity profiles in the channel to mL. Typical large reactors have inner volumes from 100 mL up
appear typically parabolic in shape, which can lead to a to several liters. Plant reactors have, for example, a volume of
relatively broad residence-time distribution. However, the 30 m3, that is, 30 000 L.[23]
slip-flow of gases, which occurs at high temperatures, low Specific reactor surface area: For those reactor volumes
pressures, and/or narrow channels is a notable exception. The mentioned above, microstructured reactors have inner sur-
concentration profile for a HagenPousenille distribution also face areas of several tens of thousands m2 m 3, whilst larger
takes a parabolic form when fully developed. Extreme cases reactors typically only have a surface area of approximately
exist for flows from species with higher diffusion constants in 100 m2 m 3.
narrow channels. Axial and radial diffusion can dominate in Specific phase interface: Depending on the dimensions,
these cases, which leads to a plug concentration profile with flow type, and process parameters, flows in microchannels
respect to the channel cross section.[63] exhibit specific interfaces from approximately 5000 to
The description of single-phase flows in microchannels is 50 000 m2 m 3 for liquidliquid mixtures.[61] The respective
significantly older than microprocess engineering itself.[25, 64] values for gasliquid mixtures are slightly lower. Maximum
The effects of heat transport have been thoroughly inves- values of over 20 000 m2 m 3 have been determined for a
tigated and possible anomalies and peculiarities that result falling-film microreactor. Many conventional apparatus for
from miniaturization have been described and ques- corresponding applications achieve only limited interfaces,
tioned.[6569] Many results referring to these aspects have e.g., 100 m2 m 3. Conventional special apparatus, such as
been challenged by some experts and are thus still the subject impinging jet reactors for gasliquid contacting achieve
of intense discussion.[70] It is generally true that many approximately 2000 m2 m 3.
microfluidic phenomena, which have been known for approx- Film thickness: Film thicknesses of 25 mm have been
imately two decades, still wait to be applied in microprocess measured in falling films running through microchannels.[34]
engineering investigations. These are approximately a factor of ten smaller than for
Multiphase flows in microchannels of microstructured macroscopic falling-film reactors. Even thinner films can exist
reactors have been documented for liquidliquid and gas between Taylor bubbles and channel walls in gasliquid slug
liquid mixtures.[33, 71, 72] The Weber number, which is the ratio flow, as in the case of annular flows with same-fluid mixtures.
of inertia to surface forces, is suitable for their description. Due to experimental difficulties exact values do not exist.
Weber numbers of flows in microchannels are low, typically Mixing time: In optimized mixers typical mixing times for
less than one. A value of 10 3 was determined for flows in a liquid mixtures amount to under one second.[53] In some cases,
falling-film microreactor.[29] In particular the flow-pattern millisecond mixing times have also been proved.[53] This is
maps of gasliquid flows are equivalent to the well docu- faster than most conventional stirrers, which have mixing
mented flows in monoliths, that is, in mesochannels.[71] The times from one up to several tens of seconds.
first simulation studies were dedicated to describing multi- Heat transfer: Very high heat-transfer coefficients of up to
phase flows in microchannels.[2831] An understanding of 25 000 W m 2 K 1 have been measured in micro heat-exchang-
droplet and bubble formation in micronozzles, which from ers for liquid flows.[6] This is significantly higher than the
the beginnings of micro process engineering had been known corresponding values for conventional apparatus. The same is
about, has found increasing applications in recent times.[30, 73] true for gas heat exchange (several hundreds of W m 2 K 1 for
This is also true for the use of internal circulation inside fluid microchannels). The power density of the microstructured
segments within segmented gasliquid and liquidliquid flows reactors have also been measured, for example, with values
(capillary flow; slug flow).[32] The first description of pulse from 2000 W L 1 for gas heat exchange, thus increasing
operation in single-phase or multiphase flows in microchan- significantly the existing state-of-the-art.
nels has also recently appeared.[63, 74, 75] Energy: The few investigations available limit themselves
Several investigations on fluid equidistribution in micro- to investigating the power input for static mixers. The
channels have been carried out, which are of special relevance required energy input in a micromixer and a turbine mixer
Angewandte
has been measured for the generation of emulsions with equal 3. Liquid-Phase Reactions
Sauter diameter.[78] It has been shown under set conditions
that the power input for the micromixer is ten times less. 3.1. Microstructured Reactors for Liquid-Phase Reactions
The following functions of a reactor must typically be

2.4. Perspectives for Reactions in Microstructured Reactors fulfilled for the processing of a chemical reaction:
* Thecomponents must be efficiently mixed,
Thus far, it appears that microtechnology has been * time and space for the reaction must be available,
noticed mostly by process engineers and less by chemists * the heat of reaction must be dissipated, and
from the non-industrial research arena. This can be explained * a phase interface must be available for multiphase
by the fact that several years passed until the new technology reactions.
was available to demonstrate its potential. In the meantime In conventional vessels, components are mixed through
many of the known chemical syntheses, such as the intensive stirring, while in microstructures this process is
Wittig,[79, 80] Knoevenagel,[80] Aldol,[81] Ugi,[80, 82] Michael-addi- mainly realized through diffusion.[2426] Despite laminar flows
tion,[80] Hantzsch,[80, 83, 84] DielsAlder,[85] Azo-coupling ,[51, 86] in microstructures, molecules have short paths to overcome so
Suzuki-coupling,[80, 87] and Enamin[80, 88] reactions, to name but that a nearly complete mixture is achieved within a few
a few, have been carried out successfully, and in most cases seconds, and often as little as a few milliseconds.[24, 26, 138]
with improved results, in microstructured reactors as com- Depending on velocity the reaction can be run directly in a
pared to their macrostructured counterparts.[80] Fluorina- flow chamber located after the inlet structures (thus, in the
tion,[34, 8993] chlorination,[48] nitration,[32, 36, 9497] hydrogena- mixer) or in a connected residence-time module.[53, 139, 140]
tion,[98101] and oxidation[39, 40, 56, 102110] reactions have been Various principles can be applied for the mixing of liquids.
described in numerous examples. The spectrum of chemical Multilamination[24, 26] is a simple and, therefore, frequently
conversions includes many known chemical reaction types, applied principle that, for example, in the interdigital mixer of
such as additions,[56, 102, 105, 106, 111] eliminations,[74, 99, 112116] nucle- IMM [24, 53, 117, 139141] (Figure 2) and mgt mikroglas technik AG
ophilic substitutions on aliphatics,[117] electrophilic substitu-
tions on aromatics,[34, 91, 9496] cycloadditions,[85] and radical
polymerizations[47, 49] (For more information, see also
Refs. [3, 4]). The feasibility of large-volume industrial proc-
esses, such as the Andrussov process[118] and the synthesis of
ethylene oxide[56, 102, 105, 106, 108] could also be demonstrated on a
smaller scale.
It has also been shown that enantioselectivities[80, 119, 120]
and isomer selectivities[95, 121] (e.g., concerning regio- or E/Z
isomerism) are also modifiable. Reactions can be quenched in Figure 2. Slit-interdigital micromixer: a) Method of operation; b) con-
milliseconds (e.g., for isolation from intermediate prod- struction from metal and stainless steel (source: IMM, Mainz[24]).
ucts[86, 122]) and thus syntheses that were previously forbidden
due to safety reasons are, even in the laboratory, now (both in Mainz, Germany; Figure 3)[117, 142] is employed. With
manageable with relatively low risk.[40, 91, 107] As new ideas the help of geometrical focusing, mixing times for miscible
about combinatorial synthesis and material screening liquids are possible in the millisecond time regime.[140] Contact
arise,[123, 124] they naturally generate a demand for small between immiscible liquids[117, 143145] or of gases with liq-
reactors that can vary process parameters quickly and uids[27, 146] is of a more complex nature. In the example of
precisely, as well as consume the minimum amounts of liquid jet decay, the liquids are combined in the mixing zone
materials.[125, 126] There are, therefore, many good reasons for and fragmented into droplets. By changing the geometry of
the chemist to embrace microtechnology! The aim of this the mixing chamber and the wetting properties of the
Review is to take such people into consideration by summa- employed microstructured material, it can be determined
rizing many activities from a chemist's point of view. whether fluid lamellae or fluid cylinders develop. Moreover
While published overviews on microtechnology have to
date mainly dealt with chemical-process issues,[25, 7, 42, 80, 127137]
the emphasis of this Review essay lies on typical reaction
types, where the advantage of this new reaction technology in
comparison to traditional reactors becomes clearer. The
details within this Review concentrate on work published
since 1995 (with emphasis on the years 20002002) and are
structured with respect to liquid-phase, gas-phase, and
gasliquid reactions.
Figure 3. Fluid-introduction system and mixing chamber of a slit-inter-

digital glass micromixer: a) Overview; b) details of the feeding and
mixing zones (source: IMM; microstructure: mgt mikroglas technik
AG, Mainz[117]).
the choice of mixing chamber and fluid flow-rates dictates become intensely mixed. Gas intro-
whether a laminar regime (e.g., with a Rayleigh-plateau duced from the side is responsible for
fragmentation[2731]) or a turbulent regime (e.g., with a jet/ removing the reaction mixture from
towing eddy characteristic[78, 143]) exists. The droplets formed the chamber.
are either very uniform in size with a certain mean diameter The impinging jet mixer
or slightly less uniform and smaller. (Figure 6; developed by IMM) func-
tions by using a similar princi-
ple.[149151] Similarly to the impinging
jet reactor, the fluids coincide out-
side of the mixer and become mixed
within a short length of time.
The two mixers described above
were developed especially for fouling-
sensitive reactions. Plugging is here
not possible, as reactants do not come Figure 6. Design of the
into contact with each other within impinging jet mixer
Figure 4. Splitrecombine micromixers: a) Explosion diagram; b) fluid the microchannels but instead in an (source: IMM[149]).
flow (source: Little Things Factory, Ilmenau). open space and are transported by an
adjustable gas stream.
Figure 4 shows a mixer built by the Little Things Factory More complex microstructured reactors and complete
(LTF, Ilmenau, Germany), which operates according to the reactor systems are currently under development. Figure 7
splitrecombine technique. Ideally, multilaminated layers are shows a microstructured reactor (mgt mikroglas technik AG),
generated through the repeated splitting and recombining of in which a mixer, a residence-time module, and a cooler are
fluid streams. By many microprocess engineering applica-
tions, however, secondary streams up to turbulent operation
are induced due to the high fluid velocities in such mixers, so
that the majority of relevant practical flows can be catego-
rized as complex, and belonging to an intermediate regime
between laminar and turbulent flow. These additional flows
are generally advantageous for the mixing process itself,
however, they do worsen the residence-time behavior as well
as the application of simulation methods used to describe a
process. In comparison with the interditigal mixer, the split
recombine mixer type exhibits a lower pressure drop since it
has comparably larger inner dimensions. Thus, high flow rates
are possible and the operational reliability is less disturbed Figure 7. Microstructured reactor with mixer, residence-time module,
through the precipitation of particles than in other types of and heat exchanger (source: mgt mikroglas technik AG).
mixers.
Turbulent phenomena are also used for the mixing of integrated.[152] A more complicated microstructured reactor
liquids in micromixers at higher flow velocities. Figure 5 designed and built by IMM for BASF was used for a
shows a microjet mixer developed by Synthesechemie (Heus- liquidliquid two phase reaction.[23, 43, 44, 153] Here, a mixer
weiler, Germany),[147, 148] in which reactants are sprayed as with a residence-time module and a heat exchanger are
liquid jets through a diamond or sapphire nozzle (with assembled in a module composed of four microreactor
openings between 60 and 350 mm) where they then collide and elements (Figure 8).
Figure 5. Design of the microjet mixer (source: Synthesechemie Figure 8. Microstructured reactor with mixer, residence-time module,
GmbH, Heusweiler[147]). and heat exchanger (source: IMM[23]).
Angewandte
Complete reactor process plants are offered by Cellular

Process Chemistry Systems GmbH (CPC, Frankfurt), mgt
mikroglas technik AG, and IMM, in which pumps, micro-
structured reactors, residence-time modules, system control,
sensors, and online analytical instruments can be integrated.
These plants are generally based on the mixer-tube reactor
principle and are suited for exploratory investigations of
numerous organic syntheses in the laboratory.
For the optimum process operation of a chemical reaction,
the microstructured reactor plant for the relevant reaction
and mainly for the process function (e.g., increasing the yield)
must be individually set. Such special plants are available now
and are offered by certain institutes.
Figure 9. Dependence of yield (Y) on residence time (t) for a micro-
structured reactor at a reaction temperature of 50 8C.[23]
3.2. Noncatalytic reactions

