It was shown that a number (h’)of perfect-mix permeators W = mole fraction CO in high-pressure stream

in series approaches the performance of one no-mix permeator Y = mole fraction CO in low-pressure stream or permeate
with the same total area. I n the extreme as N + the per- dZ/dA = flus of CO only through membrane, a t any point
formance of the series of perfect-mix permeators should be
identical to the no-mix model. However, with N = 8 the
mole fraction H2
mole fraction CO
j
product/

correspondence was quite close, and this indicates that
proper baffling on the high-pressure side of the permeator
would result in a performance approaching the no-mix model.
Finally, the study of a two-stage permeator with both
stages operating a t the same temperature indicates that the
area requirements are much greater, the interstage stream
that must be compressed is greater and enrichment is less for
the perfect-mix case than the no-mix case, further emphasiz-
ing the need for correct flow characteristics in a permeator.
Acknowledgment
The assistance of Chemical Projects International, Rome,
Italy, and its Xanaging Director, R. G. Minet, in carrying
out this research is gratefully acknowledged.
Nomenclature
A = membrane area, ft2
F = flux through membrane, scfd/ft2
H = volume rate of high-pressure stream, scfd
L = volume rate of low-pressure stream (permeate), scfd
P H ~PCO
, = pure gas permeability coefficients, cm3-
(STP) . cm/sec . cm2 cm H g
+ ACCEPTEDJuly 11, 1972
mole fraction Hz
feed = actual local separation factor
mole fraction CO
(rrhere the compositions are measured at the same position
coordinate)
literature Cited
Atkinson, R., “‘Permasep’ Permeators for Hydrogen Separa-
tion,’’ Tech. Bull., E. I. DuPont de Nemours & Co., Inc.,
1970.
Franks, R. G. E., “ A Digital Computer Program for Simulating
Unsteady State Processes,” Engineering Dept., E. I. DuPont
de Nemours & Co., Inc., 1970.
Levenspiel, 0. “Chemical Reactor Engineering,” Chap. 6, Wiley,
Kew York, N. Y., 1962.
RIichaels, H. S., Chem. Eng. Progr., 64 (12), 31-43 (1969).
Oishi, J., Rlatsumura, Y., Hagashi, K., Ike, C., U.S. Atomic
Energy Commission, Report No. AEC-TR-5134, 1961.
Stern, S.A., Sinclair, T. F., Gareis, P. J., Vahldieck, K. P., Mohr,
P. H., Ind. Eng. Chem., 57 (2), 49-60 (1965).
Stern, S. A., Gareis, P. J., Sinclair, T. F., Alohr, P. H., J . A p p l .
Polym. Sci., 7, 2035-51 (1963).
Stern, S. A,, Walawender, W. P., Separ. Sci., 4(2), 129-59 (April
1969).
Weller, S., Steiner, W. A , , Chem. Eng. Progr., 46 ( l l ) , 585-90
(November 1950).
RECEIVED for review September 1, 1971

Kinetics of Silver-Catalyzed Ethylene Oxidation

Peter 1. Metcalf,l and Peter Harriott

Cornell University, Ithaca, N.Y. 14860

The kinetics of silver-catalyzed ethylene oxidation were studied using a differential reactor. Behavior of
various inhibitors including ethylene oxide, carbon dioxide, water, and dichloroethylene was investigated
at a number of reactant partial pressures. The rates of both ethylene oxide and carbon dioxide formation
passed through maxima with increasing oxygen pressure. The inhibiting effects of carbon dioxide and water
appeared to be rapidly reversible and to follow a noncompetitive rate law. The inhibiting effects of ethylene
oxide and dichloroethylene were only slowly reversible. These results were not completely consistent with
Langmuir-Hinshelwood type rate expressions.

