Chemical Engineering Science 56 (2001) 1029}1033

Microreactors, a new e$cient tool for optimum reactor design

O. WoK rz *, K. P. JaK ckel , Th. Richter
, A. Wolf

BASF Central Research Laboratory, Ludwigshafen, Germany

Institut fu( r Mikrotechnik Mainz GmbH, Mainz, Germany

Abstract
Microreactors have an extremely large volume-to-surface ratio and the mass transfer path is minimal. That is why they provide
information that would not be available otherwise. This kind of information can be crucial for the choice and the dimensions of
a technical reactor. By two examples it is demonstrated that process development periods can be reduced essentially and that
potentials for process improvement can be found.  2001 Elsevier Science Ltd. All rights reserved.

1. Introduction
The outstanding property of a microreactor is its
extremely large surface-to-volume ratio (Ehrfeld, Hessel,
Mobius & Russow, 1996). If we compare an ordinary
30 m reaction vessel with a microreactor having reaction channels with a diameter of 30
m, this ratio is
di!erent by a factor of 100,000. Even very fast and very
exothermic reactions can, therefore, be performed isothermally and in the case of multiphase reactions the
mass transfer path is minimal. That is why higher selectivities may result and informations are provided that
would not be available by the use of conventional laboratory techniques. Information of this kind can be crucial
for the choice and the dimensions of a technical reactor.
This will be illustrated by two examples.

2. Fluid}6uid reaction
The "rst example (Fig. 1a) is a liquid}liquid reaction. It
is a reaction, catalyzed by concentrated sulphuric acid,
which forms a second phase. The reactant is dissolved in
hexane, and the product is transferred into the acid
phase. Reactant, intermediate and product very quickly
form by-products, and that is why the yield is not quantitative. Initially, the production proceeded as a semibatch process with a yield of 70%. After many years of
production in this way, someone had the idea to perform
the reaction continuously in a combination of a mixer

* Corresponding author.

and a cooler (Fig. 1b). The mixer has a residence time of

0.2, the cooler 4. Within the mixer a temperature rise of
353C is observed. That is half of the adiabatic temperature rise, and that means, that in the mixer we have
a conversion rate of 50%. The rest of the reaction is
performed isothermally in the cooler at 503C. In this
combination the yield has gone up to 80}85%.
In order to understand this, we started kinetic investigations. But, to mix the two viscous phases, to transfer
the heat of reaction, to stop the reaction by dilution with
water and to separate the phases, took us 2 min and
we got a yield of only 25%. That means, conventional
laboratory technique is inadequate. Together with the
`Institut fuK r Mikrotechnik Mainz (IMM)a we, therefore,
developed a microreactor for this reaction. The condition
was that the temperature rise should be con"ned to
about 13C in combination with a residence time of 1.
That meant reaction channels 900
m deep and 60
m
broad, surrounded by cooling channels. Fig. 2 shows the
reaction channels. We have four elements of this kind,
that means we have 8;4"32 reaction channels. Both
reactant streams are split up into 32 partial streams. The
two reactant streams are united in pairs, and then the
reactants simultaneously get mixed and react. There is no
bottle-neck with a pressure drop, where mixing is located
* the whole reactor is practically a bottle-neck. All
volume elements have the same path, the same residence
time, that means we have no back-mixing. That is important, because we have very fast consecutive reactions. The
reactor further contains a delay tank, which can alternatively be used, and that is why the residence time can vary
between 1 s and 10 min. Then, the reaction has to be
stopped by diluting the concentrated sulphuric acid with

0009-2509/01/$ - see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 3 1 8 - 3

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O. Wo( rz et al. / Chemical Engineering Science 56 (2001) 1029}1033

Fig. 1. (a) Reaction, (b) technical reactor.

Fig. 3. Yield dependence on residence-time of the liquid}liquid reaction

at 503C () and 203C (), microreactor.
Fig. 2. Structural element of a liquid}liquid microreactor.

water. Therefore, a second microreactor is integrated.