These investigations led to a better understanding and
WDrz et al. described the potential that microstructured optimization of the industrial production processes involved.
reactors possess for the optimization of chemical processes of The obtained kinetic information could now be used to run a
industrial relevance.[23, 43, 44, 154, 155] A very fast exothermic different temperaturereaction time-window with even better
liquidliquid two-phase reaction, which was used for the reactor performance. At lower temperatures, with necessarily
industrial production of a vitamin intermediate product, was longer residence times, more careful handling of thermally
investigated. unstable reactants and intermediate products is possible, e.g.,
The reactant (dissolved in hexane) and the concentrated reactions can take place at 20 8C instead of 50 8C, which leads
sulfuric acid acting as catalyst do not form a miscible phase to an increase in yield to 9095 %. The optimum residence
with each other, and thus the product is found in the acidic time of 30 s increases the safety of the reaction and enhances
phase at the end of the reaction. As with the reactant the the control of the reaction process.
intermediate compounds generate fast by-products. In a semi- A further example, in which the higher specific phase
batch industrial process a yield of 70 % was achieved. The interface in a microstructured reactor significantly improved
process was later carried out continuously in a mixer/heat the conversion in a two-phase reaction was recently descri-
exchanger reactor combination (Scheme 1) in which the yield bed.[156] The diazo coupling of 5-methylresorcin with 4-
could be increased to 8085 %. The residence time in the nitrobenzoldiazonium tetrafluoroborate took place in an
mixer was 0.2 s and 4 s in the heat exchanger. organic phase/water system (Scheme 2). In comparison to
To understand the technical processes involved,
investigation of this reaction took place in a micro-
structured reactor (Figure 8). Figure 9 shows that the
yield is strongly dependent on residence time; the
optimum time in the reactor combination ( 3 s) lies
very near the empirically determined residence time of
4 s. Note that an extension of the residence time by ten Scheme 2. An example of diazo coupling under phase-transfer conditions in a micro-
seconds leads to a decrease in yield by approximately structured reactor.
17 %.
the macroscopic reaction, where the solution was strongly

stirred, the specific phase interface could be doubled through
the application of a microstructured reactor. Thus, the
conversion was increased from 80 % to 100 % and the
formation of insoluble by-products was reduced.
Complete modular microstructured reactor systems oper-
ating in a continuous mode are suited for fast screening of
reactor parameters such as temperature, time, concentration,
concentration ratio, or pH value. Taghavi-Moghadam
et al.[157] reported the optimization of a Grignard reaction
(Scheme 3). By testing 14 different reaction conditions, the
yield of the reaction could be increased from 49 % to 78 %
and the ratio of the regioisomers A:B could be converted
from 65:35 to 95:5.
Scheme 1. Synthesis of an intermediate product in a hexane/sulfuric Skelton et al. described a further example of a fast
acid two-phase system. optimization of an organic synthesis (Scheme 4).[158, 159] They
sponding dipeptide (Scheme 6). Using continuous flows, a

quantitative yield of the dipeptide was obtained after 20 min,
whereas traditional batch operation only gives 4050 %
conversion. The application was expanded to multistep
syntheses[120] and was also used for the generation of optically
Scheme 3. The reaction of a Grignard reagent and cyclohexanone. active peptides[163] where it was observed that racemization
was reduced by using a microstructured reactor.
Scheme 4. The Wittig reaction between 2-nitrobenzyl triphenylphos-

phonium bromide and 4-formyl methylbenzoate.
Scheme 6. Peptide synthesis in a microstructured reactor. (Dmab = 4-

[N-1-{(4,4-dimethyl-2,6-dioxocyclohexylidene)-3-methylbutyl}-3-amino]-
investigated the Wittig reaction of 2-nitrobenzyl triphenyl- benzyl; Fmoc = 9-fluorenylmethoxycarbonyl).
phosphonium bromide with 4-formyl methylbenzoate in a
microstructured reactor made of borosilicate glass with a
channel width of 200 mm and channel depth of 100 mm; liquid Two further examples of organic syntheses in micro-
mixing took place in a microstructure with a T-shaped structured reactors by Haswell and co-workers employ liquid
geometry. Transport of reactant and product solutions occur- transport through electroosmosis (Scheme 7),[111] the results
red by applying a constant and controlled voltage through the
electroosmotic flow (EOF).[160, 161] It was found that the yield
and the E/Z isomer ratio of the olefin could be optimized
through the change of the relative concentration of the
reactants and the aimed variation of the concentration
gradient. With an aldehyde-to-phosphonium-salt ratio of 2:1
the yield in the microstructured reactor increased from 60 %
Scheme 7. Addition of enolates to a,b-unsaturated carbonyl com-
to 70 % as compared to a conventional batch synthesis. The E/
pounds.
Z isomer ratio could be varied between 0.57 and 5.2 in this
case (compared with 3 in a batch operation).
The first continuous, computer-controlled heterocycle of which were heavily dependent on the flow path used.
synthesis was described by Garcia-Egido et al., who inves- During a continuous operating mode a conversion of only
tigated the Hantzsch thiazol synthesis as model reaction 15 % was achieved. However, if the flow was stopped after
(Scheme 5).[83, 84] Solutions of 4-methylbromoacetophenone 2.5 s for a duration of 5 s and subsequently switched back on,
conversion increased to 34 %; this could be increased to 100 %
by stopping the flow for 10 s. Thus, the conversion was 22 %
higher than that obtained by batch operation. The authors
explain that the increase in conversion occurs because the
flow interruption extends the residence time and the mixing is
improved through diffusion. This investigation is a good
example of the importance of appropriate process procedures
Scheme 5. The Hantzsch 2-aminothiazol synthesis.
in microstructured reactors. The microreactor itself is not a
panacea; it is often more difficult to find the optimum
operating conditions with these techniques than for conven-
and an N-acylated thiourea were pumped through borosili- tional stirring reactors.
cate-etched microchannels by electroosmosis. The channels A significant acceleration of the aldol reaction of silyl enol
were heated to 70 8C through a Peltier element. At 500 V, an ethers with aldehydes in the presence of tetrabutylammonium
increase in conversion up to 19 % was achieved in the fluoride (TBAF, Scheme 8) was observed in a four-channeled
microchannel, compared to conventional batch operation. microstructured reactor.[81] Quantitative conversion was ach-
Watts et al. carried out the first investigations on the ieved after only 20 min, compared to 24 h in conventional
synthesis of peptides in microstructured channels. [80, 119, 120] To systems.
demonstrate the feasibility of such reactions an achiral b- One objective for microstructured reactor applications is
peptide was initially made.[162] It was shown that reaction of an to combine many functions, such as synthesis, separation,
Fmoc-protected pentafluorophenylester of b-alanine with the analysis, and screening within one microdevice to generate
carboxylic acid protected b-alanine could give the corre- compound libraries. It is has been proven that solution
Angewandte
reactor through the precipitation of pigments. Thus, the raw

pigments are dissolved in concentrated sulfuric acid and
pumped through a nozzle of the microjet mixer (e.g.,
pressure = 50 bar), while water is simultaneously pumped in
Scheme 8. Aldol reaction of a silyl enol ether with 4-bromobenzalde- at the same pressure through a second nozzle. The suspen-
hyde.
sions evolving after the collision of the jets in the mixing
chamber are carried out of the reactor by an air jet, and the
produced pigment can be isolated using standard procedures.
transport for such a task is not favored by electroosmosis, Using a tetracopper phthalocyanine raw pigment, it was
since this is strongly dependent on solvent properties such as shown that the specific surface area increased from 13 to
pH value and ionic strength, hence the choice of solvent is 29 m2 g 1 and the average particle size decreased from 34 to
strongly limited. Fernandez-Suarez et al. recently showed that 26 nm. The pressure of the liquids can be increased, as
this disadvantage can be overcome through the use of required, up to 3800 bar.
pumps.[85] A domino reaction was investigated consisting of
a Knoevenagel condensation and an intermolecular hetero-
DielsAlder reaction (Scheme 9). The four examples given 3.3. Catalytic Reactions
showed that the results were reproducible without optimiza-
tion and similar conversions were reached as in a batch The Suzuki reaction (homo- and heterogeneous) was
reactor. investigated as a rare example of a catalytic liquid-phase
reaction in a microstructured reactor.
Schwesinger et al. described the conversion
of 3-bromobenzaldehyde with 4-fluoro-
phenyl boronic acid in the presence of a
dissolved Pd catalyst (Scheme 11).[3, 167]
Figure 10 shows that through the applica-
tion of a micromixer/residence-time
module combination, the yield could be
Scheme 9. Domino reaction: A Knoevenagel condensation and an intermolecular
hetero-DielsAlder reaction. Catalyst = ethylenediamine diacetate (EDDA).
increased under continuous operation from
50 to 90 %, as compared to the con-
ventional mode.
Werner, Hessel, and co-workers described the first
application of an impinging jet mixer (Figure 6), which was
specially developed for organic syntheses that are prone to
fouling. The formation of a quarternary amine from 4,4-
bipyridyl and bromoacetic acid ethyl ester was investigated as
model reaction (Scheme 10).[149] It was shown that this solid- Scheme 11. An example of a Suzuki reaction in a micromixer/
residence-time module combination.
Scheme 10. Formation of a quarternary amine salt of 4,4-bipyridyl.
forming reaction could be operated up to 8 h continuously

with a yield of 75 %, a value comparable with the perform-
ance of a batch operation. The work describes for the first
time a continuous operation for strongly fouling-prone
reactions with acceptable reactor efficiency. A normal
micromixer or other microstructured reactor would be Figure 10. The Suzuki reaction: Comparing the yield (Y) for a labora-
plugged within a few minutes under the same conditions. tory reactor with a micromixer/residence-time module combina-
The impinging jet mixer prevents this and, in a vertical tion.[3, 167]
arrangement, can also use straight tubes with suitable
dimensions for longer residence-time operation. With this The heterogeneous version of this reaction was recently
reactor configuration a larger number of solid-sensitive investigated by Greenway, Skelton, and co-workers,[87, 168] who
processes can be run. used microstructured borosilicate glass with a channel width
Several patents have been published for applications of of 300 mm and depth of 115 mm. 1.8 % Pd/SiO2 was employed
the microjet mixer (Figure 5).[164166] Fine particles with a very as a catalyst, carried to the surface of the microstructures as a
narrow particle-size distribution can be produced in this suspension; adhesion was achieved by heating to 100 8C for
1 h. The reaction of 4-bromobenzonitrile and phenylboronic Organometallic reactions can also be carried out in
acid was chosen as a model reaction (Scheme 12). Liquid microstructured reactors with higher efficiency than in
transport occurred through electroosmosis, with the flow of batch reactors, as exemplified by the studies of Haswell,
Fletcher, and co-workers,[80, 176] who investigated the Kuma-
daCorriu reaction by reacting 4-bromoanisol with phenyl-
magnesium bromide in the presence of the Merrifield-resin-
immobilized salen-type nickel complex A (Scheme 15), which
Scheme 12. An example of a heterogeneously catalyzed Suzuki reaction
in a microstructured reactor.
the phenylboronic acid solution being continuous and the

bromobenzonitrile solution injected at intervals. After opti-
mization of this procedure, yields were achieved that were
10 % higher than those achieved by a conventional batch
process.
Wilson et al. described the acidic, heterogeneously cata-
lyzed dehydration of alcohols in microstructured reactors,
which were prepared through photolithography and chemical Scheme 15. An example of a KumadaCorriu reaction in a microstruc-
etching of glass. The cover plate, made of polydimethylsilox- tured reactor using an immobilized salen-type nickel complex as a
ane, served as both the heat source and as the carrier of the catalyst.
employed catalyst (sulfated zirconia).[169, 170] The dehydration
of 1-hexanol to hexene at 155160 8C was investigated
(Scheme 13), in which the liquid transport took place through in the form of small pellets were packed into capillaries of 1
an injection pump. A conversion of 8595 % was recorded and 2 mm diameter; the reagents were then pumped through
no by-products were detected. This compares favorably to the these microstructures. The reaction rate constant was deter-
30 % conversion achieved by conventional reactors. mined through kinetic measurements, which determined that
continuous flow in microchannels led to an increase in the
rate by a remarkably large factor of 3.4 L 103 compared to a
conventional batch reactor. In other words, the yield obtained
in 24 h in a batch reactor could be achieved within a few
Scheme 13. Dehydration of 1-hexanol in a microstructured reactor.
minutes in a microchannel. This effect was explained as
arising from the high pressure through the microstructure,
Wan et al. recently reported a series of oxidation reactions which pushes the reagents deeper into the pores of the resin,
over a coating of titanium silicalite 1 (TS-1) in microchan- and thus a greater number of catalytic sites are reached than
nels.[173175] The silica-etched channels were either 500 or in the conventional process.
1000 mm wide and had a depth of 250 mm and a length of De Bellefon and co-workers have introduced a new
33 mm. Growth of the TS-1 crystals occurred in the open concept for the high-throughput screening (HTS) of homo-
structures, the surfaces of which were initially treated with 3- geneously catalyzed reactions in multiphase systems, by
(trimethoxysilyl)propylthiol to improve the adhesion of TS-1. investigating isomerization in a two-phase system
After the deposition of TS-1 seed crystals a hydrothermal (Figure 11).[175179] The organic phase, substrate, and water
reaction was carried out, which led to a uniform 3-mm thick were continuously pumped into an interdigital mixer (IMM)
catalyst coating. The epoxidation of 1-pentene with hydrogen and analyzed after flowing through a residence-time module.
peroxide was then investigated (Scheme 14). The authors
Scheme 14. Epoxidation of 1-pentene with hydrogen peroxide on TS-1

in a microstructured reactor.
found that increasing the surface-area-to-volume ratio

