Ethylene Oxidation On Silver Catalysts e

Chem. Eng. Commun. Vol. 44 pp.
53-74
0098-644518614406-0053$25.00/0
0 1986, Gordon and Breach Science Publishers S.A.
Printed in the United States of America.
ETHYLENE OXIDATION ON SILVER

CATALYSTS: EFFECT OF ETHYLENE OXIDE
AND OF EXTERNAL TRANSFER
LIMITATIONS
MICHAEL STOUKIDES
Department of Chemical Engineering,
Tufts University, Medford, MA 02155
and
Downloaded By: [HEAL-Link Consortium] At: 14:52 1 October 2009
STAVROS PAVLOU
Department of Chemical Engineering,
University of Patras,
Patras 261 10, Greece
(Received June 10, 1985; in final form December 9, 1985)
Ethylene oxidation to ethylene oxide and to carbon dioxide over silver catalysts was studied in a
CSTR. The effects of two factors on the catalyst performance were examined. The first was the
presence of excess ethylene oxide in the feed. A kinetic model was introduced which assumed that
ethylene and ethylene oxide compete for the same sites on the catalyst surface. This model provided
reasonable quantitative agreement with kinetic and potentiometric measurements. The second factor
that was studied was the presence of external heat and mass transfer limitations. It was found that
such limitations cause a significant decrease of the selectivity to ethylene oxide. This decrease is a
result of the temperature difference between the catalyst surface and the bulk of the gas phase and of
the fact that the activation energy of ethylene combustion is greater than that of ethylene epoxidation.
The contribution of other factors such as inhibition by CO, o r possible incomplete mixing in the
reactor is shown to be insignificant.
KEYWORDS Catalytic ethylene epoxidation Ethylene oxide selectivity
Solid electrolyte potentiometry Oxygen activity measurement
Selectivity of polycrystalline silver External transfer limitations
INTRODUCTION
Ethylene oxide is produced commercially from ethylene oxidation over supported

silver catalysts. There is a general consensus (Sachtler et al., 1981; Voge and
Adams, 1967), that the kinetics can be described by means of a triangular
scheme:
5( + hyC z hyO( + 3 o J
GH, 12(+301)- 2 [COZ+ H@l
The activation energies and reaction orders for the three reactions have been
investigated by numerous groups and their results have been summarized by
54 M. STOUKIDES AND S. PAVLOU
Voge and Adams (1967), Kilty and Sachtler (1974) and recently by Sachtler,
Backx and Van Santen (1981) as well as by Barteau and Madix (1982). A number
of parameters that affect the selectivity to ethylene oxide (moles of ethylene oxide
produced per mole of ethylene consumed) has been reported so far including
halogen compounds (I(ilty and Sachtler, 1974; Kilty et al., 1972), crystal size and
orientation (Kummer, 1956; Harriot, 1971; Johnson and Verykios, 1983) as well
as y-preirradiation (Carberry, 1972). The inhibiting effect of reaction products
and other species on the reaction yield and selectivity has also been studied
extensively (Voge and Adams, 1967; Sachtler el al., 1981; Cant and Hall, 1978;
Hayes, 1960). Nevertheless, despite the large number of investigators and some
very interesting recent experimental findings (Wachs and Kelemen, 1981; Ghazali
et al., 1983; Campbell and Paffett, 1984; Haul et al., 1984; Grant and Lambert,
1985(i), 1985(ii)) no generally accepted reaction mechanism has been established.
The very wide scatter of the published parameters make it impossible to draw
unambiguous conclusions on the mechanism from such data.
The present communication is focusing attention on a) the effect of ethylene

