Studies in Surface Science and Catalysis 130

A. Corma, F.V. Melo, S.Mendioroz and J.L.G. Fierro (Editors)

9 2000 Elsevier Science B.V. All fights reserved. 2741

Synthesis of ethylene oxide in a catalytic microreactor system

H. Kestenbaum ~, A. Lange de Oliveira ~, W. Schmidt ~, F. Schtith 1,
W. Ehrfeld 2, K. Gebauer 2, H. Ltiwe 2, Th. Richter 2

t Max-Planck-Institut fur Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mtilheim/Ruhr,

Germany
2 Institut fur Mikrotechnik Mainz GmbH, Carl-Zeiss-Str. 18-20, D-55129 Mainz, Germany

Abstract. The synthesis of ethylene oxide by direct oxidation with air or oxygen over a
supported silver catalyst is a well established process for more than sixty years. Therefore the
reaction can be used to investigate the potential of a microstructured reactor in comparison to
an industrial process. In this work we used a microreactor, which was designed and
constructed by IMM. Silver foils (126 channels: length 9 mm, height 50 lam, width 500 lxm)
served as the catalytically active component. In this paper we demonstrated the possibility to
run the microreactor within the explosion limits and were able to reach space-time-yields
above the value which is usually observed for industrial reactors. Selectivities were low, but
one has to take into account that unpromoted silver was used in our study.

1 Introduction
Since T. E. Lefort discovered the oxidation of ethylene to ethylene oxide by silver catalysts,
the industrial production of ethylene oxide by direct oxidation with air or oxygen over A1203
supported silver catalysts has become a widely used process [ 1]. In 1995, the world capacity
for ethylene oxide was near 11.2 x 106 tons per year. For this reason much research has been
focused on this reaction from a fundamental point of view, as well as with respect to industrial
application. This was the reason to choose the synthesis of ethylene oxide as an ideal
benchmark to test the performance of catalytic microstructured reactors and to compare it with
existing industrial processes.
Ethylene may react in a selective oxidation process with oxygen to form either ethylene oxide
or carbon dioxide and water by total oxidation. Furthermore, ethylene oxide may be oxidized
further to carbon dioxide and water as illustrated in Fig. 1. The selective partial oxidation of
ethylene is a moderately exothermal reaction (-105 kJ/mol), whereas the total oxidation of
ethylene and ethylene oxide is highly exothermal (-1327 kJ/mol and -1223 kJ/mol). The total
heat of reaction in a conventional industrial reactor reaches -350 to -550 kJ/mol, causing "hot
spots" and heat removal problems [2].
2742

C~N~ AH=-105
1/20kJ/mol
2 ~ C2H40
AH=-1327ld/rno~, 5/2j0~=-1223kJ/mol

2 CO 2 + 2 H20

Fig. 1: Reaction network for ethylene partial oxidation and competing combustion reactions.
The microreactor is a useful tool to investigate the "hot spot" problem. The enhanced surface-
to-volume ration of microreactors enables an effective heat management. Dr. O.-U. Langer
and T. Stief at the DECHEMA calculated temperature profiles, which show a maximum
temperature deviation of a Kelvin at most, even at high ethylene conversions. Furthermore it
is possible to use gas compositions within the explosive limits of the reactants since
microstructured reactors show an inherent explosion safety. Hazardous gas mixtures can be
handled safely since the quench distance for ethylene oxygen mixtures is larger than the
characteristic dimension of the microstructured channels. Thus, microreactors allow reaction
conditions not possible in conventional reactors, like ethylene in pure oxygen.