(through replacing a 1000 mm channel with a 500 mm channel)
approximately doubled the yield due to the higher catalyst
concentration. The disadvantage remains that after a contin-
uous operation of more than 100 h catalyst deactivation took
place, which could not be reversed even after calcination in Figure 11. Apparatus for the high-throughput screening of homogene-
air. ous catalysts using an interdigital mixer.[177]
Angewandte
The catalyst solution was injected in pulses through a Above the reaction channel, in which the liquid flows
commercial valve. Complete mixing took place in the micro- downwards due to gravity, a rectangular-shaped open space
mixer with a residence time of 10 2 s, with catalyst amounts of lies in the top cover of the housing through which the reactant
12 mmol being sufficient. This technique is particularly gas flows. The gas inlet is formed in an analogous way to a gas
advantageous if the catalysts are available only in small diffuser, thus distributing the gas homogeneously. The
amounts due to difficulties in their synthesis. For example, dimensions of the cooling channels correspond to the width
from a catalyst library, the RhCl3tris(m-sulfonatophenyl)- and depth of the reaction channels. To limit the reaction in the
phosphane (TPPTS) catalyst was found, which catalyzed the cooled region, contact with the gas in the non-cooled region is
isomerization of 1-hexen-3-ol to the desired ethylpropyl- prevented by covering with a contact-zone mask.
ketone with 53 % conversion (Scheme 16). Figure 13 shows a stainless steel falling-film microreactor
with a viewing window. If a quartz window is used, photo-
chemical gasliquid reactions can be carried out. The high
Scheme 16. Isomerization of 1-hexene-3-ol using a RhCl3/TPPTS

catalyst.
4. GasLiquid Reactions
Even though gas-phase as well as liquid-phase reactions in

microstructured reactors have been described for some time,
few investigations on gasliquid processes have been carried
out. Recent years have seen increased interest, however, and
in the following section, reactors suitable for such reactions
are described along with the associated advantages of
applying these microstructured devices for gasliquid reac- Figure 13. A falling-film microreactor with a viewing window (source:
tions. IMM[34, 183]).
4.1. Microstructured Reactors for GasLiquid Reactions mass- and heat transport achieved in falling-film reactors can
be increased further in a falling-film microreactor by the
Two microstructured reactors suitable for gasliquid development of a thin liquid film in the microstructured
reactions have been developed by IMM and their collabo- channels. Liquid films up to 15 mm thick correspond to a
rators.[33, 34, 91, 180183] Figure 12 shows the design principle of the specific phase interface of up to 20 000 m2 m 3, a value which
falling-film microreactor.[33, 34, 91, 180182] The reactor is built is approximately ten times higher than that of most known
from four components: A bottom housing section with commercial systems, such as the impinging jet reactor.
integrated heat exchanger, a reaction plate, a contact-zone Similar results have also been achieved with the micro-
mask, and a top housing section with an open space. The bubble column, the principles of which are described in
central element of this microstructured reactor is the reaction Figure 14.[33, 34, 71, 91, 180182] The central element of the micro-
plate on which microchannels with widths from 100 up to bubble column is a static microdisperser unit made of a nickel/
1200 mm and depths from 100 up to 600 mm are arranged. copper alloy, which is manufactured through a UV-LIGA
Figure 12. Components of a falling-film microreactor (source: IMM[34]). Figure 14. Construction of a microbubble column (source: IMM[34]).
process. Flow distribution of the gas and liquid is achieved

through the construction of a pressure barrier in the feed part
of the small microdisperser unit, where the gas inlet is no
wider than 5 mm and the liquid inlet no wider than 20 mm. The
parallel operating reaction channels are arranged on a plate.
Effective thermal control is achieved through the use of a
heat-transfer medium that flows in small channels in counter-
flow to the reagents. The reaction channel plate is locked
between these heat-transfer channels on each side (the
separate parts of the stainless steel microbubble column are
shown in Figure 15). The microbubble column is a reactor
Figure 16. Packed-bed microreactor: a) Single-reactor version; b) ten-

reactor version with a flow distribution zone (source: MIT, Cambridge,
USA[5]).
Figure 15. Components of a microbubble column (source: IMM[34]).
designed for short gasliquid contact time. In addition to the

bubble-flow and spray-flow techniques are the slug-flow and
the annular-flow regimes, which are set through the appro-
priate choice of liquid and gas superficial velocities.
Figure 16 shows the gasliquidsolid microstructured
reactor developed at MIT (USA), in which microchannels
consist of conventional catalyst-powder fixed beds.[92, 185, 186] In
this way larger inner interfaces are created. This micropacked
bed reactor has been successfully employed for the hydro-
genation of conjugated olefins and the selective oxidation of
benzyl alcohol to benzaldehyde. Of particular note is the
numbering-up of ten such reactors. The difficult equidistri-
bution of the gasliquid flow was realized through specially
developed distribution structures.
Figure 17 describes the glass-cyclone mixer, [146] which was
built from 11 microstructured stacks which each contain three
groups of nozzles. The gas injection nozzle has a width of Figure 17. Glass cyclone mixer: a) Construction; b) simulated and
30 mm whilst the liquid is dosed through a 50-mm wide experimentally determined liquidliquid flow patterns (source: IMM;
opening. The bubble-forming process can be influenced by mgt mikroglas AG[146]).
the arrangement of the gas and liquid injection nozzles (either
parallel or vertical). Within the reaction area, spiral patterns
of the gas bubbles form in the liquid, similar to a cyclone A reactor developed by Chambers et al. is designed
vortex, which is also employed in liquidliquid operation. In specifically for strongly exothermic fluorination using ele-
the large reaction area, clusters of bubbles and foam are mental fluorine (Figure 18).[89, 90] The liquid and the gas are
formed in addition to isolated bubbles, and these coalesce or dosed in a nickel channel at velocities such that an annular
deform in smaller microchannels. This reactor type is thus flow is exhibited, by which the liquid is distributed as a thin
suitable for contacting catalyst slurries to the gas phase, film on the surface of the wall of a microchannel and the gas
although the nozzle width needs to be widened to 150 mm for flows through the center of the channel. Similar flow
this operation. conditions and well defined gasliquid contact interfaces are
Angewandte
Scheme 17. Fluorination of 2-chloroacetic ester in a three-channel

microreactor.
JNhnisch, Hessel, and co-workers showed that both the

falling-film microreactor (Figure 13) and the microbubble
column (Figure 14) offer advantages over conventional reac-
tors in fluorination reactions with F2.[34, 91] The fluorination of
toluene was investigated (using either CH3CN or CH3OH as
solvent; Scheme 19).The selectivities achievable for the for-
mation of monofluorinated toluene, were determined based
on the conversion and were compared to a conventional
Figure 18. Design of a single-channel reactor (source: University of
laboratory-scale bubble column. The selectivity of the for-
Durham[89]).
mation of monofluorinated toluene in a falling-film micro-
obtained by this method as for a falling-film reactor.

Recently this type of reactor was extended to a three-
channel reactor.[90] The two-channel silica reactor devel-
oped by Jensen et al. functions following an analogous
principle where the channel surface is coated with nickel in
order to improve chemical resistance.[92]
4.2. Halogenation Reactions
To demonstrate the advantage in using microstructured

reactors, the fluorination of organic compounds with Scheme 18. Fluorination of bis(3-nitrophenyl)disulfide and 4-nitrotoluene in a
elemental fluorine was attempted by many groups.[34, 8993] microstructured reactor.
This reaction is strongly exothermic and is in most cases
uncontrollable in conventional reactors. In this way, facile
access to fluorine-containing intermediates is provided.
Due to the poor solubility of fluorine in solvents often
used for this reaction (e.g., CH3CN or CH3OH) the gasliquid
reaction is found to occur at the gasliquid phase interface
where gasliquid mass transport is the rate-limiting step. Due
to the very high specific phase interfaces that serve to form Scheme 19. The fluorination of toluene was carried out in both a
the very thin liquid layer on the surface of the micro- falling-film microreactor and a microbubble column.
structures, both heat transport and mass transport are
intensified such that the formation of hot spots is suppressed
and the selectivity of the reaction is improved. reactor is significantly higher than that from a conventional
The first investigation of this problem was published in bubble column (Figure 19). A further advantage is the
1999 by Chambers and Spink[89] and was discussed in detail considerably higher spacetime yields achievable in micro-
later.[90] It was shown that b-dicarbonyl compounds could be structured reactors.The results of these studies were taken by
converted to respective fluorinated species (in formic acid de Mas et al. as a benchmark for similar investigations on the
solution) using 10 % F2 in N2 by continuous operation. The same model system in a two-channel reactor made of
reaction of ethyl 2-chloroacetoacetate in a three-channel silica.[92, 93] The authors verified the results and, moreover,
[90]
microreactor gave a conversion of 59 % and a yield of 74 %; showed for the first time experimentally that the fluorination
conventional methods in batch operation gave a significantly with F2 can be carried out at room temperature.
lower conversion and yield.[187] It was further observed that An improvement in selectivity of the chlorination of
the fluorinated nickel surface in the microchannel led to a acetic acid was recently described in a patent (Scheme 20).[188]
catalytic effect through the favored formation of the enol Using a falling-film microreactor, a conversion of > 85 % to
form (Scheme 17). Further examples of the fabrication of monochloroacetic acid was achieved, and the formation of
pentafluorosulfide compounds and the fluorination of 4- dichloroacetic acid was reduced from 3.5 % to < 0.1 %,
nitrotoluene have been reported, in which conversions up to thus sparing the need for a costly and time consuming
77 % and yields up to 78 % were achieved (Scheme 18).[90] separation process.
the isomer ratio could be changed considerably. In macro-

scopic batch reactors the isomer ratio C:D is invariably
around 1:3.6, while applying microstructures allows greater
access to the 1,5-dinitro compound C (C:D 1:2.8). The
isomer ratio of mononitro naphthalene products could also be
changed (20:1 for A:B in the industrial process, compared
with 32:1 for the microstructured reactor).
4.4. Catalytic Hydrogenation of Nitrobenzene
Yeong et al. described the heterogeneously catalysed

Figure 19. Conversion (X) and selectivity (S) in the fluorination of tolu- exothermic hydrogenation of nitrobenzene to aniline
ene in a falling-film microreactor and in a laboratory bubble column (Scheme 22) in a falling-film microreactor (Figure 13).[190]
(source: ACA, Berlin[91]).
Scheme 20. The chlorination of acetic acid, optimized in a falling-film Scheme 22. Heterogeneously catalyzed hydrogenation of nitrobenzene
microreactor. to aniline in a falling-film microreactor.
4.3. Nitrations
Pd catalysts were deposited by sputtering onto the
Loebbecke, Antes, and co-workers developed a continu- microstructured plates via the decomposition of Pd(OAc)2
ous process for the nitration of aromatics in microstructured with UV light, impregnation of g-Al2O3 with palladium
reactors, which was shown to significantly increase selectivity nitrate, or through the incipient wetness method, and hydro-
through their improved heat- and mass transport proper- genation was carried out at 60 8C and 14 bar H2. Catalysts
ties.[94, 95, 121, 189] The strongly exothermic nitration of naphtha- prepared by the latter two methods gave the best results
lene using N2O5 in both the gas phase (in situ production from (82 % conversions). However, considerable deactivation
N2O4 and O3) and the liquid phase was investigated occurred through the deposition of organic compounds,
(Scheme 21). The modes of operation of the interdigital which could be reversed by oxidation at 130 8C. In addition,
deactivation through the loss of palladium could be counter-
acted by increasing the Pd concentration. These investigations
were the first to utilize a three-phase (gasliquidsolid)
system in a microstructured reactor, and highlighted the
advantages of microtechnology for improved heat- and mass
transport in optimizing heterogeneous catalysis.
5. Photochemical and Electrochemical Reactions
Few studies describing the application of microstructured

reactors for photochemical and electrochemical reactions
Scheme 21. Nitration of naphthalene in a microstructured reactor. have been carried out. Jensen and co-workers have developed
a single-channel silica reactor in which a miniature UV lamp,
as well as in situ UV spectroscopic analysis was inte-
mixers (using the multilamination principle) as well as the grated.[191193] The main advantage in applying microstructures
microstructures (working according to the splitrecombine in photochemical reactions is that the thin layers allow
technique) were studied. Nitration in conventional batch extensive penetration of the solution and thus a more efficient
operation requires temperatures from 50 to 20 8C, while use of the energy due to light. The large specific phase
the same reactions can be carried out in microstructures interfaces give rise to high heat-transfer rates, which make
under continuous processing at 30 8C with a flow rate of isothermal reaction processes a possibility.
1 mL min 1 at a residence time of 3 s. The preferred mono- Jensen et al. investigated the radical formation of pinacol
nitro derivatives A and B are formed, as well as the dinitro from benzophenone and 2-propanol (Scheme 23). Technical
compounds C and D, while the formation of higher nitrated reaction data, such as the dependence of the flow velocity on
products was quantitatively suppressed. Interestingly, through conversion and quantum-yield values were determined, and
varying the reaction conditions and the choice of reactor online analysis of the reaction mixture was achieved. The
geometry, not only could the level of nitration be set but also results of these studies provide a tool with which the intrinsic
Angewandte
the selectivity of the desired side-chain chlorinated deriva-

tives decreases, since without photochemical induction chlori-
nation prefers to take place at the aromatic core.
Scheme 23. Photochemical reductive coupling of benzophenone in a Another interesting field of application for microstruc-
single-channeled microstructured silica reactor. tured reactors are reactions in which explosive or toxic
compounds are formed. Due to the small volumes involved,
the hazard potential can be greatly reduced in such reactions.
reaction kinetics of photochemical reactions can be deter- Wootton et al. recently described the production of singlet
mined without the influence of mass transport. oxygen through the photochemical stimulation of oxygen in
JNhnisch, Ehrich, et al. reported that a falling-film micro- the presence of catalytic amounts of Rose Bengal in a single-
reactor (Figure 13) can be used for photochemically induced channeled glass reactor;[86] a [4+2]-cycloaddition of a-terpi-
gasliquid reactions, such as the photochlorination of toluene- nene led to the formation of ascaridole (Scheme 25). This
2,4-diisocyanate (Scheme 24).[194] The reaction was carried
Scheme 25. The reaction of a-terpinene and singlet oxygen to give