oxide on the reaction rates and b) the effect of external diffusional effects on the
catalyst activity and selectivity. Conflicting results exist so far on the role of
ethylene oxide on the reaction selectivity. A linear decrease of the selectivity with
increasing ethylene oxideloxygen ratio has been reported by Temkin and his
co-workers (1962; 1979). Force and Bell (1975) however observed an increase in
selectivity with increasing ethylene oxide concentration although this increase was
not permanent.
In the present work kinetics are combined with in situ electrochemical
measurement of the activity of oxygen adsorbed on the catalyst surface using the
technique of Solid Electrolyte Potentiometry (SEP). This technique has already
been used in conjunction with kinetic measurements in order to study the
mechanism of various catalytic oxidations (Vayenas et al., 1981; Stoukides and
Vayenas, 1980; Stoukides and Vayenas, 1981). Reactor cells similar to the one
used in this study have been used so far to enhance the rate of NO decomposition
and C O hydrogenation (Pancharatnam et al., 1975; Giir and Huggins, 1981), as
well as in high temperature fuel cells (Etsell and Flengas, 1971; Vayenas and
Farr, 1980).
EXPERIMENTAL METHODS
A schematic diagram of the experimental apparatus is shown in Figure 1. It

consists of the flow system, the reactor cell and the analytical system. The reactor
cell was a 8% yttria stabilized zirconia tube of 2cm2 cross sectional area and
30cm3 volume. The Ag catalyst film was deposited on the flat bottom of the
zirconia tube. A similar Ag film was deposited on the outside bottom wall of the
reactor as shown in Figure 2. This film was exposed to air and sewed as the
reference electrode. T o deposit the film, a few drops of a silver suspension in
butyl acetate (Stoukides and Vayenas, 1980) was used, followed by drying and
calcining at 400C. The Auger spectrum of the catalyst showed (Stoukides and
S c h m t i c nlagran of A"paratur
IR: Infrared Cn2 h a l y z e r
GC: Gar Chmratnsraph
TC: lcmpcraturr C o n t r o l l e r
DV: Dlff~rentlal V o l t m e t e r
FIGURE 1 Schematic diagram of apparatus

Ag w i r e
/
FIGURE 2 Schematic diagram of reactor cell

Vayenas, 1980) that the silver surface was fairly clean. Trace impurities including
some CI (less than 1 % of a monolayer) might have been responsible for the
relatively high selectivities obtained. The catalyst surface area was estimated
using oxygen chemisorption followed by reaction with ethylene as it has been
described in detail elsewhere (Stoukides and Vayenas, 1980). It was thus found
that the catalyst could adsorb approximately 1.8 x moles of oxygen at 300C.
A silver wire, enclosed in a pyrex tube was used to make contact with the
internal Ag film catalyst-electrode (Figure 2). The reactor temperature was
controlled within 2C by means of a Leeds and Northrup temperature controller.
A J. Fluke voltmeter was used to monitor the open-circuit EMF of the cell.
Matheson certified gases (ethylene oxide, ethylene, oxygen) diluted in nitrogen
were used as reactants. The feed and product composition was determined by
means of a Perkin-Elmer Gas Chromatograph with a TC detector. A molecular
sieve 5A column was used to separate N2 and O2 and a Porapak Q was used to
separate air, C 0 2 , ethylene and ethylene oxide. The CO, concentration in the
products was also monitored by a Beckman 864 Infrared Analyzer.
Measurement of Surface Oxygen Activity

The technique of Solid Electrolyte Potentiometry (SEP) provides a continuous in
situ measurement of the thermodynamic activity of oxygen adsorbed on the
catalyst surface. It has been established (Wagner, 1970; Stoukides and Vayenas,
1980), that the open circuit EMF of the cell reflects the difference in chemical
potential of oxygen adsorbed on the two silver electrodes:
1
E = -[po,(Ag catalyst) - po,(Ag reference)] (1)
4F
The chemical potential of oxygen adsorbed on the reference electrode which is in
-
contact with air (Po, 0.21 bar) is given by
po,(Ag reference) = &(g) + RT ln(0.21) (2)
where &(g) is the standard chemical potential of oxygen at the temperature of
interest. The activity a, of adsorbed oxygen can be defined by:
Thus a; expresses the partial pressure of gaseous oxygen that would be in

thermodynamic equilibrium with oxygen adsorbed on the catalyst surface, if such
an equilibrium were established. Therefore, combining Eqs. (I), (2), and (3) one
obtains:
I::[
a, = ( 0 . 2 1 ) ' ~exp -
The above equation is always valid, irrespective of whether thermodynamic