E t h y l e n e is easily oxidized with a silver catalyst. Two prod- is approximately first order in ethylene and three-halves
ucts are produced in this reaction: ethylene oxide and carbon order in oxygen a t low partial pressures of ethylene and
dioxide. oxygen. The rates of both reactions increase as the pressure
of ethylene is increased, pass through maxima, and then
0 decrease. A maximum in the rate of carbon dioxide formation
with increasing oxygen pressure was suggested by Harriott
(1971), but no maximum in the rate of ethylene oxide for-
CH?=CH? + 302 2C02 + 2H20 (11) mation with increasing oxygen pressure has been reported.
Buntin (1961) and Klugherz and Harriott (1971) found
Earlier studies by Bolme (1957), Buntin (1961), and that the reaction products-ethylene oxide, water, and
Klugherz and Harriott (1971) have shown t h a t the reaction carbon dioxide-inhibit the reactions. liargolis et al. (1962)
has shown t h a t various other elements more electronegative
1 Present address, E. I. du Pont de Xemours & Co., Inc.,
Wilmington, Del. 19898. To whom correspondence should be than silver-such as bismuth, sulfur, and chlorine-also
addressed. inhibit the reactions.

478 Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972
 Klugherz and Harriott (1971) explained these results b y a
kinetic model in which the reaction takes place between a n
ethylene species and a n oxygen species, both of which are
competitively adsorbed on top of a layer of oxygen chemi-
sorbed by the silver catalyst. I n this model, the reaction
products are also adsorbed by the chemisorbed oxygen
layer thus inhibiting the reaction.
I n this study, a differential reactor was used to measure
the effects of carbon dioxide, water, ethylene oxide, and
dichloroethylene on the rates of ethylene oxide and carbon
dioxide formation. ;Ilso, the effect of oxygen was determined
over a much wider range of partial pressures than in a n y pre-
vious work. The data were fitted to Langmuir-Hinshelwood
rate expressions, although some inconsistencies were noted.
Further discussion of the results and alternate theories is
given in the thesis byhletcalf (1971).
Apparatus
The ethylene oxidation reaction was carried out in a
packed-bed reactor consisting of a in. o.d., 0.430 in. i d . ,
piece of stainless steel tubing packed with a mixture of
10.0 grams of 20-28 mesh a-alumina-supported silver
catalyst and 15.0 grams of 20-30 mesh Ottawa sand. T h e
length of the bed was approximately 71/2 in. long. A '/8 in.
thermowell was held in the center of the reactor, and the
reactor centerline temperature was measured by a thermo-
couple which fit tightly inside. Reaction temperature mas
controlled by immersing the reactor in a n electrically heated
fluidized bed of sand. The fluidized bed temperature was
controlled a t 219" * 0.2"C by a temperature controller. T h e
average temperature rise between the fluidized bed and the
reactor center was usually less than 1-2"C, although peak
temperature rises as high as 8°C were occasionally observed.
The feed to the reactor contained ethylene, oxygen, helium,
and various trace gases. The helium was used as a diluent.
The feed gases were metered from their cylinders with pre-
cision needle valves. The gas flow rates mere measured with
either rotameters (at high flow rates) or capillary flow meters
packed with sand (at low flow rates). K a t e r was added to
the feed with a saturator. The total feed rate to the reactor
varied between 25 and 1000 scc/min. At 1000 sccimin, the
pressure drop across the reactor was about 0.03 atm.