Scheme 24. An example of photochlorination in a falling-film micro- ascaridole.
reactor.
process could be run continuously, which avoided the enrich-

out under continuous operation using both a nickel and an ment of the explosive endoperoxide ascaridole and delivered
iron reaction plate. Figure 20 shows how these systems very high conversions after an exposure of only 5 s. In this
compare with a conventional batch reactor (a mercury example, light penetration through the liquid layer plays an
vapor lamp submerged in a reaction flask). The results show important role as the dissolved photosensitizer Rose Bengal
possesses a large extinction coefficient and all of the light is
absorbed over a rather short distance.
JNhnisch et al. showed that the falling-film microreactor
(Figure 13) is also suitable for the continuous photochemical
generation of singlet oxygen in the presence of dissolved Rose
Bengal. For example, a [4+2] cycloaddition reaction of cyclo-
pentadiene with singlet oxygen was investigated
(Scheme 26).[195] The explosive endoperoxide, which appears
as an intermediate, was reduced with thiourea to give 2-
cyclopenten-1,4-diol, which is of pharmaceutical impor-
tance.[196]
Figure 20. Selectivity (S) for the formation of 1-chloromethyl-2,4-diiso-

cyanatobenzene with respect to the conversion (X) of toluene-2,4-diiso-
cyanate (source: ACA[194]).
Scheme 26. Photooxygenation of cyclopentadiene in a falling-film
microreactor.
that with similar conversions a significant increase in selec-
tivity is observed in the falling-film microreactor compared to
conventional working methods. The application of a nickel LDwe et al. developed an electrochemical microstructured
plate gives the highest selectivity, while the iron plate reactor that was suitable for electroorganic syntheses
exhibited catalytic activity that favored ring substitution as (Figure 21).[197] The main component of this reactor is a
a side reaction. microstructured electrically nonconducting layer, which is
The advantage of microstructured reactors, in terms of sandwiched by the electrodes. The microchannels have a
selectivity and spacetime yield, stems from the better width of 80 mm, a depth of 25 mm, and a length of 64 mm, and
penetration of photons and the higher mass-transfer rates in are operated at a flow rate of 6 mL h 1 and a pressure drop of
the thinner liquid films. Chlorine radicals are located over the 1.1 bar. An integrated cooling element ensures an effective
total film volume and high local radical concentrations, which control of temperature.
lead to recombination, are avoided. In a conventional reactor, In this reactor, the technically important oxidation
the radical concentration near the light source is high while, in reaction of 4-methoxytoluene to 4-methoxybenzaldehyde
contrast, it is very low at the center of the reactor. As a result was investigated (Scheme 27). Best results were achieved at
Scheme 28. Electrochemical synthesis of highly-functionalized deriva-

tive D in an electrochemical microstructured reactor using the cation-
flow method. (R1, R2 = alkyl, cycloalkyl; R3, R4 = H, alkyl, cycloalkyl;
X = O, CH2).
Figure 21. a) Microstructured reactor with an integrated cooler for
electrochemical processes; b) explosion diagram (source: IMM[197]).
where the flow of the reactants can be controlled. A carbon-
fiber anode and a platinum-wire cathode was employed, and
Bu4NBF4 was used as the conducting salt. The N-acyliminium
ions B were detected by in situ IR spectroscopy.
Menegaud, Ferrigno, and co-workers recently described
the coupling of a ceramic electrochemical microstructured
reactor with a mass spectrometer.[200203] In their study the
Scheme 27. The anodic oxidation of 4-methoxytoluene in an electro-
electrochemical dimethoxylation of furan-2-carboxylic acid
chemical microstructured reactor.
methylester was investigated (Scheme 29). This combination
allows mechanistic studies of electrochemical reactions and
a voltage of 4.5 V (Figure 22), where a selectivity of 86 % at a identification of unstable intermediate steps.
conversion of 88 % was recorded. In contrast with conven-
tional processes, it was also possible to perform the reaction
Scheme 29. Electrochemical dimethoxylation of furan-2-carboxylic acid

methylester.
6. Gas-Phase Reactions
Apart from organic liquid-phase reactions, gas-phase

reactions are the most frequently investigated processes in
microstructured reactors. Aside from the economic and
scientific value of such investigations, microstructured reac-
tors seem technologically well suited to such reactions.
Figure 22. Dependence of conversion (X) and selectivity (S) on the According to WDrz,[23] processes with high reaction rates
electrode potential (E) in the electrochemical oxidation of 4-methoxy- together with a high release of heat should be investigated in
toluene (source: IMM[197]).
microstructured reactors, especially if the reactions take place
in different phases.
without a conducting salt, and selectivity up to 98 % was The former aspect is true for several gas-phase reactions,
achieved with small concentrations, compared to 85 % for such as oxidations, which can be completed in several
the conventional process. The increase in selectivity can be milliseconds, mainly at significantly high temperatures. Most
explained by the fact that both the short distance between the gas-phase reactions are carried out over a catalyst, and these
electrodes and the nature of running a reaction in micro- two-phase (solid and gas) reactions are especially suited to
channels leads to intense mass- and heat transport. In microprocess engineering. Many industrial and laboratory
addition, over short residence times, a homogeneous current gas-phase processes are carried out in flow-through reactors,
density and velocity distribution existed such that the electro- which are, at least, a formal equivalent to a microstructured
chemical reaction could be run under precisely defined reactor.
operating conditions. While microstructured reactors and conventional reactors
Suga et al. developed the so-called cation-flow method for gas-phase reactions resemble each other in their process
for the continuous production of very reactive acyliminium operation, they are often different in terms of catalyst
ions B in microreactors, which were immediately converted in technology. Conventional reactors mainly use catalyst in the
a C C bond formation reaction to substituted derivative D form of pellets (fixed-bed technology) or fine, agitated
using various nucleophiles C such as allylsilanes or enol silyl powders (fluidized-bed technology). The use of thin catalyst
ethers (Scheme 28).[198, 199] The reaction takes place over short layers on the reactor walls is almost exclusively used in
residence times and is suitable for combinatorial synthesis microstructured reactors. Washcoats, such as those applied in
Angewandte
exhaust-gas cleaning in automobiles, as well as in monolith

reactors, are often applied as a carrier on the microchannel
wall. Then, for example, wet-chemical impregnation can be
carried out. Beds in microstructured reactors are generally
not employed as they cause a large pressure drop and a
change the laminar flow.
Figure 26. Multiplate-stacked reactor with a two-part housing: a) Com-

6.1. Microstructured Reactors for Gas-Phase Reactions
ponent parts, b) detailed view of a stack of plates (source: IMM[3]).
6.1.1. Multiplate-Stacked Microstructured Reactors
One of the more frequently used reactor types contains a simply by means of surface pressure.[56] However, the micro-
stack of plates, each of which possesses parallel microstructured plates can also be irreversibly connected, for
channels.[9, 48, 56, 60, 74, 100, 101, 105107] Such stacks are either welded example, through laser welding[48, 204] or through diffusion
together externally (Figure 23),[48, 204] encased by a cover bonding.[100, 101, 212, 213] Diffusion-bonded plates are also sur-
rounded by a housing. The compactness of such configura-
tions can be optimized, thus giving large active areas for a
given volume.
Examples of housed microstructured stacks include those
prepared by Schouten et al., which is a manufactured reactor
for the investigation the oxidation of ammonia,[60, 214] and
those of Richter and Cominos et al., which are designed for
the synthesis of ethylene oxide[56, 105] and for methanol steam
reforming, respectively.[215, 216] Schubert and co-workers have
Figure 23. Overview (a) and more detailed view (b) of an externally optimized the diffusion bonding of microstructured stacks,
welded multiplate-stacked reactor (source: IMM).
which also exhibit excellent heat transfer despite being
uncoated.[6, 9, 20, 205, 206, 217, 218] In addition, a range of reactors
(Figure 24),[9, 100, 101, 205, 206, 212, 213] have end plates containing exists that are available for flow rates of a few 10s of L min 1
fluidic connections (Figure 25),[74, 207, 208] or are directly for liquids and of a few 10s of m3 min 1 for gases.[6, 20, 205, 219]
inserted into a two-part housing unit with a pocket
(Figure 26).[56, 60, 105107] If required, graphite gaskets (or other 6.1.2. Multiplate-Stacked Microstructured Reactors for Parallel
materials) divide single fluidic areas on the plates and isolate Catalyst Testing
the plates from each other.[74, 207] The housing is often sealed
with screws, resulting in an even pressing of the surface of the A special form of multiplate-stacked reactors are those
plates. Tightening of the housing parts is possible also without consisting of similar plates but with different cata-
internal sealing of the plates using graphite or similar foils, lysts.[125, 220, 221] A multiplate-stacked reactor (35 plates) was
designed and constructed by Zech and HDnicke, together with
co-workers from IMM.[125, 220] The central component of the
process plant that surrounds the microstructured reactor is a
300-mm-wide aligned capillary, which automatically collects
samples from each plate (Figure 27). Later Kolb et al.
constructed a 10-fold stacked reactor to carry out two
Figure 24. Overview (a) and more detailed view (b) of a diffusion-
bonded multiplate-stacked reactor (source: Forschungzentrum
Karlsruhe[205]).
Figure 25. A multiplate-stacked reactor with an end plate: a) Overview, Figure 27. Microstructured reactor module with 35 stacked frame
b) single plate with gasket (source: IMM[184]). plates (source: Universit Chemnitz; IMM[220]).
functions.[221] Depending on the end plates used, a parallel or

serial operation can be carried out using the same reactor
core. Primary screening and catalyst optimization are thus
possible within the same reactor set-up without changing the
channel geometry.
6.1.3. Single-Plate and Single-Channeled Microstructured Reac-

tors
Single-plate reactors have the advantage that problematic

fluid distribution is limited to the microchannels.[222] A special
case is the single-channeled reactor, a simply built example of
which was designed by Veser et al.[39, 40] Two plates, one with a
channel and wire, and the other with cover plate, were
sandwiched together.
Ajmera et al. described a single-channeled microstruc-
tured reactor that incorporates catalyst powder or particles
(Figure 28).[223, 224] To compensate for local differences in the
particle-size distribution, the channel has a specific length,
which achieves a uniform flow distribution from both sides by
applying a bifurcated cascade.
Figure 29. A T-shaped membrane-based microstructured reactor:
a) view from above; b) cross section through a reaction channel;
c) longitudinal section through a reaction channel; d) photo of the
microreactor; e) regularly arranged free-standing Pd membranes
(source: MIT Cambridge[5, 228, 231]).
Membrane-microstructured reactors with permeable

membranes can be used for the coupling and separation of
a reaction, which through permanent product removal
increases the conversion, according to the law of mass
action.[116, 231233] Thin membranes are therefore fitted over
the opening of a plate, which serves to separate the reactant
and product gas streams from each other.[231]
6.1.5. Two-Channeled Microstructured Reactors with Counter-

Current Flow
Two-channeled microstructured reactors can be used for

counter-current flow operation.[22, 60, 107, 207] Thus, an exother-
mic reaction can heat up its own reactant stream.[22] It is also
possible to couple exothermic and endothermic reactions in
this way.[207]
Figure 28. a) Cross-flow microstructured reactor chip made of silicon;
b) microstructured reactor packed with 50 mm glass beads; c) SEM 6.1.6. Chip-Microstructured Reactors
image of a microstructured reactor; d) inlet region and pressure bar-
rier (source: MIT[223]). Many gas-phase microstructured reactors are designed by
using the silicon micromachining technology of microelec-
6.1.4. Membrane-Microstructured Reactors tronics. Chip systems are mostly formed of two or more joined
silicon (or glass) wafers,[54, 225230, 234] but occasionally relatively
Franz et al.[54, 225] and Jensen et al.[226228] introduced a complex multiplate systems, which can have several functions
single-channeled microstructured reactor which incorporated in every layer, are employed.[21] A groundbreaking silicon
numerous pressure and temperature sensors along the chip, designed by MIT and DuPont, was fabricated with such
reaction zone.[229, 230] The microstructured reactor is closed an architecture (Figure 30).[21]
from above by a thin impermeable membrane which contains
a Pt thin-film catalyst (Figure 29). Depending on the strength 6.1.7. Microreactors Without Microchannel Feeding Systems
and material of this membrane, and thus its ability to allow
heat to dissipate, numerous operating modes are available for A microreactor without microchannel guidance was
certain reactions, such as ammonia oxidation. recently described by Wolfrath et al.,[233] in which filaments
Angewandte
In a conventional form, catalyst powder or particles are

introduced in a channel as miniature fixed beds.[223] Alter-
native or more complex catalyst forms also find applications
such as catalyst filaments,[233] wires,[40] and membranes.[116, 231]
Most coatings in microchannels are prepared by the
washcoat route with subsequent wet-chemical impregna-
tion.[74, 207, 235] Zeolites are another class of industrially used
catalysts that can be directly grown into microchan-
nels.[173, 174, 236] The anodic oxidation of aluminum channels is
frequently used in order to generate nanoporous carrier
layers.[213] Thin-film technologies such as CVD[207] and PVD
(especially sputtering[231]) can be used to generate compact,
thin catalyst films. Other types of catalyst/carrier systems can
be prepared through aerosol techniques,[225] solgel techni-
ques,[237] plasma electrochemical processes,[238] or electroly-
sis.[239]
Figure 30. Explosion diagram of an integrated microstructured
Detailed descriptions of prepared catalyst/carrier systems
reaction system made of silicon (source: DuPont, Delaware[21]).
in microchannels can be found for both washcoat sys-
tems[74, 235] and for zeolite growth[173, 174, 236] . The so-called
were inserted into the product stream and miniature active Fill in/Wipe off method is a typical procedure for catalyst
areas were produced. preparation using washcoats.[74, 207]
It is likely that many similar microreactors will find future Few review papers to date have appeared that are
applications, simply due to costs. They will always be dedicated entirely to the subject of catalyst/carrier systems
advantageous as long as the fundamental elements of micro- and especially their basic characterization (e.g., with respect
process operation technology are fully understood in advance. to morphology, porosity, consistency). Even so, many reports
This knowledge then also allows alternative solutions to be contain useful information regarding heterogeneously cata-
found, and optimal process operations to be applied. The lyzed gas-phase reactions. In particular, SEM imaging docu-
target factor to be achieved always has priority in process ments the macro- and microstructure of catalysts.[56, 105] In
development and optimization. Thus, the manufacture of many cases, analysis of cross-sectional profiles (perpendicular
microstructured elements is no longer based purely upon the to the flow direction) show that a nonuniform layer thickness
criterion of a supposedly necessary, partly exaggerated exists (Figure 31). Large differences in layer thickness have
structural precision. On the contrary, there is room for been found, especially in the lower half of channels.[225, 237, 240]
compromised solutions where the dimensions of the struc-
tures are not so accurately defined as in microtechnological
manufacturing processes.
6.2. Catalyst/Carrier Systems for Gas-Phase Reactions In

