Applied Catalysis, 18 (1985) 87--103 87

Elsevier Science Publishers B.V., Amsterdam -- Printed in The Netherlands

A KINETIC MODEL OF STEADY STATE ETHYLENE EPOXIDATION OVER A SUPPORTEDSILVER

CATALYST

L. PETROV, A. ELIYAS and D. SHOPOV

I n s t i t u t e of Kinetics and Catalysis, Bulgarian Academy of Sciences, Sofia 1113,
Str. Acad. G. Bonchev bi.11, Bulgaria.

(Received 12 December 1984, accepted 16 A p r i l 1985)

ABSTRACT
A k i n e t i c study of selective ethylene oxidation to ethylene oxide over a s i l v e r
c a t a l y s t has been carried out by the c i r c u l a t i o n flow method. The s i l v e r was
promoted by a Ca a d d i t i v e and was supported on alumina. The experiments were con-
ducted under steady state conditions in the temperature i n t e r v a l 210 - 292°C and
at atmospheric pressure. As a r e s u l t of t h i s k i n e t i c study two rate equations, f o r
the p a r t i a l and f o r the complete o x i d a t i o n reactions, are proposed. A reaction
scheme is put forward, according to which adsorbed molecular oxygen produces
ethylene oxide, whereas the atomic oxygen is responsible f o r the complete oxidation
reaction. The empirical k i n e t i c model corresponds to a Rideal-Eley type of mecha-
nism. S e l e c t i v i t y decreased with temperature increase and with decrease of the
oxygen content in the feedstock.

INTRODUCTION
Since the pioneering work of Lefort [ I ] in 1931 and the f i r s t i n d u s t r i a l r e a l i z a t i o n
of direct catalytic ethylene epoxidation in 1937 a great number of investigators
have studied the k i n e t i c s of t h i s process in order to elucidate i t s mechanism.
A wide range of physical methods has also been applied to gain knowledge of the
intermediates e x i s t i n g on the s i l v e r surface under the reaction conditions.
The existence of adsorbed atomic and molecular oxygen on the s i l v e r surface
seems to have found almost general acceptance. However, the opinions of the authors
d i f f e r as f a r as the role of these two species is concerned. Three working hypo-
theses have been put forward up to now:

ZO2 ÷ C2H40 ~C2H40 ZO,~ C2H40

ZO 2~,,)~
ZO ~ CO2 + H20 CO2 + H20 CO2 + H20
Scheme I Scheme I I Scheme I I I

Most investigators favour reaction scheme I , according to which adsorbed molecular

oxygen produces ethylene oxide, whereas the atomic oxygen is responsible f o r the
complete oxidation reaction [2-7]. Other authors argue in favour of scheme I I .

0166-9834/85/$03.30 © 1985 Elsevier Science Publishers B.V.

88

They consider adsorbed atomic oxygen as a common precursor f o r both C2H40 and f o r
CO2 ÷ H20 [8-13]. A number of studies suggests a scheme in which the molecular
oxygen species reacts with ethylene to give both epoxide and carbon dioxide -
scheme I I I [14-18,39].
A Rideal-Eley mechanism is proposed by the majority of the authors. They conclud~
that gaseous or weakly adsorbed ethylene i n t e r a c t s with chemisorbed oxygen [2-4,6,
8,10-15,17,18]. Other authors, contemplating the data on the dependence of reaction
rate on C2H4 p a r t i a l pressure, which is not l i n e a r over the e n t i r e range, propose
a Langmuir-Hinshelwood type of mechanism, according to which both ethylene and
oxygen are chemisorbed and i n t e r a c t in the adsorbed state on the Ag surface [7,9,
19-21]. There is also spectroscopic evidence suggesting an adsorbed ethylene i n t e r -
mediate [9,16].
The p r e v a i l i n g number of studies support a single s i t e mechanism. In the case
of a Langmuir-Hinshelwood mechanism, a competitive adsorption of oxygen and ethylen~
on the same type of active sites is assumed. The nature of the a c t i v e s i t e is Ag20,
according to [4,14,15,17] or a single s i l v e r surface atom [22]. A dual s i t e mechani!
is proposed in [19,20,23,24]. According to t h e i r concept, oxygen adsorbs on com-
p l e t e l y reduced s i l v e r atoms, while ethylene adsorption requires a p o s i t i v e l y
charged s i l v e r atom.
Twigg concluded in early work [8] that oxygen adsorption is the slowest and
therefore the r a t e - c o n t r o l l i n g step. However, in more recent studies, an agreement
exists between the investigators that the rate-determining step is a surface
reaction. This i s , in f a c t , the only point in the mechanism t h a t has found general
acceptance.
A p a r a l l e l - c o n s e c u t i v e scheme dominates over the p a r a l l e l scheme of the reaction
which means that f u r t h e r oxidation of C2H40 is considered h i g h l y probable by most
of the authors.
The object of the present paper was to study the k i n e t i c s of ethylene oxidation
over a supported s i l v e r c a t a l y s t and to propose a reaction scheme and a k i n e t i c
model of the process.