equilibrium is established between gaseous and adsorbed oxygen or not. In the
special case where thermodynamic equilibrium indeed exists between adsorbed
and gaseous oxygen, then a: = Po,.
ETHYLENE OXIDATION ON SILVER 57
EXPERIMENTAL RESULTS
The catalytic oxidation of ethylene was studied in presence of excess ethylene

oxide in the feed stream at temperatures 280-400C and atmospheric total
pressure. Under the flowrates employed in this study, it has been shown
(Stoukides and Vayenas, 1980) that the reactor is well mixed (CSTR). Absence of
external or internal diffusional effects has been established in previous studies
using the same reactor under similar temperature and Bow conditions (Stoukides
and Vayenas, 1981).
The rate of net production of ethylene oxide (in moles of ethylene oxidels) was
calculated from the raw kinetic data using the appropriate mass balance
where x ~ ~ 0 . and
i " XETO,,,, are the mole fractions of ethylene oxide in the feed
and outlet respectively and G is the total molar flowrate. Due to the dilution of
the reactants in N, the change in G from the stoichiometry of the reactions was
less than 1% and hence G was considered constant. The rate of CO, formation
r o , was calculated from the steady state material balance:
The rates of ethylene oxide formation, ethylene deep oxidation and ethylene
oxide oxidation have already been studied-in absence of excess ethylene oxide
in the feed-using the same apparatus, reactor and catalyst preparation (Stouk-
ides and Vayenas, 1980; 1981). It was found that for excess air in the reactor the
three reaction rates could be described rather accurately by the equations:
The validity of Eqs. (7) through (9) was verified by repeating the experiments at
temperatures 280-400C. The values of the rate constants K , , K,, K 3 , K,, KETo
that best fit the experimental data were:
M. STOUKIDES AND S. PAVLOU
10600
KETo = 3.3 X lo-' exp(l) bar-'
i.e. very close to the values reported previously.

The effect of excess ethylene oxide in the feed stream on the rate of C 0 2
formation rc0, as well as on the net rate of ethylene oxide formation rET, is
shown in Table I. Each one of the data resulted from the average of two
measurements. The partial pressure of ethylene oxide in the reactor varied from
TABLE I
Effect of ethylene oxide on reaction rates
FIGURE 3 Rate o f CO, production vs. P,,,,. Po, = 0 . l bar, P,., =O.OlOS bar
FIGURE 4 Rate of ethylene oxide formation vs. P,,,. Po, 1 0 . 1 bar, PET=0.0105 bar.
60 M. STOUKlDES AND S. PAVLOU
0.0006 to 0.024 bars while the partial pressure of ethylene and oxygen were kept
constant (within 5%-10%). Figure 3 shows the effect of ethylene oxide on rco,
Only a slight increase is observed with increasing PETOat all temperatures
examined. The corresponding effect of ethylene oxide on rETo is shown in Figure
4. A considerable decrease on rETo with increasing PETOis observed, the effect
being more important at high temperatures. Finally, the surface oxygen activity an
was found to depend on PETOin the way shown in Figure 5. At all temperatures
examined, a, seems to depend very weakly (slightly decreasing) on PET,.
In a separate set of experiments the effect of external transport phenomena on
the selectivity to ethylene oxide was studied. First, it was necessary to determine
the range of flowrates within which external transport phenomena became
dominant. To this end, the rate of ethylene consumption was measured while
varying the total volumetric flowrate between 160 and 720cm3/min at 440C.
Ethylene oxide was not introduced in the feed. The data are shown in Figure 6,
FIGURE 5 Dependence of surface oxygen activity on P,,,. P,,=O.l bar, PET=0.0105bar.

