Progress in Catalyst for Ethylene Oxide (EO) Production and

Epoxidation Mechanism
Katsumi Nakashiro
Process 2 Laboratory, Petrochemicals Research Center, Mitsubishi Chemical
Corporation, 1, Toho-cho, Yokkaich-city, Mie, Japan

Abstract
Reactivity of adsorbed O
2
molecule and O atom adsorbed on Ag surface for
ethylene oxide (EO) formation and complete oxidation were examined with density
functional (DF) method. Ag clusters of Ag
3
to Ag
10
, of which surfaces were
constructed similar to Ag (111) facet, were modeled for EO catalyst. DF studies have
shown that not only the size of the clusters, but also the configuration of the Ag atoms
decisively effects on HOMO level of the clusters and, thus energy of O
2
adsorption,
indicating that both parameters are important for an accurate simulation of O
2

adsorption.
Investigation of reactivity of adsorbed O
2
molecule and O atom has shown that EO
is formed by both of the O species. In order to understand complete oxidation route,
H-migration and H-abstraction leading to acetaldehyde, radical intermediate,
respectively, were examined. It has been proven that energy of transition state for the
H-migration is lower than that for the H-abstraction in oxidation by both the O species,
suggesting the H-migration route as complete oxidation.
It is interesting to note that reactivity of adsorbed O
2
molecule has been proven to
suppress complete oxidation because the energy of transition state for complete
oxidation is much higher by ca. 28 kcal/mol than that for epoxidation. On the other
hand, adsorbed O atom has given rise to EO formation slightly more than or almost as
much as complete oxidation, since EO formation is little easier by ca. 4 kcal/mol. In
conclusion, EO selectivity of O
2
molecule adsorbed on Ag surface is remarkably high,
while O atom is slightly selective.
Finally, an upper limit of EO selectivity (85.7% on a C
2
H
4
basis, corresponding to
50% on an O
2
basis) under a mechanism, in which adsorbed O
2
molecule and O atom
lead to epoxidation, combustion, respectively, is supposed to be invalid even by either
oxygen species.
Introduction
Ethylene oxide (EO) has been an important chemical substance until now. At
present EO is produced with the amount of ca. 12 million tons per year. A several
percent growth rate of an EO demand has been continuing until now and been predicted
successively in future. More than a half of EO produced is hydrated into ethylene
glycol (EG) for a resource of polyester resin (i.e. fiber, film and bottle), of which a
major product is polyethylene telephtalate (PET). Other than polyester, EO is


80
90
100
consumed for an intermediate of surfactant, antifreeze, etc. In some decades, a
demand of polyester resin, especially fiber in Asia, is expected to grow successively in
future and, thus EO as an intermediate.
A higher selectivity of ethylene for EO has been eager, since a cost of EO
production is strongly dependent on that of ethylene consumed. A selectivity for EO is
summarized in Fig. 1.
40
50
60
70
1920 1940 1960 1980 2000
C
2
H
4

s
e
l
e
c
t
i
v
i
t
y

f
o
r

E
O

/
%
Chlorohydrine
Direct oxidation
High s elect ive cat.
Upper limit ?
Figure 1. Improvement of EO catalyst performance
In direct oxidation of ethylene, an improvement of EO selectivity has been carried
out by process developments, then by catalyst developments as follows:
1) Deposition of highly dispersed Ag particles (Shell, at 1972)
1