EXPERIMENTAL
Apparatus
The reaction rates were measured by a glass c i r c u l a t i o n flow system at atmos-
pheric pressure. The block diagram of the apparatus is shown in Figure I . The
pressure regulators (P) f i x the same pressure (1.5 atm) f o r the three gases fed
i n t o the system - C2H4, 02 and Ar. The gases are dried in the f i l t e r s (F), con-
t a i n i n g molecular sieve 5A. The Matheson m u l t i p l e mass flow c o n t r o l l e r , model 8249
(M), controls the flow rates (the precision is ±1% of the set flow r a t e ) . The
initial gas mixture flows through the six-way sampling valve (C) and then i t is
fed into the reactor (R). The f i x e d bed reactor with preheater contains 25 g of
c a t a l y s t and i t is placed in an oven (0). The e l e c t r o n i c thermoregulator (T)
 89

FIGURE I C i r c u l a t i o n flow system. P: pressure regulator, F: molecular sieve f i l t e r ,

M: mass flow c o n t r o l l e r , C: six-way valve, $I: 0.25 ml sampling loop, $ 2 : 2 ml
sampling loop, R: f i x e d bed reactor, O: reactor oven, T:thermoregulator, PP:
c i r c u l a t i o n pump, Q:Porapack Q column, DC:thermal c o n d u c t i v i t y detector, MP:
microprocessor system, T1:thermostat, T2: column thermostat, T3: detector thermostat.

maintains the desired oven temperature constant: the deviation does not exceed ±I°C.
The electromagnetic four valve piston pump (PP) provides f o r the intensive c i r c u -
l a t i o n of the reaction mixture: the rate is about 700 - 800 1 h - I .
The converted gas mixture flows out of the c i r c u l a t i o n cycle and passes through
the second s i x way sampling valve (C) so that a sample is taken f o r analysis of
the o u t l e t gas composition. The c i r c u l a t i o n cycle and the valve are placed in the
thermostat (TI) at 110°C to avoid water vapour condensation.

Gas chromatographic analysis

The analysis was carried out by means of a Tsvet 110 gas chromatograph, equipped
with a thermal c o n d u c t i v i t y detector (DC) and a 2 m Porapack Q column (Q). Column
temperature was 115°C and the c a r r i e r gas was Ar (flow rate 30 ml min-1). Detector
response was s p e c i a l l y calibrated f o r each of the reagents .... C2H4, 02 , C02, H20
and C2H40. The volumes of the sampling loops are 0.25 ml f o r the i n l e t gas sample
($I) and 2 ml f o r the o u t l e t gas sample ($2). The microprocessor system ISOTCHROM
(MP) automatically processes the data from the GC analysis.

Conditions
The experiments were carried out at atmospheric pressure and at four d i f f e r e n t
temperatures of the c a t a l y s t bed - 2i0, 240, 264 and 292°C. At each temperature
 90

four series of experiments were conducted with four d i f f e r e n t feedstock compositions:

I ) 50.0% 02 , 25.0% C2H4, 25.0% Ar
2) 33.3% 02 , 33.3% C2H4, 33.3% Ar
3) 25.0% 02 , 50.0% C2H4, 25.0% Ar
4) 20.0% 02 , 60.0% C2H4, 20.0% Ar
Within each series the c a t a l y s t bed temperature and the feedstock composition
were kept constant and only the contact time was varied. The contact time was
defined by W/Fe, where W is the c a t a l y s t mass in grams and Fe is the ethylene flow
rate in moles h-I and i t varied from 119 to 1905 g-cat h mole-1. The degree of
ethtlene conversion varied from 0.5% to 70.0%.

Catalyst
The c a t a l y s t used in t h i s k i n e t i c study of ethylene epoxidation was synthesized
in our laboratory. I t has the f o l l o w i n g c h a r a c t e r i s t i c s :
- 20% s i l v e r supported on alumina, promoted by a Ca additive
- spheroidal p e l l e t s , 6 mm in diameter
s p e c i f i c surface area, 0.14 m2 g-cat - I , determined by the BET method (adsorption
of Kr)
t o t a l pore volume, 0.06 cm3 g-cat -I
- p r e v a i l i n g pore radius, 200

Steady state
About 30 minutes a f t e r the beginning of the operation the system comes to a
steady state. This was established by the s t a t i s t i c a l method of Wald-Wolfowitz [27].
That the reaction was proceeding in the k i n e t i c region was checked by the
Corrigan c r i t e r i o n [26].