The rates of Reactions I and I1 were determined by mea-
suring the composition of the product stream with a gas
chromatograph equipped with a thermal conductivity de-
tector. A '/8 in. 0.d. 6-ft-long column packed with 100-120
mesh Poropak Q was used to separate the components.
The catalyst used in this study was approximately 8.1%
silver supported on Alcoa T-71 a-alumina with a surface area
of 0.5 m2/g. The catalyst was prepared in the same manner
as t h a t used by Klugherz and Harriott (1971).
Experimental Procedure
The reactor was operated with lorn ethylene conversion,
but the inhibiting effects of the products plus changes in the
catalyst activity required a special procedure to get consistent
kinetic data. The effect of the products was evident from a
large decrease in reaction rate t h a t followed immediately after
a decrease in feed rate. The change could not be explained by
the slight decrease in average reactant pressures or b y
evternal mass transfer. Figure 1 shows t h a t the rates of forma-
tion of ethylene oxide and of carbon dioxide follow the simple
kinetic laws
- 15.0
I I I I
W
L
0)
5.0
\
9
c
10% Conversion)
I I I I
0.01 0.02 0.03 0.04
2, (Atm)
Figure 1. Effect of conversion on rate
E t 0 formation
A Cop formation
PEO = 0.259 atm
pori = 0.250 otm
where 2 , is the sum of the average product concentration
generated by the reaction.
The catalyst activity gradually changed with time. The
selectivity of the reaction ordinarily decreased as the catalyst
activity increased. The catalyst activity usually increased
during operation a t low conversions and high temperatures,
and decreased during operation a t high conversions and low
temperatures. These changes in catalyst activity did not ap-
pear to affect the coefficients a1 and b1 in Equations 1 and 2.
They had the values 50 atm-I and 100 atrn-l for standard
runs regardless of catalyst activity.
The fact that al and bl were constant simplified measure-
ment of the catalyst activity. The rate could be calculated
from the conversion of ethylene to form ethylene oxide and
carbon dioxide under standard operation conditions: pEt =
p o 2 = 0.263 atm; feed rate = 400 sccm. The measured rate
was then corrected using Equations 1 and 2 to the rate which
would have been measured if the feed rate had been adjusted
so that 2, = 0.01 atm.
The experimental procedure consisted of alternating
kinetic runs made a t the feed composition and flow rate being
studied with standard runs made a t standard operating con-
ditions. The rates measured a t the standard conditions rrere
corrected to 2, = 0.01 a t m using Equations 1 and 2. The rates
measured for the kinetic runs were divided by the average of
t h e corrected rates obtained from the bracketing standard
runs to obtain the relative rates (denoted R E ~ O and R c ~ ? ,
respectively).
Relative rates and corresponding 2,'s mere measured a t
a t least four different flow rates for a feed gas with a constant
composition. The reciprocals of the measured relative rates
were plotted against 2, and a straight line was drawn through
the data to obtain the relative rates corresponding to 2, =
0.01 a t m (denoted ROE~O and ROco,) I
Experimental Results
Effect of High Oxygen Pressures. T h e oxidation of
ethylene was studied at high oxygen (1.31-13.1 a t m ) a n d
low ethylene (0.026-0.062 a t m ) pressures t o test for t h e
existence of a maximum r a t e a n d t o see if t h e selectivity
is markedly affected b y these extreme operating conditions.
Ind. Eng. Chem. Process Der. Develop., Vol. 11, No. 4, 1 9 7 2 479
 1 .o
.,
.
-\
RoEtO
0.5