2) Addition of Cs for silver modification (Shell, at 1976)
2

3) Surface-area enlargement of support and its modification (Nippon
Shokubai since 1983,
3
later Mitsubishi Chemical,
4
recently Shell)
4) Addition of Re, W, etc. to Ag-Cs component for high selective catalyst
(Shell since 1988,
4
later Mitsubishi Chemical
5
)
It is found that a current EO selectivity has become superior to that in chlorohydrin
method, and that Shell had played an important role in development of EO catalyst. At
present, the highest selectivity reported in patent seems higher than an upper limit,
which used to be predicted by a mechanism, in which adsorbed O
2
molecule and O
atom exclusively lead to epoxidation and complete oxidation, respectively, which is
abbreviated to the adsorbed O
2
mechanism. In general, the adsorbed O
2
mechanism
has prevailed since studies by Kilty et al. in 1970s.
6,7
The adsorbed O
2
mechanism,
however, seems controversial in these days. On the other hand, epoxidation by
adsorbed O atom has now been suggested, which is abbreviated to the adsorbed O
mechanism. The reason is that the upper limit of EO selectivity is unlikely to be true,


as shown in Fig. 1, and that O
2
molecule adsorbed on Ag surface is much lower in
stability than O atom, which is demonstrated with TPD and LEED,
8,9
and STM.
10

From viewpoint of theoretical chemistry, several reports have been published with
the extended Hckel,
11,12
LCAO-X ,
13
Hartree-Fock (HF) + MP3,
14
GVB-CI
15,16
and
density functional (DF) method.
17,18
However, a comparison between energetics in EO
formation and complete oxidation has been made in few reports. Reactivity of
adsorbed O atom and O
2
molecule as an oxidant has rarely been understood by a
difference in energetics of both the oxidations.
Carter and Goddard III evaluated energetics in both epoxidation and complete
oxidation on GVB-CI level,
15,16
but an oxidant of ethylene was only adsorbed O atom.
It was concluded that an energy barrier in H-radical abstraction followed by complete
oxidation was so high that ethylene oxidation should be selective for EO formation.
Nakatsuji et al. investigated in detail reactivity of adsorbed O
2
molecule and O atom
with HF + MP2 and SAC-CI method using their original model, dipped adcluster model
(DAM) consisting of Ag
2
cluster.
19-21
However, it was difficult to describe with the
DAM complete oxidation route, in which dynamic electron transfer is allowed to
represent the positively or negatively charged state by both oxygen species.
The objective of this work is to evaluate reactivity of adsorbed O
2
molecule and O
atom to ethylene into EO formation and complete oxidation with a DF method, in order
to clarify reaction mechanisms of both oxidations. On EO catalysts Ag clusters from
Ag
3
to Ag
10
, of which surfaces are constructed similar to Ag (111) face, were modeled,
since Ag (111) facet is mainly generated in industrial EO catalysts, in which Ag
particles are from sub-microns to microns in diameter. For detailed studies of EO
formation and complete oxidation, a Ag
5
cluster was applied to EO catalyst. For
complete oxidation, two routes, i.e. acetaldehyde formation via H-migration and vinyl
radical intermediate formation via H-abstraction were evaluated.
Details of Calculation Method
A DF method used in this work is the hybrid of HF and DF methods.
22,23
This
method is implemented in Gaussian 98 program. Parameterization is the one
suggested by Pople et al.,
23
i.e., 0.2, 0.8, and 0.72 for the HF, Slater,
24
and Becke
exchange functionals,
25
and 0.19 and 0.81 for the Vosko-Wilk-Nusair
26,27
and
Lee-Yang-Parr
28
correlation functionals. The Los Alamos effective core potentials
(ECP) is used for the 1s to 4p electrons of Ag atoms along with the corresponding
valence basis sets.
29-31
For H, C, and O atoms, Dunning-Huzinaga full double zeta
(D95) basis set is used, (10s5p)/[3s2p] and (4s)/[2s], respectively.
32

The DF method calculations are performed is as follows: At first, the structures of
local minima and transition states are optimized using the basis sets just mentioned.
Then, at the equilibrium structures, the energies are reevaluated with a larger basis set,
in which the diffuse s and p functions of = 0.059 and the polarization d functions of
= 2.704 and 0.535 are added on the O atoms, as used by Nakatsuji et al.
19-21

Throughout this work, the structure of Ag clusters is fixed, and the structure and relative