2 Reactor and Preparation

In this study, a microreactor, designed and constructed by IMM especially designed for the
heterogeneously catalyzed reaction of ethylene to ethylene oxide was used. The microreactor
is constructed for use under reaction condition analogous to those applied on an industrial
scale, i.e. temperatures up to 575 K and pressures up to 25 bar. It contains a mixing unit, in
which reactants are injected from opposite sides. The specific channel geometry directs the
gases in a ninety degree angle in order to achieve exact arrangement of the single gas streams
above each other. The thickness of each layer is about 200 lam while the width of the channels
increases from 148 lam up to 469 jam in order to establish a constant pressure drop [3]. As
shown in Fig. 2, a diffusion zone of 1 mm length is located between the mixing unit and the
catalyst zone for establishing a homogeneous gas mixture before entering the catalytic area.
Silver foils in parallel flow geometry where used as catalytically active compound. Realizing
the catalyst as microstructured components from the catalytically active metal silver itself
leads to a uniform heat distribution and therefore enhanced process performance. The catalyst
structure was realized by excimer laser ablation of a resist material (in this case PMMA)
followed by an electroforming process employing silver. The reactor section contains a stack
of 14 foils with 9 channels each, with 9 mm length, 50 prn height and 500 prn width [4].
 2743

Fig. 2: Mixing unit3 (left side), diffusion zone (in between) and silver catalyst4 (fight side).
Since the catalyst is made of polycrystalline silver, an attempt was made to increase the
catalytically active surface by using a modified OAOR process [5]. During this procedure the
catalyst was oxidized at 530 K in oxygen atmosphere at a volume flow of 0.5 1/h oxygen and
followed by reduction at 630 K in hydrogen atmosphere at the same flow rate. A precise
measurement of the surface area was not possible, an approximate value of the geometrical
surface area has been used for all calculations. Chemisorption data suggest an increase in
surface area by a factor of two to three, but the precision of the data is low due to the low total
surface area. Additionally, this preparation step was helpful in removing organic impurities
from the catalyst surface resulting from the microstructuring process.

3 Reactor Operation

Heating of the reactor was applied externally, by placing the microreactor into a forced
convection flow oven, to generate the necessary temperatures ranging from 480-630 K. The
reactant gas tubes were guided through the oven in order to preheat the gases before entering
the microreactor. Gas concentrations were regulated using mass flow controllers, adjusting the
gas concentration of ethylene from 0.75-15 vol-% and oxygen from 5-85 vol-% respectively.
Nitrogen has been used as carrier gas in part of the experiments. The total gas flow varied
from 1-5 1/h at pressures between 1-20 bar.
In order to avoid condensation of synthesized ethylene oxide, the exhaust gas tube between
microreactor and gas chromatograph was heated. Product gas mixture analysis was carried out
via on-line GC with a FID/TCD combination. Thus, concentrations of ethylene oxide and
carbon dioxide could be obtained simultaneously, which was sufficient to close the mass
balance and to determine selectivity. Other than in the industrial process, no chlorine
compounds have been added to the feed so far. Also no supported silver catalyst has been
used as yet.
2744

4 Results and Discussion

The new microstructured silver foils showed no catalytic activity. Even after treating the silver
foils with the OAOR process, a slight increase in catalytic activity was observed. During the
first 100 h of operation at reaction conditions the previously known catalyst formation of
silver was occurred. Further on in the reaction process, the catalyst produced a sufficient
amount of ethylene oxide for analysis. The catalyst activity observed is in agreement with the
range of values given in literature. At a temperature of 555 K, a pressure of 5 bar and a feed
composition of 6 vol-% ethylene and 33 vol-% oxygen, a reaction rate of 2.8 x 10 -4
mol-nm-2 has been observed, which is fairly close to the value of 1.7 x 10-4 mol-~m-2 reported
by Tsybulya et al. for silver powder [6].
It was found that the selectivity in the microreactor depends on the partial pressure of oxygen.
Thus, the yield of ethylene oxide increases with increasing oxygen pressure even at a slightly
increase of conversion. As shown in Fig. 3, the conversion of ethylene increase with the
concentration of oxygen added. However, an increase in selectivity was noted unexpectedly
up to an oxygen concentration of approx. 33 %. This experiment was conducted at a constant
ethylene concentration of 3 %, a total pressure of 5 bar, a gas flow of 41/h at 550 K. The
positive influence of oxygen concentration has been reported earlier by Neubauer et al. [7].
However, due to safety reasons one can normally not operate at higher oxygen concentration
(note that Neubauers exp. were carried out under high vacuum conditions). The microreactor
for the first time provides a technology to handle such conditions safely.