FIGURE 6 Effect of volumetric flowrate on the rate o f ethylene consumption. T=440"C,

Po, = 0.1 bar.
where the ratio APETIPETis plotted vs. the reciprocal flowrate l / Q . Here PET is
the partial pressure of ethylene in the reactor and APET = PET,;- PET,where PET,i
is the partial pressure of ethylene entering the reactor. At 440C both rates rl and
r2 (Eqs. (7) and (8)) are practically first order in ethylene (Stoukides and
Vayenas, 1981). Hence, one may write
r, = KIKETPET
rz = KZKETPET
or
and consequently:
Therefore, in absence of diffusional effects, APETIPETplotted vs. Q-' should

give a straight line. It can be seen in Figure 6 that this is true for flowrates greater
than 250 cm3/min. At 440C and for Q values lower than 250 cm3/min, transport
phenomena have a significant effect on the measured reaction rates.
The effect of external transport phenomena on the selectivity (S) to ethylene
oxide was studied by measuring reaction rates at various flowrates. Results are
summarized in Table I1 for 400 and 440C. The rates r, and r2 were calculated
TABLE 11
Etfect of flowrate on reaction rates and selectivity
from the equations:
Q
r , = r , - r --PETO
'-RT
and
The approximations in the above equations were based on kinetic data

reported previously (Stoukides and Vayenas, 1980, 1981), which indicate that the
rate r3 is negligible compared to the rates r, and r2.
The selectivity S was calculated as
The effect of Q on r, and r2 as well as on S is shown in Figures 7 and 8. With

decreasing flowrate, both rates r, and r2 decrease (Figure 7 ) , but the decrease in r,
is larger than the decrease in r2 and thus the selectivity decreases (Figure 8).
FIGURE 7 Effect of volumetric flowrate on rates of ethylene oxide and CO, formation.
P,, = 0,005-0.0067 bar, Po, = 0.085 bar.
FIGURE 8 Effect of volumetric flowrate on reaction selectivity. Po, = 0.085 bar, P, = 0.005-
0.007 bar.
DISCUSSION
In a ~ r e v i o u scommunication (Stoukides and Vayenas, 1981) a kinetic model for

ethylene oxidation on polycrystalline silver films was proposed. The experimental
-
results resented here were obtained under similar temDerature and gas com~osi-
tion and with the same reactor. Moreover, the catalyst preparation was identical
to that followed previously (Stoukides and Vayenas, 1980, 1981).
According to the previously presented kinetic model two types of adsorbed
oxygen are assumed, i.e. molecular, being responsible for the ethylene epoxida-
tion and atomic, being responsible for C 0 2 and H 2 0 formation. Ethylene and
ethylene oxide were assumed to compete for the same sites following Langmuir
adsorption kinetics. Ethylene oxide was considered to adsorb primarily as a dimer
(Stoukides and Vayenas, 1980).
However, since under the reaction conditions the partial pressure of ethylene
oxide was very small (PETo<&PET) the coverage of ethylene adsorbed on the
catalyst was calculated from the following equation:
This is valid only for OETo = 0. Excess oxygen was used in all the experiments, so
that the rate expressions for epoxidation and deep oxidation to C 0 2 were given
by Eqs. (7), (8) and (9). Finally, in agreement with previous studies (Sachtler et
al., 1981; Cant and Hall, 1978) it was found that for no ethylene oxide in the feed
stream and for low conversions (<25%) r, was small enough to be neglected.
In the present experiments, excess ethylene oxide was introduced in the feed
and therefore the assumption OETo30 cannot be valid. A satisfactory kinetic
model for ethylene oxidation under these conditions should account not only for
the kinetics (Figures 3, 4), but also for the surface oxygen activity behavior
(Figure 5). Furthermore, it should not contradict the results previously reported
(Stoukides and Vayenas, 1980, 1981).
Along these lines and assuming thermodynamic equilibrium between surface
and gaseous ethylene as well as between surface and gaseous ethylene oxide one
may write:
and
Using Eqs. (21) and (22) we could modify Eqs. (7), (8), and (9) as follows:
where the values of K , , K,, K,, KETo and K , are the same as those shown in
Eqs. (10) through (14).
In presence of excess ethylene oxide the rates rco, and rETo can be written as:
rco, = rz + r3 = K 2 + KP 3 K~E T~O ( P E T 0 ) 2