I I I
0.10 0.20 0.30

I I I

P 0 p ( At m.)

Figure 2. Effect of high oxygen pressures on rate of ethylene

R O , I':
oxide formation
PEt, O t m
0 0.026
A 0.062
, ,_1
0.1 0.2 0.3
PCO, ( A t m . )
The results of these experiments are shown in Figures 2 and
3. The rates of oxidation to ethylene oxide and to carbon Figure 4. Effect of carbon dioxide on oxidation rates
dioxide pass through maxima in the range of 2-5 a t m of
PEt, PO?, PH20t
oxygen pressure. These maxima shift to higher oxygen pres- atm atm atm
sures as the pressure of ethylene is increased. A t the highest 0.259 0.250 0.004
oxygen pressures, both reactions are about first order in
ethylene and -0.3 order in oxygen. The selectivity for ethyl- The possibility of interaction between water and carbon
ene oxide formation also goes through a maximum in the dioxide was studied by measuring the rate of oxidation as a
range of 2-5 a t m osygen pressure and then starts to decrease. function of carbon dioxide pressure a t various levels of water
Effect of Carbon Dioxide Pressure. Carbon dioxide was vapor pressure. The results of this study are summarized in
added in amounts varying from 0.004 t o 0.36 a t m to a feed Tables I and 11. The dat'a in these tables indicate that,
with constant partial pressure of 0.263 a t m ethylene and \Tithin the limits of experimental error, the ratios of the
0.263 a t m oxygen. T h e rate of oxidation both t o ethylene relat'ive rates a t two different' levels of carbon dioxide pressure
oxide and to carbon dioside decreased rapidly with the are independent of water pressure.
addition of increasing amounts of carbon dioxide (Figure This would indicate noncompetitive inhibition, but the
4). T h e selectivity increased rapidly a t first, but ap- results are not conclusive. The competitive adsorption model,
proached a constant value a t high carbon dioxide pressures. Equation 9, predicts that the ratio in the last column of
The rate of ethylene osidation t o form ethylene oxide fell off Table I would change from 0.73 to 0.78 over the range of water
with increasing carbon dioxide pressure to the -0.25 power pressures given, and this difference is about the same as the
a t low carbon dioxide pressures and to the -0.5 power a t standard deviation of the measured ratios. There is better
high pressures. The rate of oxidation to form carbon dioxide evidence against competitive inhibit,ion of carbon dioside
fell off ivith the -0.45 power of carbon dioxide pressure formation, with a predicted change in ratio from 0.48 to
throughout the range of pressures studied. The lines in 0.56, compared to a decrease from 0.42 to 0.39 as shown in
Figure 4 are based on Equation 9, which predicts much too Table 11.
low values a t high carbon dioxide pressures.

2.01 I 1 1 , I I I I 1 I I I I I Table 1. Interaction Between Carbon Dioxide and

Water: Ethylene Oxide Rate Dataa
RoEto(pco2= 0.014 atm) RoEto(pco2= 0.024 atm)
p ~ ? oatm
, RO~to(p~o,= 0.004 a t m ) R0~to(p~o2= 0.004 atm)
0 004 \ 0 80 i 0 07 0 71 =t0 06
0 014 0 83 i 0 07 0 74 * 0 07
0 024 0 81 k 0 07 0 74 * 0 07
a Data for pEt = 0.259 atm, PO? = 0.250 atm

Table 11. Interaction Between Carbon Dioxide and

111115.0
1111111111 10.0
Water: Carbon Dioxide Rate Data.
Pg,(Atm.) Rocozlpco?= 0.014 otm) R0co2(pco2= 0.024 atm)
atm
PH~O, RaCo2(pCo2= 0.004 atm) Rocol(pco,= 0.004 otm)

Figure 3. Effect of high oxygen pressures on rate of carbon 0 004 0 55 i 0 05 0 42 i 0 04

dioxide formation 0 014 0 50 i 0 05 0 39 L 0 0.1
PEt, a t m
0 024 0 52 i 0 05 0 39 *
0 04
0 0.026 a Data for p~~ = 0 2.59 atm, PO? = 0.250 atm
A 0.062

480 Ind. Eng. Chem. Process Des. Develop., Val. 11, No. 4, 1972
 I I I I I I

Table 111. Effect of Carbon Dioxide on Rate of

Ethylene Oxidation at Various Reactant Pressures.
RE~O(PCO* = 0.024 atm) F!coI(pco2 = 0.024 atm)
p ~ t atm
, po2, atm RE&CO~ = 0.004 atm) Rco,(pco2= 0.004 otm)
0.062 0.052 0.72 i 0 . 0 6 0.48 i 0 . 0 6
0.062 1.31 0.70 * 0.06 0 . 4 2 =k 0 . 0 5
0.01 0.02
0.259 0.250 0.71 i 0.06 0.41 =k 0.05
1.32 0.055 0 . 9 2 + 0.08 0.95 * 0.11 PH,O ( A t m . )
a Data for PH?O = 0.004 atm.
I I I I I I