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orientation of ethylene and oxygen with respect to the cluster is optimized.
The stabilization energy was defined as follows:
E = {E(Ag cluster) + E(C
2
H
4
) + x E(O
2
or O) } - E(combined system),
where x is 1 or 1/2 depending on oxygen molecule or atom, respectively. Positive
value in E means exothermic adsorption or reaction, i.e. thermodynamically easy
step to proceed.
Results and Discussion
1.1. Adsorption of O
2
Molecule on Ag
n
Clusters (n=3-10)

Eight Ag
n
clusters with n = 3 to 10 were constructed, and twelve configurations of
O
2
adsorption on them were studied in energetics. Their optimized structures are
summarized in Fig. 2. Dependence of O
2
adsorption energy on Ag number of the Ag
n

clusters is presented in Fig. 3. It seems that the larger number of Ag in the clusters
gives the smaller O
2
adsorption energy, though the dependence is not always strict.
The reason of this complicated behavior is because energy of O
2
adsorption is
dependent on HOMO energy level of the clusters, rather than the cluster size. That is,
HOMO level results not only from the Ag number in the clusters, but also from the
configuration of Ag atoms and the spin multiplicity of the cluster electronic states,
which depends on electron number (even or odd), since a Ag atom is d
10
s
1
valence in
electron configuration.
0
5
10
15
20
25
30
35
40
45
2 3 4 5 6 7 8 9 10 11
Ag Number in a cluster
E
n
e
r
g
y

o
f

O
2

A
d
s
o
r
p
t
i
o
n

/

k
c
a
l
/
m
o
l
0
5
10
15
20
25
30
35
40
45
-5 -4.5 -4 -3.5 -3
HOMO / eV
E
n
e
r
g
y

o
f

O
2

A
d
s
o
r
p
t
i
o
n

/

k
c
a
l
/
m
o
Figure 4. Dependence of the O
2

adsorption energy on the HOMO level
Figure 3. Dependences of O
2
adsorption
energy on Ag number of the Ag
n
clusters
Dependence of the O
2
adsorption energy on the HOMO level is plotted in Fig. 4.
It shows that the higher HOMO level leads to the higher energy of O
2
adsorption,
indicating electron transfer from the clusters to adsorbed O
2
molecule. For example,
adsorbed O
2
molecule on a Ag
5
cluster is negatively charged totally at -0.580e (ca.
-0.29e in each O atom). In conclusion, not only the size but also the spin multiplicity

and the atomic configuration of model clusters should be taken care of in order to
investigate O
2
adsorption systems.
A model cluster is requested to have enough area to represent both epoxidation and
complete oxidation, where O
2
molecule or O atom and C
2
H
4
are coadsorbed and react
mutually. Therefore, a Ag
5
cluster with lozenge configuration was selected for further
investigation. A HOMO level and O
2
adsorption energy with the Ag
5
cluster have
been calculated to be -3.62 eV and 15.7 kcal/mol, while -4.74 eV and 16-25 kcal/mol
determined with UPS,
33
adsorption measurements,
6
respectively. Thus, our values
obtained with DF calculation are in good agreement with those measured
experimentally. Discussion on reaction mechanisms is focused on comparison
between two competing reactions.
1.2. Oxidation by Adsorbed O
2
Molecule on Ag (111) Surface
It is reported that adsorption of O
2
and C
2
H
4
on Ag surface takes place as follows
34
:
1) O
2
is adsorbed on Ag surface at room temperature,
2) C
2
H
4
is not adsorbed on clean Ag surface, but does on Ag surface after
O
2
adsorption.
On the other hand, adsorbed O
2
molecule on Ag surface has been known to be so
reactive to dissociate for two of adsorbed O atoms even at room temperature, which is
much lower than a temperature of 200-300 in EO formation, as published with TPD
and LEED,
8,9
and STM.
10