This second reaction is even more exothermic than the
"rst one, but the selectivity is no longer temperature
sensitive, that means, a temperature rise can now be
tolerated.
Fig. 3 shows the "rst results, the dependence of the
yield on the residence time at a temperature of 503C
* that is the temperature of the reactor combination. It
can be seen, that at a residence time of 4 we have a yield
of 80}85%. That means, the microreactor really represents the reactor combination. When the residence time
gets longer, the yield goes down rapidly. At 15 the yield
has fallen to about 65%. We remember, that with conventional laboratory technique we need 2 min and have
a yield of only 25%. We understand now, why the reactor
combination has a better yield. We could have saved
many years of production with the low yield of 70%, if we

had had our microreactor at the beginning of the process

development. Meanwhile, we have started to vary the
reaction conditions. Fig. 3 also shows the dependence of
the yield on the residence time at the lower temperature
of 203C. At 30 we have a maximum with a yield of
90}95%, an improvement of about 10%. This is a signi"cant and essential improvement, because the di!erence to
a 100% is less than half, compared with 80}85%. We
produce less than half of the by-products.
The common prejudice against microreactors is the
danger of blockage. If somebody could look at our reactant or product mixture, he would not assume that it can
be transported in a microreactor. And we, too, assumed,
that this would be our greatest problem. But our microchannels were conceived and constructed very carefully, we
have neither temperature nor velocity gradients, and that is
why we have, amazingly, no problem with blockage.

O. Wo( rz et al. / Chemical Engineering Science 56 (2001) 1029}1033

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Fig. 4. Oxidative dehydrogenation: scale-up problem.

3. Heterogeneously catalyzed gas-phase reaction

The second example is an oxidative dehydrogenation
of an alcohol to an aldehyde. The industrially most
important dehydrogenation is the synthesis of formaldehyde. It is a heterogeneously catalyzed gas-phase reaction. The catalyst is silver. The production is carried out
in a pan-like reactor (Fig. 6). A 2 cm thick layer of
catalyst particles is placed upon a gas-permeable plate.
At almost quantitative conversion we get a selectivity of
95%. This reactor works on a small scale as well as on
a large scale up to a diameter of 7 m. This process was
developed by BASF about 100 years ago, and I take my
hat o! to these colleagues.
Several years ago, a very similar process (Fig. 4) had to
be developed, and we were sure, that we could do it in the
same way as in the case of formaldehyde. In a pan-like
reactor with a diameter of 5 cm we got a selectivity of
90% at a conversion rate of 50%. Then we built a production reactor with a diameter of 3 m, and the selectivity
fell to 40%. It was a real disaster, because that was one
step of a multi-step production process. Many theories
were formulated to explain this scale-up problem, our
favourite was the following one. It can be roughly calculated, that in case of the laboratory pan-like reactor
about 50% of the reaction heat escapes through the walls
of the reactor. But a reactor of this kind with a diameter
of some meters works entirely adiabatically. In the case of
formaldehyde synthesis that does not matter, because all
reactants and products are stable. But in our case reactants and products obviously are not stable enough, and
that is why the selectivity decreases so rapidly, when the
reactor is scaled-up. This problem should be solved using
a multi-tubular reactor, that works isothermally, because
the heat is transferred. But experiments in a single tube
gave bad selectivities. The residence time is too long, and
tricks like dilution of the catalyst with inert material did
not help us. We presumed, therefore, that we had to

construct a reactor, which is the optimal compromise

between a short residence time and total heat transfer.
And, therefore, we conceived a multi-short-tubular reactor with extremely short * about 10 cm * and extremely
narrow tubes * 12 mm. That has to be compared with
a conventional multi-tubular reactor, where the tubes
have a length of several meters and a diameter of
25}60 mm. The above-mentioned reactor is a very good,
nearly two-dimensional heat exchanger (Q:Coolant). We
now operated one of these tubes on laboratory scale and
got excellent selectivities. But with a pan-like type of
reactor on laboratory scale we got these selectivities, too.
That means, our theory could only be proved by building
a multi-short-tubular production reactor. We did it and
got almost the same selectivity as on lab-scale. But this
development again took several years and did cost us much
money, because all the time we had the low selectivity.
In a microreactor, it should be possible to realise
simultaneously an even shorter residence time and an
even better heat transfer compared with a multi-shorttubular reactor. Together with the `Forschungszentrum
Karlsruhea we, therefore, developed a microreactor for
this reaction (Fig. 6). It is made of silver, the catalytically
active material. So we did not have the problem of how to
"x the catalyst in active and stable form onto the walls of
the reaction channels. This was the main reason to
choose this reaction. The microreactor is a 1 cm cube.
That means, the residence time is one magnitude lower.
And the heat transfer coe$cient, being about
20,000 W m\ K\, is at least one magnitude higher. We
have 200 channels for the reactants and the same number
for the coolant. The rectangular cross-section of the
channels is 0.32;0.40 mm. We chose the cross-section
as small as necessary in order to have excellent heat
transfer, and as large as possible in order to reduce the
danger of blockage.
Fig. 5 shows one of our "rst series of experiments,
selectivity versus conversion. The selectivity of the