Microchannels
Catalysts and their carriers are applied onto microchan-

nels in different forms using various coating methods. In a
simple variant, the material of the microstructured reactor
forms the catalyst itself without requiring a carrier.[56, 118, 206]
The microchannel walls act as the catalyst surface, so that only
small specific surface areas are available. Applications thus
remain limited to fast reactions, or more generally to process
operations with low flow rates.
With the development and optimization of methods,
particularly for microchannel coatings, catalyst/carrier layers
with thicknesses of 150 mm are often applied. Thus, diversity
is possible with respect to porosity, material, consistency, size,
form, and (crystal) structure.[292] In the design of catalyst/
carrier systems onto microchannels, surface forces naturally
play an important role such that non-optimized coatings in
rectangular or semicircular channels often lead to V-shaped
Figure 31. a) SEM image of a cross section of a semicircular micro-
profiles. In some cases, the surfaces of semicircular channels channel with a g-alumina washcoat layer (Source: IMM[184]); b) depth
can be almost uniformly coated so that the catalyst surfaces profile of catalyst, carrier, and microstructure concentration (source:
possess semicircular profiles.[184] Universitt Kaiserslautern[292]).
In one case, the simulation of temperature profiles inside an upon Pt loading. Numerical simulations have suggested that
alumina layer was performed.[60] isothermal behavior in optimized microstructured designs can
be achieved under conditions that correspond to an adiabatic
temperature increase of up to 1400 8C.
6.3. Oxidations Further studies by Rebrov et al. showed that the material
6.3.1. Ammonia Oxidation that carries the catalyst also has an influence on the selectivity
achieved. When, for example, platinum is used instead of
Rebrov et al. initially compared three reactor systems aluminum, N2O selectivity is reduced to 20 %.[60] The lower
with microscale flow chambers (based on parallel plates, thermal conductivity of platinum leads to a greater temper-
monolith, and microstructured plate stack concepts) with ature difference within the microstructured reactor.
respect to the oxidation of ammonia to nitrogen dioxide Jensen et al. carried out the same reaction, but used a
(N2O); later the work was completed with the investigation of silicon chip microstructured reactor in which an etched
a microstructured reactor/heat exchanger (Scheme 30).[60, 214] channel was covered by a thin membrane.[54, 225230, 234] The
membrane held the catalyst at its base (exposed to the
microchannel) as a thin layer while its top side incorporated
heating elements and temperature sensors. Through the
Scheme 30. The oxidation of ammonia over a Pt catalyst. thermal conductivity of the materials used and the thickness
of the membrane the reaction temperature could be con-
trolled as heat was dissipated exclusively through convection,
In this system an external jacket provided fast heating and which occurs over the membrane and out towards the Si walls.
cooling inside the module. Microstructured reactors of Oxidation reactions with ammonia usually have an
various forms could be positioned inside the space formed. ignition/extinction mechanism that governs autothermal
A kinetic model for the oxidation of ammonia was behavior. At a fixed temperature the reaction starts (if the
coupled with a hydrodynamic description and analysis of heat added exceeds the heat dissipation of the reactor). The
heat development.[214] Using regression analysis, reaction temperature suddenly increases through heat production up
rates and selectivites for all products at equilibrium were to a state where the heat input and output are stabilized. The
predicted. Experiments proved that with optimum reactor reaction can now proceed without additional external heat-
designs, N2O selectivities up to 50 % were achieved with ing, that is autothermally. As the microstructured reactor now
complete NH3 conversions in a temperature range of 300 has a dramatically superior heat output compared to conven-
380 8C (Figure 32). Complete conversion at the lowest tem- tional reactors, it is possible for the reaction to be investigated
perature was achieved by the microstructured stacked plate in temperature regions that otherwise would not be accessible
reactor, which incorporated the highest Pt loading. Normal- (Figure 33). This behavior was exhibited in the study of Franz
ization of the activities based on a single catalyst atom divides et al. for three different membranes (1 mm SiNx, and 1.5 and
the investigated reactors into distinct two groups, suggesting 2.6 mm Si).[225] While the 1 mm membrane exhibited ignition
the existence of either Pt clusters or single atoms dependent behavior up to 570 8C at low power and autothermal
operation up to 500 8C thereafter, the 2.6 mm membrane
showed opposite behavior. Over a wide power range, a
gradual increase in temperature was observed followed by
only a small increase in temperature through ignition (from
270 to 330 8C). In contrast to conventional reactors, an
ignitionextinction hysteresis did not truly occur. The 1.5 mm
Si membranes show intermediate behavior; a fast increase up
to 520 8C with a developed hysteresis.
Figure 32. NH3 conversion (XNH3) and N2O selectivity (SN2O) for the Pt-
catalyzed oxidation of ammonia in various multiplate-stacked micro-
structured reactors (parallel-plate (A), monolith (B), and multiplate-
stacked microreactor (C)) with respect to reactor temperature. 0.022
0.543 mg Pt/Al2O3 ; 6 vol % NH3, 88 vol % O2, balance He; 600 (A1),
1175 (A2), 4430 (A3), 580 (B), and 4290 cm3 min 1 (C) under standard
temperature and pressure (STP). Reactors AC differ in their micro-
channel geometries and in the amount of catalyst carrier Al2O3. Reac- Figure 33. Ignition and extinction curves for the oxidation of ammonia
tors A1A3 differ in the amount of loaded Pt, with similar internal over Pt in various membrane-based silicon-chip microstructured reac-
dimensions of the microflow (source: University of Eindhoven[60]). tors with respect to heating output (P) (source: MIT[225]).
Angewandte
What use is the precise temperature control exhibited by To begin their study, Kestenbaum et al. used a multiplate-
microstructured reactors through the choice of membrane stacked microstructured reactor made of polycrystalline silver
type and heating power input? The selectivity of exothermic, foil (Figure 34) in which they achieved selectivities up to 49 %
high-temperature reactions, such as the oxidation of ammo- at a conversion of 12 %.[56, 105] Since pure oxygen was used for
nia, responds to the operating temperature. Yet, due to the
above-mentioned reasons, this temperature control was not
available for conventional reactors; this is now possible with
microstructured reactors. Besides the N2O/N2 slectivity, the
NO/N2 selectivity is also a sensitive parameter that increases
with increasing reaction temperature. In a chip-microstruc-
tured reactor an increase of the latter parameter is observed
from 0.5 to 2.5 in the temperature region of 340570 8C.
Note also that the microstructured reactor allows investiga-
tions in the temperature region below 340 8C for the first time.
Here an increase in NO/N2 selectivity is surprisingly found,
which is an indication of an altered mechanistic behavior.[225]
Thus, the investigations of Franz et al. show that chip-
microstructured reactors with precise temperature control
can be used to carry out reactions with better, and especially Figure 34. Spacetime yield (Y) for the synthesis of ethylene oxide in a
multiplate-stacked microstructured reactor, with respect to pressure
well-controlled selectivity. It is possible to operate previously and temperature (0.2352.350 s; 15 % ethylene, 85 % oxygen; 1 L h 1;
high-temperature reactors at lower temperatures. Even source: MPI-Kohlenforschung, M#lheim[56]).
though the oxidation of ammonia to NO is achieved at
lower yields, these operations pave the way for future partial
oxidations of hydrocarbons to other valuable products, such their experiments, safe-working limits in the explosive regime
as anhydrides, ketones, or alcohols. Aspects of industrial could be documented shortly afterwards. Using polycrystal-
relevance allow such microstructured reactors to investigate line silver the selectivity increased to 65 % without the use of
over large operating windows (here, over a wide temperature industial promoters, such as 1,2-dichloroethane.[56] This level
range). They are already a vital tool for improving the of selectivity is considerably better than that found elsewhere
accuracy and applicability of kinetic studies in heterogeneous in the literature for this unpromoted catalyst; best values
catalysis. achieved elsewhere were 69 % with promoters, and 80 % with
a combination of promoters and another catalyst, Ag/Al2O3.
Remarkably, the spacetime yield for a microstructured
6.3.2. Oxidation of Ethylene to Ethylene Oxide reactor (0.78 t h 1 m 3) exceeds that of an industrial reactor
(0.130.26 t h 1 m 3), at least if one defines the reactor volume
Kestenbaum, SchRth, and co-workers have carried out a to be only that of the microchannel, that is, the inner reaction
very detailed investigation of the oxidation of ethylene to volume. By considering the plate volume and thus also the
ethylene oxide in a microstructured reactor, where good external dimensions of the reactor, a maximum value of
temperature control and the ability to conduct nonhazardous 0.13 t h 1 m 3 is obtained, which is still within reach of the
work in a generally explosive synthetic area are the funda- industrial performance. SchRth et al. carried out further
mental motives of their work.[56, 105] The reaction enthalpy of studies on the influence of microtechnological manufacturing
the total oxidation to carbon dioxide and water is more than processes (especially regarding the roughness of the micro-
ten times greater than that of the partial oxidation channel), the residence time, the temperature and pressure,
(Scheme 31). Thus, very high local temperature regions and the partial pressures of ethylene and oxygen in the
(hot-spots) with negative consequences for the course of the ethylene oxide process (Table 1).
reaction can occur. Even though results are very encouraging, industry has yet
to apply such reactors. Prior to this taking place, the
selectivity must be increased to above 80 % as the cost of
ethylene makes up 80 % of the cost of the overall process. In
addition, further production demands (whether in small or in
large levels) have to be taken into account, for example,
reliability, process control, and many other factors.
Kursawe and HDnicke have also investigated the ethylene
oxide synthesis, working at high conversions up to 60 %.[102, 108]
Within the limits of their investigated process window, Ag/
Al2O3 was found to be better suited than Ag/Al layers, despite
a slightly lower selectivity. The thickness of the Ag coating on
Scheme 31. Above: Oxidation of ethylene to ethylene oxide in a micro- Al had a strong influence on the conversion and selectivity
structured reactor. Below: Enthalpies of epoxidation and total behavior (Figure 35).[108] In this case, selectivities up to 60 %
oxidation. were achieved at a conversion window between 5 and 30 %.
Table 1: Operating parameters and reactor performance for the ethylene oxide synthesis (Scheme 31) in corresponding aldehyde
three multiplate-stacked microstructured reactors that differ in the choice of microstructured plates. The(Scheme 33).[19, 23, 43, 154, 241] Since
values are compared to those of industrial processes.[56] then, BASF have successfully
Industrial Microreactor Microreactor Microreactor used an analogous formaldehyde
process (Laser-LIGA) (etched) (Aluchrom) synthesis from methanol with high
C2H4 concentration [vol %] 1540 1.56 315 15 conversions. It was expected that
O2 concentration [vol %] 59 1041 585 85 the synthesis of substituted alde-
CH4 concentration [vol %] 160 hydes would also present few prob-
Temperature [8C] 220275 240290 240290 270 lems. The new reactions, carried
Pressure [bar] 1022 5 220 5
out with a reliable pan-like reactor
Residence time [s] 0.91.8 0.10.2 0.11.5 1.2
C2H4 conversion [%] 715 215 520 26
(pan diameter: 5 cm), gave results
Selectivity [%] 80 4469 3869 4258 that were initially satisfying. At
Spacetime yield [t h 1 m 3] 0.130.26[a] 0.010.07[b] 0.030.13[b] 0.010.06[b] 50 % conversion, a selectivity of
0.140.78[c] 0.180.67[c] 0.080.36[c] 90 % was achieved. When a pro-
[a] Reactor. [b] Plate. [c] Channels. duction reactor with a diameter of
3 m was used, the results were
rather sobering; at 50 % conver-
sion now only a selectivity of 40 % was achieved. The reason
seemed clear; due to the large heat build-up (as a result of the
heat of reaction) an increase in temperature occurred (a hot
Figure 35. Selectivity (S) and conversions (X) for a Ag/Al microstruc-
tured reactor, as a function of the Ag-layer thickness. (250 8C; 3 bar;
20 vol % ethylene in oxygen; 0.232 s. Source: Universitt
Scheme 32. Above: Oxidation of 1-butene to maleic anhydride in a
Chemnitz[108]).
multiplate-stacked microstructured reactor. Below: Enthalpies of
synthesis and total oxidation.[102]
Furthermore, safe working within the explosion regime has be
proven for ethylene oxide synthesis in a microstructured
reactor.[108] Sputtered silver, as well as solgel-grown Al2O3/
silver layers on microstructures made of an aluminium alloy
(AlMg3) were investigated. Neither explosions nor flames
were observed. The cross sections of the microchannels were
200 L 200 mm2 and 700 L 300 mm2.
6.3.3. Oxidation of 1-Butene to Maleic Anhydride
Kah et al. carried out the oxidation of 1-butene to maleic

anhydride in a multiplate-stacked microstructured reactor
over a V2O5/P2O5/TiO2 catalyst (Scheme 32).[103] Selectivities
of 33 % were achieved at conversions between 7385 %. Figure 36. Spacetime yield (Y) of maleic anhydride (MA) as a func-
tion of 1-butene conversion (X) in two microstructured reactors (& and
An increase in the spacetime yield by a factor of five
~), which differ in both their dimensions and the number of parallel
compared to a fixed-bed reactor was achieved (Figure 36).
operating plates, and in a fixed-bed reactor (*). (400 8C; 0.4 %
These reactions were carried out safely within the explosive
1-butene in air; 0.1 MPa).[103]
regime.
6.3.4. Oxidation of Alcohols to Aldehydes
WDrz et al. investigated the partial oxidation of a sub- Scheme 33. Oxidation of an alcohol to an aldehyde in a microstruc-
stituted alcohol over a silver catalyst, which led to the tured reactor.
Angewandte
spot exceeding the reaction temperature by 160 K) that 6.3.5. Oxidation of Isoprene to Citraconic Anhydride
overshot the set operating temperature. In the formaldehyde
synthesis this was marginal, while for the aldehyde synthesis Citraconic anhydride is currently manufactured using
both the reactants and products were unstable, and a result, complex synthetic methods. An alternative to these methods
thermally induced side reactions took place. could exist through the heterogeneous catalytic oxidation of a
With this in mind, the actions needed to be taken were suitable hydrocarbon, such as maleic or phthalic anhydride. In
obvious: a decrease in hot spots, a decrease in the overall this context Liauw, Walter, and co-workers investigated the
operating temperature and, at best, a significantly reduced partial gas-phase oxidation of isoprene in a microstructured
contact time. The ideal combination of all these requirements reactor (Scheme 34).[207, 240] The excellent heat-transfer prop-
can only be set in a microstructured reactor. WDrz et al.
successfully obtained a selectivity to 96 % at a conversion of
55 % (without a hot spot). However, all conventional
solutions that take one aspect into account above the other,
show results that are superior to a panlike reactor, but inferior
to a microstructured reactor (Figures 37 and 38). Thus, a
Scheme 34. Oxidation of isoprene to citraconic anhydride.
erties of microstructured reactors are essential in this case,

since these reaction release large amounts of heat
( 1000 kJ mol 1). When overheating occurs, total oxidation
to water and carbon dioxide can dominate in the reaction.
The same authors showed that selectivities (up to 28 %)
and conversions (up to 100 %) comparable to operation in a
fixed-bed reactor were achieved in a microstructured reactor,
however the microstructured reactor achieved its maximum
performance at 400 8C, whilst the fixed bed delivered
optimum results at 360 8C (Figure 39). This illustrates the
Figure 37. Various reactor configurations for the selective oxidation of
excellent heat dissipation in the microstructured reactor. In
an alcohol to an aldehyde in the gas phase (source: BASF, Ludwigs- the fixed-bed reactor the catalyst temperature lies 40 8C
hafen[19]). higher that in the set reactor temperature, which was proven
by placing a thin thermocouple in the reactor bed. The
catalyst from the fixed-bed experiments (V30Ti70Ox) was
inserted in the microchannels in the form of a silicic acid
suspension. Although, the chemical composition was slightly
modified (V30Ti70Ox/SiO2), this had no influence on the
Figure 38. Comparison of the reactor performance of a short multitub-