According to above observations reported, oxidation by adsorbed O
2
molecule is
assumed to occur after O
2
adsorption and, then O
2
-C
2
H
4
coadsorption on Ag surface, in
the Rideal-Elay mechanism. Structures in O
2
, O
2
/C
2
H
4
and EO adsorption states were
optimized, and then transition states between both the states were pursued. Thus, two
transition states (TS1, TS2) were determined, showing that the above reaction scheme is
reasonable. The energy diagram obtained is presented in Fig. 5. It is found that
O
2
-C
2
H
4
coadsorption is less stable than O
2
adsorption, and that the first transition state
(TS1) between them exists, suggesting that O
2
-C
2
H
4
coadsorption is a process with
activation energy. This phenomenon is consistent with experimental results.
34
It is
noticeable that the next transition state (TS2) is the least stable in the EO formation
route, while the first transition state (TS1) has similar stability to reactant state.


0
15.7
-1.6
4.3
-5.2
33.5
29.2
-28.9
58.9
-30
-20
-10
0
10
20
30
40
50
60
Ag + O2 Ag-O2 TS1 Ag-O2-
C2H4
TS2 Product
F
o
r
m
a
t
i
o
n

e
n
e
r
g
y
/

k
c
a
l
/
m
o
l
EO
acetaldehyde(CO2/H2O)
TS2 for EO
1.481
1.515
1.855
TS2 for acetaldehyde
1.379
1.489
1.332
1.377
1.531
Figure 5. Energy diagram in epoxidation and complete oxidation by adsorbed O
2
On the other hand, for studies of complete oxidation route, H-migration for
acetaldehyde and H-abstraction for radical intermediate, the corresponding transition
state (TS2) was searched, since we assumethat the TS1 is common for all the routes.
It is found that H-migration is slightly more plausible than the H-abstraction by
comparison of both TS energies. The structure and energy for H-migration into
acetaldehyde (TS2) as complete oxidation route are superimposed in Fig. 5. The TS2
is surprisingly much more unstable than TS2, indicating that the first O atom of
adsorbed O
2
should bring about EO formation in high selectivity, in consistent with
results of Nakatsuji et al.
19-21
Large difference (23.7 kcal/mol) in activation energy for
EO formation and complete oxidation means that the first atom of O
2
may give almost
100% in EO selectivity.


After TS2 for EO and H-migration for acetaldehyde, large stabilization energies
account for change in the heat of formation (from C
2
H
4
to EO or acetaldehyde) and the
adsorption energy by O atom (13.0 kcal/mol), which is remained after consumption of
the first O atom of adsorbed O
2
molecule.
1.3. Oxidation by Adsorbed O Atom on Ag (111) Surface
Oxidation by adsorbed O atom seems to occur with the Redeal-Eley mechanism
similar to that by adsorbed O
2
molecule, discussed in a previous section. Generation
of adsorbed O atom on Ag surface is supposed to results from either dissociative
adsorption of O
2
molecule or consumption of the first O atom from adsorbed O
2

molecule. Optimization of structures in O, O-C
2
H
4
and EO adsorption states was
performed and a transition state before EO formation was pursued. The energetics in


0
13
19.8
2.2
18.1
16.2
-1.5
45.9
-30
-20
-10
0
10
20
30
40
50
60
Ag + 1/2 O2 Ag-O Ag-O-C2H4 TS Product
F
o
r
m
a
t
i
o
n