The interaction among carbon dioxide and the reactants

was studied by measuring the rate of oxidation with 0.02 a t m
carbon dioxide added to the feed at various levels of oxygen
and ethylene partial pressures. The results of these experi-
ments are tabulated in Table 111.Increased ethylene pressures
appear to reduce the relative effect of carbon dioxide, sug-
gesting t h a t ethylene and carbon dioxide compete for the
same sites. Increased oxygen pressures do not affect the
relative effect of carbon dioxide addition significantly,
though little effect is expected at these pressures, xhere the
reactions are nearly first order to oxygen.
Effect of Water Vapor Pressure. T h e effect of water on
t h e oxidation of ethylene was tested by adding small
amounts (0.010 a n d 0.020 atni) of water t o t h e reactor
feed. F o r feed compositions of 0.263 a t n i ethylene and 0.263
a t m oxygen, t h e rate of ethylene oxide formation declines
in proportion t o t h e -0.25 power of t h e average water
vapor pressure, \vhile t h e rate of carbon dioxide formation
falls off with t h e -0.20 power of the average water vapor
pressure (see Figure 5).
The interaction among water and the reactants n-as tested
b y measuring the rate of oxidation with 0.02 a t m water
added to the feed at various levels of oxygen and ethylene
pressures. The results of these experiments are tabulated in
Table IV. The effect of oxygen and ethylene is similar to that
found in the study of the interaction among carbon dioxide,
oxygen, and ethylene. The addition of ethylene reduces the
inhibiting effect of water. Greater oxygen pressure has little
effect on the inhibition of ethylene oxide formation by
water, but may even enhance the effect of water on carbon
dioxide formation.
Effect of Ethylene Oxide Pressure. T h e addition of 0.005
a t m of ethylene oxide t o t h e standard feed gas caused a n
immediate 50% reduction in t h e r a t e of oxidation t o
ethylene oxide, b u t almost no reduction in t h e rate of oxi-
dation t o carbon dioxide. T h e catalyst activity then
trended steadily downward over a period of 3 h r until al-
most no ethylene oxide or carbon dioxide was being formed.
K h e n t h e ethylene oxide addition was stopped, t h e rate of
ethylene oxide formation jumped almost back to the original
Figure 5. Effect of water on oxidation rates
0 pco, = 0.004 atm
A pco? = 0.014 atm
pcog = 0.024 atm
P E ~= 0.259 atm
PO, = 0.250 atm
carbon dioxide generation. N o data on the relative rate of
ethylene oxidation as a function of ethylene oxide partial
pressure was gathered since the ethylene oxide apparently re-
acted slowly to inactivate the catalytic sites rat'her than being
reversibly adsorbed on the sites as in the case of the reactants
and the other product gases. Holyever, the reversible effect of
the combined products could be accounted for by the presence
of carbon dioxide and water.
Effect of Dichloroethylene Pressure. Dichloroethylene
(DCE) is a strong inhibitor for t h e silver-catalyzed osida-
tion of ethylene. Figure 6 illustrates t h e effect of adding
several different concentrations of DCE to t h e standard
feed. T h e rate of ethylene oxide formation falls rapidly.
T h e rate of carbon dioxide (not, shou-n) follows a siniilar
pattern. As the Oxidation rates fall, selectivity is gradually
increasing. Selectivities as high as 75% were obtained as
t h e activity approached zero, compared with the normal
!i0.02
v)

v
1
value while there mas little immediate change in the rate of

Table IV. Effect of Water on Rate of Ethylene

02
8
.-
O.O'
0.005
t
e
DCE Added (Standard Operating
Oxidation at Various Reactant Pressures.
RE&H~O = 0.024 atm) R C O ~ ( P H ~ O= 0.024 atm) 0.002
2 4 6 8
PEt, atm PO*,atm REto(pH20= 0.004 atm) R C O * ( P H ~ O= 0.004 otm)
Time (Hrs.)
0.062 0.052 0.60 i 0.05 0 . 7 3 =& 0.07
0.062 1.31 0.54 i 0.05 0 . 4 7 =t0 . 0 5 Figure 6. Transient response of t h e rate of ethylene oxide
0.259 0.250 0.66 *
0.06 0.72 I 0 . 0 7 formation to dichloroethylene addition
1.32 0.055 0.88 i 0.08 0 . 8 8 =t= 0 . 0 9
0160ppbDCE
a Data for PCO, = 0.004 atm. B320 ppb DCE
A 640 ppb DCE