60,0% *
I yield [%]
/
m conversion [%]
50,0%
.
121selectivity [%]
. . . . . . . . . . . . . .

40,0%
el r
a.,

/
30,0%

20,0%-
N
/
10,0%-

0,0%- .i/ 5% 15% 20% 33% 41,25%

Fig. 3: Effect of the oxygen concentration on conversion, yield and selectivity.

In comparison, a selectivity of about 50 % is lower than the values established in industrial
processes. However, industrial conditions include the presence of chlorine compounds such as
1,2-dichlorethane. If in the microstructured reactor the temperature is decreased to moderate
values, e.g. 510 K, a selectivity of about 65 % can be reached at the concentration given above
 2745

and a conversion of 6.8 x 10-s mol~m 2. These values exceed those being observed for
polycrystalline silver catalysts [8]. Variation of the reaction temperature between 510 K and
600 K, enabled calculation of the activation energy under the process conditions already
mentioned. The observed value of 48 kJ/mol corresponds to the data (45-62 kJ/mol) given in
the literature8.
The performance of the microreaction system was investigated under demanding conditions.
By using a gas composition of 15 % ethylene and 85 % oxygen, a flow rate of 1 l/h, 5 bar and
565 K, we observed a reaction rate of 2.2 x 10-4 mol-~m-2 at a conversion of 20.4 % and a
selectivity of 53,8 %. On the basis of this results it was possible to calculate space-time-yields
for the microreactor from 0.18 up to 0.67 th-~m-3. In comparison to the reported space-time-
yields of 0.13 to 0.26 th-lm ~ for the industrial process this seems to be superior. In addition to
these experiments we found out, that an increase in pressure upon 5 bar does not lead to an
increase in conversion as expected. Instead constant conversion and yield were observed.
The catalyst has been in operation for over 1000 h under reaction conditions without any
deactivation. Fig. 4 shows two SEM-images of the surface of a reaction channel. It can be
clearly seen, that the catalyst surface in the channels has been roughened during the reaction
process. Moreover, the surface is pitted substantially. Furthermore, an agglomeration of silver
particles on the surface can be observed. This result of the interaction between silver and
oxygen has already been described by Ertl et al. [9].

Fig. 4: Silver surface before (left) and after 1000 h time-on-stream (fight).
2746

5 Conclusions

In general, the results which are obtained by using a microreactor for ethylene oxide synthesis
are similar to the well developed industrial process. For the microreactor selectivities of about
50 % were found. The industrial process is operating with a higher selectivity up to 80 % if
pure oxygen is used as the oxidant at similar conversion levels. However, industrial results
were obtained in the presence of chloride and usually other promoters on the catalyst, unlike
to the pure silver investigated in this work. In contrast to the industrial process, it is possible
to carry out the oxidation of ethylene in pure oxygen which would not be used in a
conventional reactor design. This enables us to reach space-time-yields higher than the ones of
industrial processes. The performance in presence of chlorine compounds will be investigated
in the near future to further increase the selectivity. Moreover, experiments in the presence of
hydrogen for mechanistic investigations are still under way and will be presented. Whether
such reactors will ever be used in industrial practice certainly will depend on economic
factors, in particular the opportunity to increase the selectivity above 80%. At present 80% of
the cost of the process are depending on the price of ethylene. This means that increase of
selectivity can decide, if a new process will be used. A goal set in order to reach selectivity
above 80% at space-time-yields similar or even better then the industrial process.

6 Acknowledgments

The authors would like to thank Thomas Scholl at IMM for valuable help in microreactor
development and D. Wolf (ACA) for valuable discussions. Furthermore the authors would
like to thank the BMBF (German Ministry of Education, Science, Research and Technology)
for funding this work and all the partners within this project for their cooperation and
discussions.

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Microreactors: Components and Integrated Systems", in: Process Miniaturization: 2 no
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