e
n
e
r
g
y

/

k
c
a
l
/
m
o
l
EO
acetaldehyde(CO2/H2O)
1.488
1.294
1.331
1.470
TS for acetaldehyde
Figure 6. Energy diagram in epoxidation and complete oxidation by adsorbed O
atom
epoxidation by adsorbed O atom are summarized in Fig. 6.
On the other hand, complete oxidation routes by adsorbed O atom H-migration for
acetaldehyde and H-abstraction for radical intermediate were also estimated, similar to
those by adsorbed O
2
molecule. Corresponding transition states were obtained. It is
found that adsorbed O atom gives H-migration proceeds slightly more easily than
H-abstraction, which is the same tendency as adsorbed O
2
molecule. Energetics for
complete oxidation is presented also in Fig. 6, accompanying with those for epoxidation.
Formation energy of adsorbed O atom from Ag cluster and 1/2 O
2
molecule is
calculated to be 13.0 kcal/mol. As shown in Fig. 6, both transition states for
epoxidaiton (TS) and complete oxidation (TS) have the highest energies on the path.
It is important that difference between energies of both transition states is only 3.7
kcal/mol and much smaller than that with adsorbed O
2
molecule, suggesting that EO
selectivity of adsorbed O atom is much lower than that of O
2
molecule, though adsorbed
O atom is still selective to some extent. This result is consistent with reports by
Nakatsuji et al.
19-21
And the reason why our results are different from those of Carter
and Goddard III seems that their complete oxidation route is not H-migration but
H-radical abstraction.
Here, consider relationship between difference in activation energies for
epoxidation and combustion, and selectivity for EO. For example, if the difference
would be nothing in oxidation by adsorbed O atom, EO selectivity should be 50%,
corresponding to 85.7% on a C
2
H
4
basis due to a following equation:



H
2
C CH
2
O
H
2
C CH
2 O
2
+ CO
2
+ 7 6 2 H
2
O + 2 6
Therefore, selectivity of adsorbed O atom is supposed to be slightly higher than
85.7%, since adsorbed O atom is slightly selective by ca. 4 kcal/mol. Selectivity of
adsorbed O
2
molecule is much higher than 85.7%, since the first O atom of adsorbed O
2

molecule seems nearly 100%, while the second O atom has the same selectivity as
adsorbed O atom. It is concluded that selectivity of O should be higher than 85.7% on
a C
2
H
4
basis, even under the adsorbed O or O
2
mechanism. This seems to disagree
against actual selectivity of EO catalyst, as observed in Fig. 1. It is supposed that
further investigation is necessary in order to clarify this point.
Conclusion
It is concluded that epoxidation into EO is reasonably brought about by both O
2

molecule and O atom adsorbed on Ag surface, and that complete oxidation which is
supposed not H-abstraction but H-migration into acetaldehyde, radical intermediate,
respectively, is ascribed to adsorbed O atom only. In case of adsorbed O
2
mechanism
epoxidation of C
2
H
4
may precede dissociative adsorption of O
2
molecule.
It is, however, unclear which oxygen species are responsible for EO formation at
the present study. The reason is partly because EO selectivity observed in actual EO
catalysts is lower than that expected by this theoretical study, i.e. higher than 85.7%. It
seems that lower selectivity of actual EO catalysts imply epoxidation by adsorbed O
atom, since the difference between activation energy of epoxidation and combustion is
small, but that activation energy observed in O
2
-C
2
H
4
coadsorption suggests the
adsorbed O
2
mechanism. According to our results, an upper limit of EO selectivity
(85.7% on a C
2
H
4
basis), which is expected by the adsorbed O
2
mechanism, maybe
negligible. We have found that further studies are necessary to clarify which oxygen
species bring about epoxidation. Many kinds of elements like alkaline as a dopant and
halogen compounds as a reaction moderator, which has been utilized in industrial
EO/EG process, may control these reaction routes.
Finally, it is pointed out that consideration of modeled clusters and understanding of
all reaction routes proposed, e.g. epoxidation, combustion (via H-migration,
H-abstraction), are important for investigation of reaction mechanisms. For this
purpose, DF method is found to be useful.
Acknowledgement
This work has been collaborated with Hisayoshi Kobayashi, Professor of Kurashiki
University of Science and the Arts, Japan. I thank Professor Kobayashi so much for
accomplishing difficult DF calculation, discussing reaction mechanisms.


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