ular reactor (&) and a multiplate-stacked microstructured reactor (^)
in the selective oxidation of an alcohol to an aldehyde (source:
BASF[23]).
single-tube reactor can be operated almost isothermally, yet

its considerably long residence time reduces selectivity. A Figure 39. Isoprene conversion (Xisoprene) and citraconic anhydride
multitubular reactor with many short tubes can, in compar- selectivity (SCA) in the partial oxidation of isoprene at various flow
rates in a) a fixed-bed reactor, and b) a microstructured reactor.
ison, achieve significantly shorter residence times with
(^ = Xisoprene (120 ml min 1), ^ = Xisoprene (300 ml min 1), * = SCA
acceptable heat transfer (conversion 50 %; selectivity 85 %; (120 ml min 1), * = SCA (300 ml min 1); 0.6 vol % isoprene, 20 vol %
hot spot 60 8C). Again, a microstructured reactor gives oxygen; 1.2 bar; V30Ti70Ox (fixed bed); V30Ti70Ox/SiO2 (microstructured
superior results for both of the measured parameters. reactor; source: Universitt Erlangen[240]).
catalyst properties in the fixed-bed experiments. In compar- 6.3.7. The Andrussov Reaction
ison to the (ceramic) fixed-bed reactor the yield found in the
(metallic) microstructured reactor was slightly reduced, due Hessel et al. have investigated the Andrussov synthesis, in
to the blind activity of the total oxidation in the micro- which hydrogen cyanide is formed from methane, ammonia,
structured reactor that results from, among other things, the and oxygen, by using a microstructured reactor with a mixer,
high surface-to-volume ratio. and a structured catalyst foil with microchannels and a heat
exchanger (Scheme 36).[118] It is noteworthy that temperatures
6.3.6. Partial Oxidation of Methane (Production of Syngas)
Mayer, Fichtner, and co-workers have investigated the

manufacture of syngas (a mixture of carbon monoxide and Scheme 36. The Andrussov reaction to form hydrogen cyanide.
hydrogen) through the partial oxidation of methane over a
rhodium catalyst at temperatures between 1090 8C und
1190 8C (Scheme 35).[206, 242] The conversion of methane to exceeding 1000 8C were recorded in parts of the catalyst
syngas is part of a strategy where the structure. With increasing temperature, yields of hydrogen
gases in subsequent process steps are cyanide up to 31 % (approximately half the value found in the
converted to liquid products such as industrial process) were obtained with a near complete
Scheme 35. Manufac- methanol which are easier to transport. conversion of methane. The ammonia selectivity of 62 % is
ture of syngas through A microstructured reactor was within the region of the industrial process, however, methane
the partial oxidation of used whose structure consisted of a selectivity (30 %) is considerably lower because total oxida-
methane in a micro- solid Rh monolith with 120 mm micro- tion reactions take place in addition to the formation of
structured reactor. channels. In comparison to laboratory hydrogen cyanide (Figure 41).
fixed-bed reactors or conventional
extruded monoliths, which are coated
with the catalyst, microstructured reactor monoliths differ
mainly in their decreased dimensions, the decreased pressure
drop through the optimized flow paths, and the application of
a solid catalyst material. A good heat distribution over the
microchannels is achieved. As a result, the conversion and the
hydrogen and carbon monoxide selectivities are higher than
corresponding laboratory reactors (Figure 40). In combina-
Figure 41. The Andrussov process: Comparison of products from a

complex microstructured reactor and an optimized industrial plant
(source: IMM[118]).
When one compares the yield with that of laboratory

reactors (e.g., monoliths), microstructured reactors are shown
to be superior to laminar operating systems, exhibiting only a
slightly lower performance than a monolith under turbulent
operation (yield 38 %). Although results from the micro-
structured reactor do not approach industrial levels, the
feasibility of an industrial three-component reaction at very
high temperatures was demonstrated. A six-party industrial
Figure 40. Syngas production: CH4 and O2 conversions (X), as well consortium was established and measurements were carried
as CO, CO2, and H2 selectivites (S) at various temperatures for a Rh out at BASF and Rhodia (Lyon, France). It can also be argued
multiplate-stacked microstructured reactor (CH4/O2 : 2; 0.12 MPa; 0.2 that these results demonstrate that microstructured reactors
3 ms; 7.8 U 105 L h 1 (STP); source: Forschungszentrum Karlsruhe[206]). does not suit every chemical process.
6.3.8. Oxyhydrogen Gas Reaction
tion with the lower pressure drop, a higher spacetime yield is The reaction between hydrogen and oxygen was inves-
obtained. A study of the influence of parameters such as tigated by Hagendorf et al. as a basic study of the technical
temperature, total pressure, CH4/O2 ratio, space velocity, and process,[107] and by Veser as a detailed mechanistic analy-
inert gas dilution was also presented. These studies high- sis[39, 40] (Scheme 37). Both investigations proved that this
lighted the influence of the elementary reactions (total reaction, which lies in the explosive regime (for most p, T, and
oxidation and reforming) and carbon deposits on the catalyst c values), could be handled safely in microstructured reactors.
during the course of the reaction. Veser speaks of an intrinsic safety when working under
Angewandte
Scheme 37. Catalyzed oxyhydrogen reaction in a microstructured

reactor.
atmospheric pressure as soon as sub-millimeter dimensions

are attained.[40] Hagendorf et al. showed that complete
conversion is achievable and thus that the corresponding
reaction mixtures can exist outside of the explosive regime.[107]
At high mass flows, a large amount of heat is naturally
released that cannot be completely dissipated, even in good
microheat exchangers (Figure 42). The device heats up in
certain areas, as proved by thermographic analysis.
Figure 43. Shift of the kinetic (&, &) and thermal explosion limits (*,
* for Twall = RT; ~, ~ for Twall = Treaction) for the reaction of hydrogen and
oxygen for a conventional reactor (1 m; &, *, ~) and a microstruc-
tured reactor (300 mm; &, *, ~; source: MPI-Kohlenforschung[40]).
Franz et al. carried out the oxyhydrogen reaction in a Pd-

membrane-microstructured reactor to investigate the possi-
bility of combined reaction and separation.[231] A hydrogen/
nitrogen flow runs parallel to a flow of oxygen, with both
streams separated by a membrane, which can withstand a
pressure of 5 bar; water was shown to form by this process.
6.4. Hydrogenation
Figure 42. Reaction temperature of an oxyhydrogen reaction in a multi-
plate-stacked microstructured reactor at various residence times and 6.4.1. Hydrogenation of Polyenes and Arenes
reactant flows (source: MPI-Kohlenforschung[105]).
Wiemeier, HDnicke, and co-workers have investigated
the hydrogenation of cis,trans,trans-1,5,9-cyclododecatriene,
A quartz microstructured reactor could function at 1,5-cyclooctadiene, and benzene in an Al multiplate-stacked
temperatures above 1000 8C without degrading the microreactor that was anodically oxidized at the microchannel
device.[40] Veser achieved this by increasing the amount of surface to create nanopores,[100, 101, 213, 243245] which were sub-
hydrogen in steps at a given synthetic air flow rate. A second sequently impregnated with a Pd salt (Scheme 38). All of the
reactor with improved thermal-loss properties and a Pt above-mentioned substrates possess several double bonds
contact showed no evidence of homogeneous reactions, for and thus can undergo several hydrogenation steps. However,
example in the form of flames or explosions. Kinetic analysis technically useful and valuable products are not always the
based on a radical-chain mechanism determined the three end products, but unsaturated intermediates such as cyclo-
explosion limits of the oxyhydrogen reaction as a function of dodecene, cycloctene, and cyclohexene. Microstructured
the characteristic diameter. By decreasing the diameter from reactors were investigated in order to establish whether
1 m down to between 1 mm and 100 mm, a shift in these limits their good mass- and heat transport, and their well-defined
was observed. Therefore, previously explosive regimes could residence time would increase the selectivity of the partial
now be handled safely. hydrogenation.
While the first explosion limit is affected mainly by the In a very illustrative experiment the hydrogenation of
diffusion path length, the third explosion limit (which is cis,trans,trans-1,5,9-cyclododecatriene was attempted using a
responsible for many explosions under normal pressure) has a conventional grain-shaped catalyst in both a fixed-bed reactor
complex dimensional dependency due to a complex inter- and in a microstructured housing with fitted microchanneled
action of elementary reactions. Investigations showed that a plates (Figure 44).[244] As an intermediate step, cut wires and
kinetic quenching of the radical-chain mechanism is respon- aluminum foil were investigated as a fixed bed, which had the
sible for the suppression of explosive behavior, and not a same nanoporous structure as the microstructured reactor;
thermal quenching due to significantly higher heat-transfer the conventional catalyst, on the other hand, had a less
rates (Figure 43). This means that reactors with slightly regular pore structure. The difference between the fixed beds
poorer heat transfer (e.g., due to an increase in productivity and the microstructured reactor was most notable in terms of
through more compact construction of many parallel reac- the flow, which followed either a path through various voids
tors) should also be intrinsically safe. This result also shows and dead volumes, or along a direct and regular route in the
that similar effects can be achieved for other radical-chain microchannel. The difference between the fixed-bed reactors
reactions. is in the administration of the catalyst: conventional or
The best results were achieved by increasing the hydrogen

partial pressure and adding CO.
The hydrogenation of benzene in a microstructured
reactor with a Pd catalyst does not proceed immediately,
and increasing the hydrogen partial pressure leads to the
undesired formation of cyclohexane.[245] Thus, a Rh/Zn
catalyst was used and methanol was added in order to
hinder the readsorption of cyclohexene (the desired product)
at the catalyst, and the partial hydrogenation reaction could
proceed. The conversion decreased from an initial value of
90 % to 10 % within 4 h; the catalyst however became more
selective. Whilst only cyclohexane was generated initially, a
cyclohexene selectivity of 36 % was eventually achieved.
6.4.2. Hydrogenation of Cyclohexene
Besser's group have carried out a detailed study of the

hydrogenation of cyclohexene to cyclohexane over a Pt
catalyst (Scheme 39).[99, 112] This reaction serves as model
reaction for understanding important industrial gas-phase
processes (e.g., hydrotreatment in
Scheme 38. Catalyzed hydrogenation of polyenes and arenes in microstruc- petrochemistry and hydrogen
tured reactors. extraction by fossil-fuel process-
ing). Dehydrogenation to benzene
also occurs as a competitive reac- Scheme 39. Catalyzed
tion, depending on the reaction hydrogenation of cyclo-
temperature. hexene in a microstruc-
tured reactor.
A microstructured reactor with
a fresh catalyst achieved a conver-
sion of 50 % with a selectivity of
60 % (cyclohexane) or 40 % (benzene) at room temperature.
However, the reaction behavior was transient, that is, the
selectivity shifed with time towards the hydrogenation
reaction. This transience was reduced by conditioning the
catalyst through increased chemisorption with cyclohexene
and hydrogen. In such a stable state at 120 8C, cyclohexene
Figure 44. Selectivity(S)conversion(X) diagram for the hydrogenation selectivity was increased to 100 % at a conversion of 95 %. On
of cis,trans,trans-1,5,9-cyclododecatriene (CDT) to cyclodocene (CDE) raising the temperature to 200 8C, however, conversion was
in a conventional Pd/Al2O3 (&) fixed-bed compared with fixed beds found to decrease again in favor of dehydrogenation to
wires ( ) and small cut foils (), which act as an anodically modified benzene, which can achieve a selectivity of nearly 80 %
microstructure. Also shown are results for a microstructural reactor
(Figure 45).
(&). (source: Universit3t Chemnitz[244]).
wire/foil catalysts both have a locally ordered nanoporous

structure. The difference between the fixed-bed wire and
foil is only in the density of their packing; the adminis-
tration of the catalyst is the same.
The reactors were compared in terms of their selectivity/
conversion ratio. The selectivity for the conventional fixed
bed decreased from 62 % to 44 % in the investigated
conversion window (80100 % conversion, respectively). In
contrast a selectivity of 73 % was found for the foil-fixed bed.
The more densely packed wire-fixed bed gave even better
results. For microstructured reactors, the best results gave a
selectivity of 84 % with complete conversion.
The selective hydrogenation of cyclooctadiene to cyclo-
Figure 45. Selectivity (S) of the Pt-catalyzed hydrogenation/dehydro-
octene gives even better conversion in microstructured genation of cyclohexene to benzene (~) and cyclohexane (~), with
reactors.[245] A selectivity of 98 % at total conversion was respect to the temperature of a silicon-chip-based microstructured
found, thus giving a yield of 98 % (116 ms; 150 8C; 110 kPa). reactor (source: Stevens Institute, Hoboken[99]).
Angewandte
In addition, the H2/cyclohexene partial pressure ratio and

the residence time were varied, and through the application of
Pt on a porous layer the influence of the porosity was
investigated. The specific surface area was increased approx-
imately by a factor of two compared to the planar Pt catalyst
coating. Here, no differences in the maximum activity could
be seen unless the H2/cyclohexene partial pressure ratio was
varied.
Perhaps the most important and striking result from these
studies was the ability to use only small quantities of reagents
by using silicon-chip reactors. For example, a 140 h experi-
ment required only 3.1 g ( 4 mL) of cyclohexene.
Figure 46. The influence of mixing (in methanol and sodium steam
6.5. Dehydrogenation flow paths) on the formaldehyde selectivity (S) in the Na-catalyzed
6.5.1. Dehydrogenation of Methanol to Formaldehyde dehydrogenation of methanol, with respect to residence time (source:
EPFL Lausanne[22]).
The endothermic dehydrogenation of methanol to form-