K ~ ~
1 + KETPET+ KETO(~'ETO),
and
FIGURE 9 Predicted rates of ethylene oxide formation, ethylene oxide oxidation and ethylene deep
oxidation at 400C. P, = 0.0105 bar. Po, = 0.1 bar.
FIGURE 10 Predicted rates o f ethylene oxide formation, ethylene oxide oxidation and ethylene
deep oxidation at 280C. P,, = 0.01 15 bar, Po, = 0 . l bar.
The values of r,, r,, r,, r,,, and rco, predicted from Eqs. (7a), (8a), (9a),
(23), and and (24) are shown in Figures 9 and 10 for 400" and 280" respectively.
The experimentally observed rates rETo and r o , are also shown. A reasonable
agreement between experimental and predicted values for r o , and rETo is
observed.
In addition to the kinetic results the behavior of a, should be in agreement with
that predicted by the model. Assuming that the measured open-circuit EMF
reflects the activity of atomically adsorbed oxygen rather than any other type of
oxygen species present on the catalyst surface one can write a steady state
material balance for atomic oxygen:
~ ~ ( P o , ) ' ~ ~( l (- 1 ~- - ~ E T O-) ~ , e , ( l - ~ E -T ~ E T O )
E T
- Y K ~ ~ E+TK ~I O ~ E T-~KO~ ~~ O ~=E0 T (25)

O
Justification of the form of adsorption, desorption and reaction terms has been
presented in detail in a previous communication (Stoukides and Vayenas, 1981).
The only term added in the present case is the last one "-K3808,0" to account
for the non-negligible rate of ethylene oxide oxidation to C o t . Dividing all terms
of Eq. (25) by KA(l - Oo)(l - eET- OETO)and taking into account Eqs. (21) and
(22) and also (Stoukides and Vayenas, 1981) that:
one obtains
Equation (27) implies that for constant PETand Po, the term (Po,)lnao should be
proportional to (pETo)'. Indeed, in Figure 11, where the experimental data are
plotted as P&:la, vs. (pETo)', a linear dependence is observed for all tempera-
tures examined.
Although the above presented analysis does not prove that the interpretation
given is a unique one to explain the experimental observations, it provides
reasonable and quantitative agreement with both kinetic and potentiometric
measurements. According then to the above model the main conclusions can be
summarized as:
a) Most probably ethylene oxide and ethylene compete for the same sites on
the catalyst surface.
b) In agreement with previous works, r3 is negligible under the usual
conditions for ethylene oxidation (excess air, low conversions). However, if PETo
increases in the reactor the secondary oxidation of ethylene oxide to complete
oxidation products may become important and consequently the reaction
selectivity drops considerably.
The results in the range of flowrates where the external transfer limitations are
significant are an indirect verification of the fact that the reaction of ethylene
combustion r2 has a higher activation energy than the reaction of ethylene
epoxidation r,. It can be seen from Eqs. (7a) and (8a) that the dependence of
both r, and r2 on the gas phase composition is the same, so the selectivity is a
function of the temperature only. Thus, the temperature gradient which is formed
between the bulk and the catalyst surface is responsible for the change in the
selectivity. Since both reactions are exothermic, the temperature on the catalyst
surface is higher than the one in the bulk and increases as the flowrate decreases.
Hence, since the activation energy of complete oxidation is higher than the
activation energy of epoxidation, the selectivity drops. The data in Table I1 can
be used to calculate the mass and heat transfer coefficients from the following
FIGURE 1 1 Dependence of surface oxygen activity on gas composition. P,,=0.0105 bar, Po,=
0. I bar.
mass and heat balance equations:
r, AH, + r, AH, = hA(Tb - T,) (29)

The subscripts "b" and "s" refer to values in the bulk and right above the surface
respectively. Of course, the mass and heat transfer coefficients increase with the
flowrate. If we assume the following dependence of the mass and heat transfer
coefficients on the flowrate
we find that the best fit to the data is obtained for C, = 1.78 X q t = 1.98,
TABLE 111
Predicted values in the range of external transfer limitations
C, = 3.41 x lo-' and q2 = 1.96 when Q is expressed in cm3/min, K,A is in m3/s