Ind. Eng. Chem. Process Des. Develop., Vol. 1 1, No. 4, 1972 48 1


Table V. Effect of 80 Ppb DCE Modification on
Rate of Ethylene Oxidation
R'rtn ROco,--.
80 PPb 80 p p b
p ~ t atm
, pox, atm pco2, atm Normal DCE Normal
Increasing oxygen pressure
0.062 0.052 0.0042 0.24 0.47 0 . 3 6
0.062 0.249 0.0036 0 . 5 3 0 . 8 6 0 . 7 6
0.062 1.31 0.0043 1 . 3 0 1 . 9 6 1.10
Increasing ethylene pressure
0.062 0.052 0.0042 0.24 0 . 4 6 0 . 3 6
0.258 0.054 0.0046 0.21 0.24 0 . 2 8
0.062 0.249 0.0036 0 . 5 3 0 . 8 6 0.76
0.259 0.250 0.0037 1.00 1 . 0 0 1 . 0 0
Increasing carbon dioxide pressure
0.259 0.250 0.0037 1 . 0 0 1.00 1 . 0 0
0.259 0.250 0.0244 0.71 0.71 0.42
selectivity of 45%. T h e catalyst activity could be restored
by feeding the standard feed overnight while raising t h e
reactor temperature to 240OC.
The rate of decline of catalyst activity varied considerably
depending on the concentration of D C E in the feed. A t 640
ppb D C E , the rate of carbon dioxide formation fell a t a rate
of approximately 90'%/hr. A t half that concentration, 320 ppb,
the rate fell a t 30%/hr; a t 160 ppb, the rate of decline was
hard to detect. Several factors may have contributed to this
highly nonlinear effect. The amount of D C E in these tests
was so low that little of the surface mas covered. Adsorbed
chlorine atoms undoubtedly deactivated sites adjacent to the
sites on which they were adsorbed. The degree of this type of
inhibition would not be expected to be a linear function of the
amount of chlorine adsorbed.
The rate of oxidation of ethylene was determined for
several pressures of ethylene, oxygen, and carbon dioxide on a
D C E modified catalyst (Table V). The catalyst was modified
by feeding 100 sccm of gas containing 0.263 a t m ethylene,
0.263 a t m oxygen, and 80 ppb D C E overnight. The activity
declined until 2 , = 0.01. Since the feed rate was 25y0 of the
usual standard feed rate, the activity of the modified catalyst
was about 25'%.of t h a t of the unmodified catalyst. It should
be noted that it is not clear how much of this reduction in
activity is due to the addition of D C E , and how much is due
to the prolonged operation of the reactor a t high product pres-
sures.
The relative rates of reaction for the various feed and
product conditions were determined in the same manner as
with the unmodified catalyst except that the alternate runs
a t standard conditions were replaced with alternate runs a t the
modified standard feed conditions of 100 scc/min of gas with
0.263 a t m ethylene, 0.263 a t m oxygen, and 80 ppb D C E . T h e
standard conversion was still defined so that Z P = 0.01 atm.
A flow of 80 ppb of D C E was maintained both for the kinetic
runs and for the modified standard runs. The selectivity of
the modified standard runs varied from 45 to SO%, but was
usually not much higher than the selectivity for the normal
standard runs.
I t is apparent from Table V t h a t D C E modification of the
catalyst reduces the activity of the catalyst relatively more a t
high ethylene and oxygen pressures than a t low pressures:
the rate maxima would be shifted to the lower pressures.
Carbon dioxide has the same relative effect on the reaction
rate with either the modified or the unmodified catalyst.
482 Ind. Eng. Chem. Process Des. Develop., Vol. 11, No. 4, 1972
This behavior indicates that the sites which remain active
after inhibition adsorb oxygen and ethylene more strongly
than the sites on the unmodified catalyst. Such behavior is
contrary to that which would be expected from a catalyst
which obeyed a Langmuir-Hinshelwood type rate equation.
DCE
A Langmuir-Hinshelwood type rate equation would predict
that the rate maxima would be shifted to higher ethylene
0.80 and oxygen pressures on the addition of a n inhibitor if the
1.07 reactants and the inhibitor are competing for the same
1.33 catalytic sites.
Analysis of Results. T h e Langmuir-Hinshelwood theory
0.80 of heterogeneous catalysis was used to summarize much of
0.13 the kinetic d a t a gathered in this study. A model was pro-
1.07 posed which explained the following observations :
1.00 (a) The rate goes through a maximum with increasing
oxygen pressure and with increasing ethylene pressure.
1.00 Klugherz and Harriott (1971) showed that the maxima shift
0.43 to higher ethylene pressures as the pressure of oxygen in-
creases. This indicates that the rate-determining step in-
volves a bimolecular surface reaction with competitive
adsorption of oxygen and ethylene.
(b) Klugherz and Harriott (1971) also showed that the re-
action order with respect to oxygen is greater than one a t high
ethylene pressures and low oxygen pressures.
(e) The inhibiting effect of water and carbon dioxide de-
creases as the ethylene pressure increases, suggesting t h a t
ethylene and the products compete for the same sites.
(d) Ethylene, carbon dioxide, and water are adsorbed only
on oxygen-covered silver-not on bare silver (Bolme, 1957).
(e) Flank (1965) demonstrated that most of the oxygen
adsorbed by silver does not evaporate a t ordinary reaction
temperatures and pressures, but can be removed by reaction
with ethylene.
(f) Changes in the reactant and product pressures have
very nearly the same effect on the rate of formation of
carbon dioxide as they do on the rate of formation of ethylene
oxide. The selectivity of the reaction for the formation of
ethylene oxide varies in the range of about 3@-60% throughout
the wide range of pressures studied. The mechanisms of the
two reactions seem to be closely related, and it seems appro-
priate to use the same kinetic model in the analysis of each.
The fraction of the silver surface consisting only of bare
catalytic sites may be denoted 8,. Three types of oxygen are
assumed to be adsorbed on the silver surface:
Species of Fraction of Schematic
oxygen s u r f a c e covered representation
/"\
atomic e1 Ag Ag
molecular e2
o=o
adsorbed
These species are assumed to be a t equilibrium with each
other so t h a t their concentrations on the surface are related to
each other by
03 Kip0201 (3)
822 = K@iOg (4)
 Ethylene is also reversibly adsorbed by the oxygen-
covered surface:
s
h d
h