aldehyde is a high-temperature reaction (700900 8C) with a concentrations (91.5 %) was also possible without danger, and
contact time in the region of milliseconds (Scheme 40). had no detrimental influence on methanol conversion or
formaldehyde selectivity. In addition, an increase in the
residence time, accompanied by an increase in conversion
from 57 % to 72 % for the 130 mm microstructured reactor,
Scheme 40. Dehydrogenation of methanol to formaldehyde in a micro- did not decrease the selectivity.
structured reactor. These experimental results correspond well to a simple
reactor model that was proposed by Gobby et al. for a
catalyst-wall plate microreactor.[246] The reaction constant k
AlTpTe et al. carried out theoretical investigations to optimize was determined from an Arrhenius plot. By using an
the fluid path and develop suitable heating and cooling approximation, which took into account the Peclet and
concepts in microstructured reactors.[22] As a result, a double- DamkDhler numbers, as well as the microchannel aspect
sided, heated microstructured design was developed, which ratio, the conversion values were calculated.
made use of counter-flow paths for reactant and product gases
to give a superior heat balance. As well as allowing ultra-short 6.5.2. Dehydrogenation of Propane to Propene
contact times to be set exactly, heating and cooling processes
could be carried out in less than 0.5 ms (at rates of Baerns, Steinfeldt, et al. have compared a multiplate-
1000 K ms 1). stacked microstructured reactor and a fixed-bed reactor for
In addition, Maurer et al. investigated the dehydrogen- the oxidative dehydrogenation of propane to propene over a
ation of methanol to formaldehyde at 700800 8C by homo- VOx/Al2O3 catalyst (Scheme 41). For both reactors the gas
geneous catalysis with sodium steam.[114] The process was
investigated using a multiplate-stacked microstructured reac-
tor system consisting of a mixer, reactor, and heat exchanger.
Preliminary investigations indicated a strong influence of
mixing on selectivity. Depending on the form of the flow path
during mixing, differences between 15 % and 70 % in
selectivity were obtained (Figure 46).
The same process, although as an oxidative dehydrogen- Scheme 41. Dehydrogenation of propane to propene in a microstruc-
ation, was also investigated by Cao et al.[113] A microstructured reactor.
tured reactor manufactured using deep-etching technology
(Deep Reactive Ion Etching, DRIE) in silicon has two
layouts; one with 70-mm and one with 130-mm-deep channels composition (C3H8/O2/Ne), temperature (733800 K), and gas
(both 600 mm wide). A silver catalyst was applied by sputter- flow rate (50150 mL min 1) were varied. Both reactor
ing through a shadow mask. The structured silicon wafers systems exhibited similar selectivity/conversion behavior in
were enclosed with pyrex glass wafers. isothermal operation.[247] The same VOx/Al2O3/boehmite
Investigations between 430 and 530 8C showed methanol suspension was used as a starting material for catalyst
conversions of 6075 % with selectivities of around 90 % (12 preparation in both cases. It was clear that a similar catalyst
91.5 vol % pure oxygen, 8.5 vol % methanol, helium as the wall coating was generated in the microstructured reactor and
remainder). Conversions and selectivities were comparable to as the packing in a fixed-bed reactor. This was proved by
industrial processes but were achieved at lower temperatures characterization of the catalyst surface with XRD, BET,
in the microstructured reactor. The use of high oxygen TEM, and ICP-OES measurements.
These studies assessed the correlation between the hot

spot of the reaction and reactor performance (in terms of
conversion and selectivity by measuring fixed-bed axial
temperature gradients and temperatures at the inlet and
outlet of the plates of the microstructured reactor against
propane and oxygen conversion (Figure 47). Depending on
Figure 48. Dehydrogenation of propane: Propane conversion (X; &, &)

and propene selectivity (S; *, *) for a filament-based catalyst (&, *)
and a conventional powder catalyst (&, *) as a function of time (t).
(550 8C; 0.14 MPa; space velocity: 1161 h 1; 3.1 s; source: EPFL Lau-
sanne[233]).
6.5.3. Dehydrogenation of Cyclohexane to Benzene
Ciu et al. have recently

designed a microstructured reactor
for the dehydrogenation of cyclo-
Scheme 42. Dehydroge-
hexane to benzene over a Pt cata- nation of cyclohexane to
lyst in the presence of a hydrogen- benzene in a microstruc-
permeable Pd membrane.[112] tured reactor.
Experimental results have not yet
Figure 47. Dehydrogenation of propane: C3H8 (a,c), O2 (b,d) conver-
sion (X), and temperature gradients DT = Tmax Tin (e,f) as a function been presented (Scheme 42).
of reactor inlet temperature (Tin) for a fixed-bed reactor (*) and a
microstructured reactor (&). a), b), e): C3H8/O2/Ne = 0.3/0.15/0.55,
Ftot = 150 mL min 1; c), d), f): C3H8/O2/Ne = 0.5/0.25/0.25, 6.6. Extraction of Hydrogen and Other Fuels
Ftot = 120 mL min 1 (source: ACA, Berlin[247]).
Fuel processing, with an aim of extracting hydrogen,
reaction conditions, temperature gradients up to 100 K were continues to gain in importance. Consequently, there have
achieved in the fixed-bed reactor, while the differences in the been numerous investigations on this subject that have been
microreactor were a maximum of 3 K. No variation in carried out in microstructured reac-
propane and oxygen conversion was observed under isother- tors.[206, 209211, 215, 216, 222, 242, 248267] These reactions are often a
mal conditions, while with increasing temperature gradient, complex network of many elementary reactions. The reac-
conversions for both gases increased more rapidly in the tions are generally assessed in terms of the amount of
fixed-bed reactor. The results showed that (strongly exother- hydrogen obtained (corresponding to the stored energy),
mic) reactions in microstructured reactors can be achieved which is typically then fed into a fuel cell to produce energy.
without axial temperature gradients, and the experimental Due to the importance of mobile applications (e.g., in cars)
data obtained under isothermal operation could be used as a the weight and size of the systems used play an important role.
basis for kinetic modeling. Very good heat exchange is essential to couple exothermic
Wolfrath et al. carried out the thermal dehydrogenation of reactions with endothermic reactions. Because of these
propane over a Pt-Sn/g-Al2O3 catalyst filament (310 mm in factors, the performance of a hydrogen-generating system
diameter).[233] A structured catalytic bed was obtained, which cannot be fixed purely on the individual parameters of the
resulted in laminar flows similar to those obtained in micro- respective reactions (e.g., selectivity) but instead must
structured channels. The filaments, arranged concentrically, achieve an overall balance.
were grouped into two zones. In the first zone, dehydrogen- It is clear that a overview of hydrogen-generating
ation over the catalyst took place. The second zone, separated reactions would fall outside the remit of this Review. There-
from the first by a hydrogen-permeable Pd/Ag membrane, fore, only three examples will be briefly discussed.
removed hydrogen from the reaction mixture and burned it
through the introduction of oxygen (Figure 48). Propane 6.6.1. Methanol and Propane Steam Reforming
conversion up to 30 % and selectivities up to 96 % were
achieved and the pressure drop was lower than an equivalent The interested reader is referred to the important studies
fixed-bed packing consisting of spherical particles. by the groups of Schubert,[222, 252] Wegeng,[249, 255, 256] and
Angewandte
Renken[253, 254] to obtain a more detailed insight into this area 6.6.2. Partial Oxidation of Methane
of research.
Cominos et al. investigated methanol steam reforming at Tonkovich et al. investigated the partial oxidation of
200300 8C in a multiplate-stacked microstructured reactor methane at 700 8C in a microstructured reactor over a Rh
over a CuO/ZnO/g-Al2O3 catalyst (Scheme 43).[215, 216] A catalyst on a silica carrier
power density of 1.8 W cm 3 and a hydrogen content of (Scheme 45; residence time:
50 vol % in the product gases were obtained. The process was 50 ms).[267] Their investigations con-
designed for a potential 100 W fuel-cell system. centrated mainly on determining
Scheme 45. Partial oxi-
selectivity under different operating dation of methane in
conditions, and using catalysts at a microstructured
different positions on the microchan- reactor.
neled plate. First, the catalyst powder
Scheme 43. Steam reforming of methanol in a microstructured reactor.
was allowed into the microchannels,
thus forming something similar to a micro fixed-bed reactor.
Kolb et al. extended these investigations through the Measurements under non-equilibrium conditions show CO
detailed screening of CuO/Cr2O3 and CuO/Mn2O3 catalysts selectivities up to 70 % and a H2 selectivity over 50 %. The
on various aluminum oxide washcoats, such as corundum, first set of values lie partly over equilibrium, while the second
boehmite, and g-alumina (Figure 49).[184] A 10-fold parallel- set reside below. Both sets tend to increase with increasing
screening reactor was used, in which each plate was coated temperature. Future investigations should offer even better
with a different catalyst.[221] It was observed that the catalyst selectivities if, for example, operation up to 900 8C is possible.
on boehmite showed the highest activity. If the catalyst is packed at the inlet region of a micro-
structured reactor, different results are obtained. Selectivities
become constant over the entire temperature range and
correspond to values that are obtained in the micro fixed-bed
reactor at operating temperatures of 700 8C and above. This
indicates significant local overheating due to the heat of the
reaction. Even with an external reactor temperature of
300 8C, temperatures of 700 8C exist at the inlet (Figure 50)
because of the large volumes used and the less well-directed
flow path in the inlet. Both experiments highlight the
Figure 49. Methanol steam reforming: Comparison of the activities of

CuO/Mn2O3 and CuO/Cr2O3 catalysts with various aluminium oxide
washcoats (source: IMM[184]). MS = mixed systems. First measure-
ment: black; second measurement (displaying catalyst deactivation):
white.
Kolb et al. carried out the propane steam reforming

process at 650800 8C in a two-plate sandwich-microstruc-
tured reactor (Scheme 44).[184] Screening tests on Rh, Pt, Pd,
Rh/Pt, and commercially available Ni catalysts loaded on g-
alumina were operated in series. The Rh sample was shown to
exhibit the highest activity. Also, impregnation of the Rh, Pt, Figure 50. Partial oxidation of methane in a multiplate-stacked micro-
and Rh/Pt catalysts with CeO2 increased both activity and structured reactor with a Rh contact. Comparison of experimental
CO2 selectivity, yet decreased the selectivity of CO and selectivities (Sexp) for CO (*), C(s) (~), and H2 ( ! ) under nonequili-
propene, which are the main by-products that arise when brium conditions, and at equilibrium (CO (*, C(s) (~), and H2 ( ! );
short residence times are employed. Complete conversion to source: PNNL, Richland[267]).
CO2, CO, and H2 (with no by-products) was achieved with a
Rh/Pt/CeO2/g-Al2O3 catalyst at 750 8C with a residence time
less than 10 ms and a steam-to-carbon ratio of three, without importance of a microchannel inlet feed path. In addition,
observing significant deactivation. they show that almost no carbon is deposited. It should be
noted that this work describes one of the first examples of an
exothermic high-temperature reaction with a contact time
less than 10 ms, and is truly pioneering work in microstruc-
Scheme 44. Steam reforming of propane in a microstructured reactor. tured reactor technology.
6.6.3. The Sabatier Reaction of reaction (165 kJ mol 1 at 25 8C). Operating under isother-
mal conditions, conversions up to 85 % at a selectivity of
The Sabatier reaction is a process for generating methane 99.4 % were obtained (60450 ms; 400 8C; 20 % CO2, 80 %
from hydrogen and carbon dioxide at temperatures around H2). This represents significant enhancement of the process
400 8C (Scheme 46).[268, 269] Initially, one fuel is converted into compared to adiabatic operation which under the given
conditions leads to a temperature increase up to 625 8C;
conversion is limited to 66 % and the selectivity decreases to
41.6 %.
Scheme 46. Sabatier reaction in a microstructured reactor.
6.7. Eliminations
another, however using hydrogen instead of methane is 6.7.1. Dehydration of 2-propanol to Propene
advantageous in terms of energy density, and thus also in
terms of freight weight in the case of mobile applications and Rouge et al. have carried out the elimination reaction of
transportation. Thus, Wegeng et al. are investigating applica- 2-propanol to propene over a g-alumina catalyst at 200 8C and
tions of the Sabatier reaction for unmanned missions to 1.3 bar, which can lead to a
Mars.[269] The carbon dioxide present in the atmosphere of bimolecular side reaction to
Mars could be converted into methane using the transported give diisopropyl ether
hydrogen. (Scheme 47).[74] Scheme 47. Dehydration of 2-
propanol in a microstructured
Tonkovich, Wegeng, and co-workers have investigated Theoretical predictions, as
reactor.
these and further reversible exothermic reactions, such as the well as investigations with a
water-gas-shift (WGS) reaction, both experimentally and laboratory fixed-bed reactor,
theoretically.[210] All these processes have in common the fact proved that periodic operation at varying concentration leads
that with reaction rates increase with increasing temperature, to an increase in the product concentration in the gas mixture
but also exhibit a lower equilibrium conversion. Thus, the and the overall yield, respectively (Figure 52). This improve-
temperature determines the interaction between kinetic and ment in reaction performance, which occurs through setting
chemical equilibrium in the reaction chamber (Figure 51). the flow rate of the reactants to zero, is considered to be a
stop effect, and is due to altered adsorption/desorption
behavior on the active sites of the catalyst during periodic
operation. From periodic measurements with the laboratory
reactor, kinetic data were obtained that led to a model to be
used with microstructured reactors.
Periodic operations in a microstructured reactor benefit
mainly from a smaller volume of reagents and a narrower
residence-time distribution, which allows for operations at
higher frequencies compared to conventional reactors. The
results of a periodic operation in a multiplate-stacked micro-
Figure 51. The Sabatier reaction: The influence of temperature on CO2

conversion (XCO2) with a fixed-bed catalyst. a = equilibrium conver-
sion; 1RU: 1 wt % Ru/61-80 (United Catalysts); 3RU: 3 wt % Ru/TiO2
(Degussa); 5RU: 5 wt % (Engelhard). Source: PNNL, Richland.[269]
They have been able to control productivity and, thus, the

necessary catalyst loading of the reactors. Optimized temper-
ature trajectories are demanded for reversible exothermic
reactions in compact systems. Whilst this problem has been
challenged so far with adiabatic reactors and heat exchangers
connected in series, or fixed-bed reactors with tube-heat
exchangers, microprocess technology apparatus can offer
entirely new possibilities. Figure 52. The concentration of 2-propanol (~), propene (U ), and di-
isopropyl ether (J) in the periodically operated dehydration of 2-propa-
This has been impressively proved by the experiments and
nol to propene in a multiplate-stacked microstructured reactor over a
simulations of Tonkovich et al.[210] The Sabatier reaction was g-alumina catalyst (change in 2-propanol concentration of
carried out in a microchanneled reactor with counter-current 0.86 mol m 3 at STP to 0 (av 0.43 mol m 3 2-propanol); 200 8C; 1.3 bar;
flow cooling (through N2 gas heat transfer) to remove the heat 0.175 s; source: EPFL Lausanne[74]).
Angewandte
structured reactor compared very well to the model predic- perhaps larger unit that is dedicated to issues in microprocess
tions. A 30 s cycle was carried out, during which the amount of technology. In particular, fine chemicals companies have
propene in the reaction mixture increased from 0.1 to turned their attention to this technology, and the subject is
0.27 mol m 3 (at standard temperature and pressure). expected to be one of the key themes of future chemical
industry.[287] Oroskar et al. have provided a description of the
potential of microstructured reactors from the industrial point
6.8. Catalyst Screening of view.[61, 288]
A recent example of a successful industrial investigation
Most of the studies concerning catalyst screening for gas- based on micro heat-exchangers was presented by Bayer et al.
phase reactions in microstructured reactors have dealt mainly (Siemens Axiva, Hoechst, Germany) based on the chlorina-
with the discovery of good new catalyst materials and less tion of alkanes. (Scheme 49).[48] Conventional tube reactors
often with the reaction itself.[125, 220, 221, 270275] Catalyst screening
is an individual and broad discipline which would exceed the
scope of this Review.
Scheme 49. Industrial chlorination of alkanes in a micromodule.
7. Industrial Applications of Microstructured