and hA is in calls. K. Namely, it is found that both the mass and the heat transfer
coefficients are proportional to the square of the flowrate. The predicted values of
rl, r2 and S using the above expressions for K,A and hA are shown in Table 111.
Comparing these values with the ones obtained experimentally we may observe
that in some cases there is a good agreement between the experimental and the
predicted values while in other cases the agreement is not so good. This may be
due to a more complicated dependence of the mass and heat transfer coefficient,
on the flowrate than the one expressed by Eqs. (30,31). Nevertheless, Eqs.
(30,31) can be used as approximations to derive qualitative conclusions on the
effect of external transfer limitations on the performance of the system. Figures
12 and 13 show the reaction rates r, and r,, the selectivity S and the temperature
of the catalyst surface T, as functions of the flowrate Q. Equations (28,29) and
(30,31) were used for computing these curves with the partial pressure of
ethylene in the bulk being PET,,= 6 x bar. It can be seen that as the flowrate
decreases, the reaction rate rl decreases while r2 initially increases, goes through a
maximum and then decreases. The temperature on the surface of the catalyst
increases as the flowrate decreases and this causes the initial increase of r2, but
the partial pressure of ethylene near the surface of the catalyst decreases and this
results to decrease of r, and r2 at low flowrates. The selectivity S decreases at low
flowrates because of increase of the temperature on the catalyst surface.
FIGURE 12 Predicted values of reaction rates r,, r, in presence of significant diffusion limitations.
FIGURE 13 Effect of diffusion limitations on catalyst temperature and reaction selectiv~ty.

Besides the temperature gradient formed between the bulk and the catalyst
surface, one could think of some other phenomena that could contribute to the
drop in the selectivity with decreasing flowrate. First of all, the approximations in
Eqs. (17,18) are not necessarily valid in the range of strong diffusion limitations.
T o that end, the rate of ethylene oxide oxidation r3 was measured independently
by introducing air and ethylene oxide in the reactor at flowrates and partial
pressures of ethylene oxide similar to those shown in Table 11. The values of r,
found were again two orders of magnitude lower than those of r, and r2 under the
same flowrate conditions. Thus, the decrease in S shown in Figure 8 cannot be
attributed to a relative increase in r, in the region of low flowrates.
Also at low flowrates the gas phase mixing in the reactor might be incomplete
and the assumption of CSTR behavior may no longer hold. This could contribute
to the decrease in r, and r2. Using the infrared C 0 2 analyzer (Stoukides and
Vayenas, 1980) we obtained the residence time distribution function over the
flowrate range of 40-300cm3/min. It was found that even for the lowest flowrate
used, the reactor behavior was very close ( < 5 % deviation) to that of the CSTR.
Thus, the observed phenomena could not be attributed to deviation from ideal
CSTR behavior.
Another phenomenon that could contribute to the drop of the selectivity with
decrease of the flowrate is the inhibiting effect that C 0 2 has on the rate of
ethylene epoxidation r, as reported by Stoukides and Vayenas (1981). As the
flowrate decreases, the reaction conversion increases and thus the C 0 2 con-
centration in the reactor increases. Moreover, the diffusion rate between the
catalyst surface and the bulk decreases upon decreasing the flowrate. This causes
a further increase of the C 0 2 concentration near the catalyst surface. Due to the
inhibiting effect of C 0 2 on r,, the selectivity is expected to decrease. However,
the inhibiting effect of C 0 2 becomes important at lower temperatures and is of
minor significance at temperatures greater than 400C. This implies that the
inhibiting effect of C 0 2 contributes very little to the decrease in the selectivity.
Therefore, we may conclude that the external temperature gradient is mainly
responsible for the observed drop in the selectivity with decrease of the flowrate.
An internal temperature gradient may also have some effect in the present case,
but as it has been stressed in various analyses (Carberry, 1975; Hutchings and
Carberry, 1966) and experimental observations (Butt et al., 1977; Kehoe and
Butt, 1972) for gas-solid catalytic reactions, the predominant temperature
gradient occurs in the external film and the catalyst itself may be taken as
internally isothermal. Also, the pore size of the Ag catalyst used in the present
study was quite large (2 1 pm) and internal diffusion was found to be negligible
(Stoukides and Vayenas, 1980, 1981).
In conclusion, the present work shows that the observed phenomenon of
considerable decrease in the selectivity in the regime of low flowrates can be
mainly attributed to the difference in activation energies of the two reactions r,
and r2 and to the temperature gradient that is formed between the bulk and the
catalyst surface. The inhibiting effect of C 0 2 on r , and temperature gradients
inside the catalyst pores may also contribute to the selectivity drop to a minor
extent. Due to the industrial importance of ethylene oxide production from
ethylene, it is highly desirable to minimize the production of COz, i.e. maximize
the selectivity. Presence of external mass and heat transfer limitations causes a
substantial decrease in selectivity. Therefore, care should be taken to operate the
reactor in the range of conditions where external transport phenomena are not
important.
NOMENCLATURE
Surface oxygen activity