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O. Wo( rz et al. / Chemical Engineering Science 56 (2001) 1029}1033

603C and a selectivity of 85%. This reactor corresponds

to a small-scale pan-like reactor. If we go over to a microreactor, the temperature can be reduced to 3903C. We
have no longer any hot-spot, the reactor works isothermally and the selectivity further improves to 96% at an
even higher conversion rate.
4. Microreactors as measuring instruments

Fig. 5. Selectivity dependence on conversion: () technical reactor, ()

microreactor.

multi-short-tubular production reactor () is compared

with the microreactor (). The selectivity increased from
85 to 96%, that means the di!erence to 100% has been
reduced to about one-fourth. The selectivity}conversion
curve has gone up about 15%. Once more we not only
understand now our scale-up problems, but also found
higher selectivities. And that is not yet the ideal reactor.
We, meanwhile, have a new microreactor with better
mixing and with a better temperature control in the
preheating zone.
Fig. 6 sums up the knowledge we now have about this
reaction. If we use a large-scale pan-like reactor we have
a maximum temperature of 5503C with a hot-spot of
1603C. That means, the reactor works adiabatically and
we get a selectivity of 40% at a conversion rate of 50%. If
we use a multi-short-tubular reactor of any scale, we have
a maximum temperature of 4503 C with a hot-spot of

Both examples demonstrate, that development periods

can be reduced signi"cantly using microreactors. And in
both cases a potential for process improvement was
found. We, meanwhile, investigated several other reactions and in all cases we got interesting and relevant
results, and the like is reported by other authors (Lerou
et al., 1996; Wie{meier, Schubert & HoK nicke, 1998). That
means, we primarily use microreactors in order to "nd as
quick as possible the optimal more-or-less conventional
reactor. As chemical reactions are very di!erent
considering number and kind of phases, reaction velocity, temperature, pressure, heat of reaction, corrosivity,
etc. we are about to develop, together with partners,
several types of microreactors in order to be able to
perform all types of reactions.
5. Microreactors in production
If the maximum selectivity of a microreactor cannot be
achieved in any kind of a conventional reactor, should we
try to produce in a microreactor in this case? In principle,
yes. But we had to meet with many problems. One or
more reactant streams had to be distributed equally
among myriads or even millions of reaction channels.
And we would have the problem of blockage, in the
reaction channels as well as in the coolant channels. We

Fig. 6. Comparison of the di!erent types of reactor.

O. Wo( rz et al. / Chemical Engineering Science 56 (2001) 1029}1033

are sceptical, therefore. But we presume, that in most

cases we get, almost, the optimum selectivity in a reaction
channel with a diameter of some millimeters. Normally
reaction channels end with a diameter of 2 cm. Our new
measuring instrument could lead to the `Millireactora.
References
Ehrfeld, W., Hessel, V., MoK bius, H., & Russow, K. (1996). Potential and
realization of microreactors. In W. Ehrfeld (Ed.). Microsystem

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technology for chemical and biological microreactors; DECHEMAMonographs, vol. 132 (pp. 1}28). Weinheim: Verlag Chemie.
Lerou, J. J., Harold, M. P., Ryley, J., Ashmead, J., O. Brien, T. C.,
Johnson, M., Perrotto, J., Blaindell, C. T., Rensi, T. A., & Nyquist,
J. (1996). Microfabricated minichemical systems: Technical feasibility. In W. Ehrfeld (Ed.). Microsystem technology for chemical and
biological microreactors; DECHEMA-Monographs, vol. 132
(pp. 51}70). Weinheim: Verlag Chemie.
Wie{meier, G., Schubert, K., & HoK nicke, D. (1998). Monolithic microreactors possessing regular mesopore systems for the successful
performance of heterogeneously catalysed reactions. In Microreaction technology (pp. 20}26). Berlin: Springer.