v v
r3

so t h a t the concentration of ethylene on the surface is given

by
5~ = KEPE& (5)
Atomic oxygen may gradually be removed from the surface
by reaction with adsorbed ethylene as well as by recombina-
tion to form molecular oxygen
CH2=CH2

Ag/"\Ag + Ag/"\Ag k7c

-

and
..
..
0
I

Ag/"\Ag -t Ag/"\Ag -%
Atomic oxygen is added to the surface by this s l o ~reaction
between molecular oxygen and the bare sites

0
..

The direct reaction of oxygen with bare sites t o form atomic

or molecular oxygen is neglected, although it would be impor-
tant at low surface coverages. These nonequilibrium reactions
for removal of oxygen are assumed to be much slower than the
equilibrium reactions or the rate-determining steps.
By making the steady state approximation for the atomic
oxygen species, one obtains
k&30 = ki5& + k&2 (6)
Both carbon dioxide and water are reversibly adsorbed on
the atomic oxygen:

O\
C
P
I

/"\
H H
\
\\ I /
I
H H

H , O + Ag
/"\
Ag - K h
Ag
/"\
Ag or Ag
The fractions of the surface covered by adsorbed carbon
P-"\ Ag

Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972 483
dioxide and by adsorbed water are given by ec and eh, respec-
tively. These fractions may be computed with the equilibrium
relationships:
Be = KcpCO2el
and
The fraction of the surface covered by each of these molecu-
lar species may be written in terms of the concentration of
atomic oxygen and the partial pressures of the reactants and
products. These equations may be combined with the con-
dition that the sum of the fractions of the surface covered by
each of these species is equal to 1.0 to obtain a series of
equations giving the fraction of the surface covered b y each of
the species in terms only of the partial pressures of the re-
actants and the products.
ii kinetic model in which the rate-determining step was a
bimolecular surface reaction between adsorbed ethylene and
molecular oxygen fit most of the kinetic data quite well for
both ethylene oxide formation and the formation of carbon
dioxide.
(1 + +UzpO2 + U31)02312 + arpEt + carbon dioxide, scc min-’ g-1
+ +
a E P E t p 0 ~ ~ ’ ~~ C P C O ~ P OahpH~OP02~’~)~
~~~~
The values for the coefficients in this equation were esti-
mated by regressing
against
P CPOO ~~ ,~ / ~ P H ? O (1932).
Po2liZ,Po2, P023i2,PEt, PEtPO2li2,P O ~ ~ ~ ~and
These estimates are tabulated along with the corresponding
t values of the estimates in Table VI. The values predicted
by these equations are plotted in Figures 2-5.
The parameters estimated for a, were zero, indicating t h a t
ke << k7kB..This implies t h a t the recombination of atomic
oxygen is slow in comparison with its rate of removal by
reaction with adsorbed ethylene. This conclusion is supported
b y experimental evidence obtained by Benton and Drake
(1932) that the rate of evaporation of atomic oxygen is
extremely slow.
484 Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972
One significant difference between the experimental data
and the predictions occurred at the highest carbon dioxide
pressures where the model predicted that the ratio would fall
off more rapidly with increasing carbon dioxide pressure than
(7) was actually observed (see Figure 4). These data were not
included in the regression analyses. Another difference was
that the relative inhibiting effects of water and carbon dioxide
were almost independent of each other, whereas the model
predicts t h a t they compete for sites with each other as well as
with the reactants. Finally, the model does not describe the
slow changes in reaction rate t h a t occurred when ethylene
oxide and D C E were added to the feed. These shortcomings
may be due to heterogeneity of the catalyst surface or to
changes in the electronic properties of the catalyst.
Nomenclature
a, = constant
k, = rate constants
K1, K z , K B , K,, K h = equilibrium constants
pco2 = average carbon dioxide pressure, atm
p~~ = average ethylene pressure, atm
PEto = average ethylene oxide pressure, a t m
pn20 = average water pressure, atm
po2 = average oxygen pressure, atm
%to = average rate of conversion of ethylene to form
ethylene oxide, scc min-l g-l
T ~ O , = average rate of conversion of ethylene to form
REto = relative rate of ethylene oxide formation
Reo, = relative rate of carbon dioxide formation
e, = fraction of surface covered by ith molecular species
2 , = sum of average product pressures, a t m
0 = superscript denoting value a t 8, = 0.01 atm
0 = subscript denoting value a t 2 , = 0.00 atm
Literature Cited
Benton, A. F., Drake, L. C., J . Amer. Chem. Soc., 54, 2186-94
Bolme, D. W., PhD thesis, University of Washington, Seattle,
Wash., 1957.
Buntin, R. B., PhD thesis, Purdue University, Lafayette, Ind.,
1961.
Flank, W.H., PhD thesis, University of Delaware, Newark, Del.,
1 Q6.i
Hiri%t, P., J . Catal., 21, 56-65 (1971).
Klugherz, P. D., Harriott, P., AIChEJ., 17,856-66 (1971).
Margolis, L. Ya., Emkeev, E., Isaev, O., Krylova, A. V., Kush-
nerov, 31.Ya., Kinet. Katal., 3, 181-8 (1962).
Metcalf, P. L., PhD thesis, Cornel1 University, Ithaca, N.Y.,
1971.
RECEIVED for review September 1, 1971
ACCEPTEDMay 11, 1972