Mass and heat transfer area, m2
Electromotive force, volts
Faraday's constant, 96,500 Cb gr equivalent-'
Total molar flowrate, molels
Heat transfer coefficient, cal s-' K-' m-2

Mass transfer coefficient, m .s-'
Kinetic rate constants, mole . s-'
Adsorption coefficients for ethylene and ethylene oxide
respectively
Adsorption and desorption rate constants for atomic oxygen
Adsorption coefficient for atomic oxygen
Partial pressure of species i, bar
Volumetric flowrate, cm31min
Rate of reactions of ethylene epoxidation (i = I), ethylene deep
oxidation (i = 2) and ethylene-oxide oxidation (i = 3)
Ideal gas constant, 1.987 cal mole-' K-'
Selectivity to ethylene oxide (moles of ethylene oxide produced
per mole of ethylene consumed)
Absolute temperature, K
Greek Symbols
dimensionless coefficient, y(KzIKl)Z 1 (Stoukides and Vayenas,
1981)
A PET PET,i-PET i.e. inlet minus outlet partial pressure of ethylene in
the reactor
@i coverage of species i
Po2 chemical potential of oxygen
~ck,(g) standard chemical potential of oxygen in gas phase
ACKNOWLEDGEMENTS
We gratefully acknowledge the National Science Foundation for financial support

through NSF Grant CPE 82-15085.We also thank Prof. C.G. Vayenas for his
useful comments on this work.
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Ethylene Oxidation On Silver Catalysts e

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Chem. Eng. Commun. Vol. 44 pp.

ETHYLENE OXIDATION ON SILVER

Ethylene oxide is produced commercially from ethylene oxidation over supported

The present communication is focusing attention on a) the effect of ethylene

A schematic diagram of the experimental apparatus is shown in Figure 1. It

FIGURE 1 Schematic diagram of apparatus

FIGURE 2 Schematic diagram of reactor cell

products was also monitored by a Beckman 864 Infrared Analyzer.

Measurement of Surface Oxygen Activity

Thus a; expresses the partial pressure of gaseous oxygen that would be in

The above equation is always valid, irrespective of whether thermodynamic

The catalytic oxidation of ethylene was studied in presence of excess ethylene

i.e. very close to the values reported previously.

FIGURE 5 Dependence of surface oxygen activity on P,,,. P,,=O.l bar, PET=0.0105bar.

FIGURE 6 Effect of volumetric flowrate on the rate o f ethylene consumption. T=440"C,

Therefore, in absence of diffusional effects, APETIPETplotted vs. Q-' should

from the equations:

The approximations in the above equations were based on kinetic data

The effect of Q on r, and r2 as well as on S is shown in Figures 7 and 8. With

In a ~ r e v i o u scommunication (Stoukides and Vayenas, 1981) a kinetic model for

catalyst was calculated from the following equation:

rco, = rz + r3 = K 2 + KP 3 K~E T~O ( P E T 0 ) 2

- Y K ~ ~ E+TK ~I O ~ E T-~KO~ ~~ O ~=E0 T (25)

mass and heat balance equations:

r, AH, + r, AH, = hA(Tb - T,) (29)

C, = 3.41 x lo-' and q2 = 1.96 when Q is expressed in cm3/min, K,A is in m3/s

FIGURE 13 Effect of diffusion limitations on catalyst temperature and reaction selectiv~ty.

Surface oxygen activity

Heat transfer coefficient, cal s-' K-' m-2

We gratefully acknowledge the National Science Foundation for financial support

Catalytic Selectivity". I. Catal. 26, 247 (1972).

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