Reactors for such processes exhibit slow temperature ramping and
thermal overshooting. Externally heated micro heat-transfer
7.1. Process Development on the Laboratory Scale modules allow for a suitable choice of operating temperature,
with a steep temperature increase possible. Such microheater
1995 witnessed the beginning of concentrated microstruc- modules, which are several times smaller than the combina-
tured reactor research activities, coming in the same year that tion of a long tube reactor and a surrounding oven, allow
scientists met for the first time at a workshop to discuss results reactants to be heated up to ten times faster.
in microprocess technology. The same year saw the develop- Although preheating was carried out with a microdevice, a
ment of two important processes, both carried out in conventional tube reactor was still used for the reaction itself,
industrial chemical laboratories. WDrz et al. described the since no process improvement was expected in this region. In
partial oxidation of an alcohol to an aldehyde; a process that addition, it was preferred due to the pressure drop and to its
BASF carried out on the production scale (see Sec- operating reliability compared to the microstructured reactor.
tion 5.3.4.).[19, 23, 43, 154, 241] With this hybrid system configuration a significant increase in
Lerou et al. carried out a number of catalytic gas-phase conversion by about 25 % and an increase of spacetime yield
reactions in microstructured reactors, which were subse- of 240 to 430 g h 1 L 1 was achieved. The key to this
quently analyzed extensively by DuPont in their investiga- process enhancement is fast and uniform initial radical
tions into high-temperature, dangerous, catalytic, and photo- formation, which stems from better thermal control of the
chemical gas-phase processes. The microstructured reactor process.
composed of a stack of silica wafers based on typical silicon-
chip architectures.[21] Each wafer had a specific function, for
example, as a heat exchanger or a catalyst room. The catalyst 7.2. Production of Organic Chemicals
was introduced in the form of solid particles, that is, as a
miniature fixed bed. For the synthesis of methyl isocyanate It is difficult to estimate how present investigations are
from methyl formamide, similar conversions as conventional divided into the various industrial areas of laboratory, pilot,
synthesis could be obtained, albeit at lower selectivities and production scale, for the reason that the disclosure of
(Scheme 48).[21] One reason for this is seen in the non-ideal results in industry is the exception rather than the rule. Thus,
temperature profiles within the reaction zone of the micro- only few examples are available for discussion. Krummradt,
structured reactor packing. Stoldt, and co-workers (Merck) provided the first industrial
example of the use of small-structured reactors, reporting an
increase in yield by 25 % for an organometallic reaction that
used an interdigital mixer rather than a batch process
(Scheme 50, Figure 53).[50]Their studies were not limited to
Scheme 48. Synthesis of methyl isocyanate from methyl formamide in laboratory scale. Since 1998 a plant at Merck has produced
a microstructured reactor. fine chemicals using five parallel-connected mini-mixers,
which have replaced the conventional stirred tank. Equidis-
Numerous industrial laboratory investigations have since
been carried out. However, many of these studies have not
been published, which illustrates their increasing interest and
industrial relevance. Economic benefits from these studies are
expected, which is reflected by the ever-increasing number of
pending industrial patents in microprocess technol- Scheme 50. An organometallic reaction in a mictrostructured reactor
ogy.[49, 276286] Almost every chemical company has a small, or that is carried out on the production scale.
static mixers in continuous operation tend to plug, the change

in fluid dynamics throughout the mixer leads to varying
concentration distributions of all the participating active
species, the result being that insoluble high-molecular poly-
mers are no longer prepared. Micromixers operate mostly
plug-free, even though the inner dimensions are much smaller
than conventional static mixers. A process with only 28 par-
allel-connected micromixers fulfilled the demands of indus-
trial production (Figure 54).
Figure 53. The search for the optimal temperature and gas composi-
tion (R) for an organometallic reaction in an interdigital micromixer Figure 54. Plan of a production plant (2000 tonnes per year) for the
tube reactor using statistical methods. a) flow rate = 0.4 L h 1, b) flow radical polymerization of acrylates in solution (source: Siemens-Axiva,
rate = 2.0 L h 1 (source: Merck[50]). Frankfurt[47]).
tribution to the mini-mixer units is technically challenging and Wille et al. (Clariant) described the first production
thus significant efforts in terms of process control are applications for producting pigments in microstructured
required. reactors.[51] Two industrially relevant azo-coupling processes
Recently Hessel (IMM), Wehle (Clariant), and co-work- were carried out that are distinguished by the coupling agent
ers described the development of a laboratory process that is and the diazonium salt used (Scheme 52). The azo coupling is
fast, strongly exothermic, and sensitive to mixing.[289] The
original batch process was very slow, with several parallel and
secondary ractions decreasing the yield to 65 % during
production. Initially, a yield of 85 % was obtained by using
an interdigital micromixer tube reactor, which increased to
90 % with optimized reaction conditions. Similarly to the Scheme 52. Azo coupling as part of a pigment synthesis, carried out in
example from Merck mentioned above, an increase in the a microstructured reactor.
internal dimensions of the micromixer achieved adequately
high flow rates for pilot-plant investigations. A so-called
caterpillar mixer[24] is the central unit of a pilot plate, which is only one step of a three-step pigment synthesis (diazotization,
currently being tested for production applications. azo coupling, and pigmentation). Initially, the two azo
couplings were successfully carried out in a laboratory
microstructured reactor at flow rates up to 80 mL min 1
7.3. Production of Polymers and Pigments (equivalent to one tonne per year). While in the first synthesis
a diazonium salt solution could be used, the success of the
Investigations by Bayer, Pysall, and co-workers (Siemens second synthesis showed that suspensions could also be
Axiva) have proved that significantly reduced fouling of the handled in microstructured reactors.
radical solution in the polymerization of acrylates is achieved The pigments obtained showed a 2040 % higher color
by using interdigital mixers (Scheme 51).[47, 49] Since in-line strength compared to standard pigments obtained through
stirred-reactor synthesis. In addition, their brightness and
transparency are 56 levels better than the standard. The
second synthesis was also carried out on a pilot-plant scale
(flow: 500 mL min 1, equivalent to 10 tonnes per year). The
microstructured reactor simultaneously used three principles
Scheme 51. Radical polymerization of acrylates in interdigital micro- to achieve higher flow rates. Initially the inner dimensions
mixers. were increased by a small amount (scale-up). Then three
Angewandte
microstructured reactors were operated in parallel and within 9. Summary and Outlook
these units were in addition several reactor plates connected
in parallel (internal and external numbering-up). The pigment Approximately 1000 publications regarding the applica-
obtained using this pilot plant has a 50 % higher color strength tions of microstructured devices paint a comprehensive
compared to the conventional technology. Brightness and picture for their possibilities in chemistry. The number of
transparency are equivalent to the good levels of the improvements achieved is impressive. The quality of the
laboratory reactor. The d50 value is 90 nm and the standard publications and thus the expertise shown has improved
deviation, s = 1.5 (conventional: d50 = 600 nm, s = 2.0; significantly. Initially feasibility studies have been superceded
Figure 55). This example is encouraging in the sense that it by detailed mechanistic descriptions and reviews dedicated to
proves that a microstructured reactor can be used for specific themes, such as organic chemistry in microstructured
processes where difficult fluid transportation, such as with reactors.[80] In addition, the variety of the studies undertaken
suspensions, is necessary, even on a pilot-plant scale. has also improved: from pure liquid- and gas-phase chemistry,
through multiphase processes, up to photo- and electro-
chemical experiments on the microscale. Furthermore, both
catalytic and noncatalytic applications have been described.
The result of this development is increasing scientific recog-
nition; regular contributions to this field now appear in all of
the big peer-reviewed journals. In particular, Analytical
Chemistry and Lab on a Chip are rich sources of such
publications.
Until now these practices have been strongly influenced
by process engineers. Increasing, for example, the yield of one
structural isomer over another or the enantioselectivity of a
reaction (despite there being only a few examples to date)
should be motivation enough for chemists to become
Figure 55. Particle-size distribution (left) and TEM image (right 14 000 interested in microstructured reactors. Ultrafast metalorganic
U ) of a pigment on an azo-dye basis. A) Product from a pilot-plant syntheses, asymmetric syntheses, and reactions with highly
microstructured reactor; B) product from a conventional stirred reac- active reactants are but three more examples of areas that
tor: d50 600 nm (source: Clariant, Frankfurt[51]). could be exploited by chemists. It is hoped that this Review
will contribute to new discoveries and the continued develop-
ment of this most fascinating area of research.
8. Market Prognoses
Received: February 5, 2003 [A577]
Prognoses for the number and volume of microstructured
devices are regularly published within the framework of a
NEXUS study. It is, however, striking that in none of these
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Weinheim, 2000; b) V. Hessel, S. Hardt, H. LDwe, Chemical
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Micro Process Engineering, Wiley-VCH, Weinheim, 2004.
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Chemistry in Microstructured Reactors

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Reviews K. Jhnisch, V. Hessel et al.

Chemistry in Microstructured Reactors

The application of microstructured reactors in the chemical From the Contents

1. Introduction Thus, the knowledge of chemistry in a small but active area,

Klaus Jhnisch studied chemistry at TH Holger L>we studied at the University of

reactors can also be used for optimizing process plants already

The following functions of a reactor must typically be

Figure 3. Fluid-introduction system and mixing chamber of a slit-inter-

Complete reactor process plants are offered by Cellular

3.2. Noncatalytic reactions

the macroscopic reaction, where the solution was strongly

sponding dipeptide (Scheme 6). Using continuous flows, a

Scheme 4. The Wittig reaction between 2-nitrobenzyl triphenylphos-

Scheme 6. Peptide synthesis in a microstructured reactor. (Dmab = 4-

reactor through the precipitation of pigments. Thus, the raw

Scheme 10. Formation of a quarternary amine salt of 4,4-bipyridyl.

forming reaction could be operated up to 8 h continuously

the phenylboronic acid solution being continuous and the

Scheme 14. Epoxidation of 1-pentene with hydrogen peroxide on TS-1

found that increasing the surface-area-to-volume ratio

Scheme 16. Isomerization of 1-hexene-3-ol using a RhCl3/TPPTS

Even though gas-phase as well as liquid-phase reactions in

process. Flow distribution of the gas and liquid is achieved

Figure 16. Packed-bed microreactor: a) Single-reactor version; b) ten-

Figure 15. Components of a microbubble column (source: IMM[34]).

designed for short gasliquid contact time. In addition to the

Scheme 17. Fluorination of 2-chloroacetic ester in a three-channel

JNhnisch, Hessel, and co-workers showed that both the

obtained by this method as for a falling-film reactor.

4.2. Halogenation Reactions

To demonstrate the advantage in using microstructured

the isomer ratio could be changed considerably. In macro-

4.4. Catalytic Hydrogenation of Nitrobenzene

Yeong et al. described the heterogeneously catalysed

5. Photochemical and Electrochemical Reactions

Few studies describing the application of microstructured

the selectivity of the desired side-chain chlorinated deriva-

Scheme 25. The reaction of a-terpinene and singlet oxygen to give

process could be run continuously, which avoided the enrich-

Figure 20. Selectivity (S) for the formation of 1-chloromethyl-2,4-diiso-

Scheme 28. Electrochemical synthesis of highly-functionalized deriva-

Scheme 29. Electrochemical dimethoxylation of furan-2-carboxylic acid

Apart from organic liquid-phase reactions, gas-phase

exhaust-gas cleaning in automobiles, as well as in monolith

Figure 26. Multiplate-stacked reactor with a two-part housing: a) Com-

functions.[221] Depending on the end plates used, a parallel or

6.1.3. Single-Plate and Single-Channeled Microstructured Reac-

Single-plate reactors have the advantage that problematic

Membrane-microstructured reactors with permeable

6.1.5. Two-Channeled Microstructured Reactors with Counter-

Two-channeled microstructured reactors can be used for

In a conventional form, catalyst powder or particles are

6.2. Catalyst/Carrier Systems for Gas-Phase Reactions In

Catalysts and their carriers are applied onto microchan-

6.3.3. Oxidation of 1-Butene to Maleic Anhydride

Kah et al. carried out the oxidation of 1-butene to maleic

6.3.4. Oxidation of Alcohols to Aldehydes

erties of microstructured reactors are essential in this case,

Figure 38. Comparison of the reactor performance of a short multitub-

Klaus Jhnisch studied chemistry at TH Holger L>we studied at the University of