Chemicals
Ethylene (grade Purum), produced by Fluka, with p u r i t y >98%, containing 1.2%
ethane, 0.33% nitrogen, 0.21% methane, 0.06% carbon dioxide and traces of carbon
monoxide, was used.
Technical grade oxygen and high p u r i t y argon (99.9%) were u t i l i z e d .

PROCESSING OF EXPERIMENTAL DATA

The experimental data were processed by means of special programs in BASIC on
a 9845 B Hewlett- Packard computer. These programs perform the f o l l o w i n g calculation~

CHROM Program f o r chromatogram processing

- calculates the p a r t i a l pressures of a l l the reactants and products ( i n atm) both
in the feedstock and in the converted gas mixture, flowing out of the c i r c u l a t i o n
cycle from the chromatographicall determined (ISOTCHROM) compositions.
- computes the material balance of each experiment w i t h respect to carbon,
 91

hydrogen and oxygen

- f i g u r e s out the degree of conversion o f a l l the reactants AXi in %
- c a l c u l a t e s the s e l e c t i v i t y S f o r ethylene oxide as the f r a c t i o n of ethylene
converted in the epoxidation r e a c t i o n in the t o t a l amount of ethylene converted
- computes the rates of consumption or accumulation of the reagents Wi (rates f o r
substances):

Wi = AXi.Fi/W (I)

where AXi is the degree of conversion o f the reagent i . Here i = I means e t h y l e n e ,

i = 2 is oxygen, i = 3 is ethylene o x i d e , i = 4 is carbon d i o x i d e and i = 5 is
water. When we c a l c u l a t e the rate f o r oxygen Fi is the oxygen f l o w rate in moles h - I ,
while in a l l o t h e r cases Fi is the ethylene flow r a t e . Wi is c a l c u l a t e d in moles h - I
g-cat - I .

LINF Program
In our r e a c t i o n system there are o n l y two l i n e a r l y independent r e a c t i o n routes:

I) C2H4 + ½02 = C2H40 (2)

I I ) C2H4 + 302 = 2C02 + 2H20 (3)

The program computes the rates along independent routes - R(1)of the p a r t i a l
o x i d a t i o n and R(2) of the complete o x i d a t i o n . Rj are c a l c u l a t e d on the basis of
the rates f o r reagents Wi , already determined by CHROM. The r e l a t i o n s h i p between
Rj and Wi is given by the expression:

n
Z Cij.R j = Wi (4)
j=1

where Cij are the elements of the transposed s t o i c h i o m e t r i c m a t r i x , i = 1,2 . . . . .

m is the number o f the reagent and j = 1,2 . . . . . n is the number o f the independent
route; n and m are r e l a t e d by the f o l l o w i n g e q u a l i t y :

n = m- q (5)

where q is the rank o f the atomic m a t r i x . Applying (4) and (5) f o r the e p o x i d a t i o n
o f ethylene we o b t a i n :

W° = -0.5 R(|) - 3 R(2)

We = - R(1) - R(2)
Weo = R(1) (6)
W = 2 R(2)
C
W = 2 R(2)
W
g2

where Wo is the rate f o r oxygen, We is the rate f o r ethylene, Weo is the rate f or
ethylene oxide, Wc is the rate f o r carbon dioxide and Ww is the rate f o r water.
The system (6) consists of f i v e equations with two unknowns, R(1) and R(2)
(Wi are determined experimentally), so i t is preset. Due to the errors in the
determination of Wi the system becomes inconsistent. For this reason we have to
f i n d i t s approximate s o l u t i o n . Overdetermined systems of l i n e a r equations may be
solved by means of the Chebyshev approximation. Mathematically the problem is
reduced to finding such a vector ~(RI,R 2 . . . . . Rn) f o r which the minimum of the
maximum deviation is achieved, i . e . the problem is equivalent to the l i n e a r pro-
gramming problem to f i n d min ~ with the l i m i t a t i o n s [28-30,32].

I!iCij Rj - Wi < ~ (7)

I t has been shown t h a t a r e l a t i v e s t a b i l i t y of the solutions exists at small

experimental errors of the substance formation rates [31]. The a p p l i c a t i o n of the
standard programs f o r l i n e a r programming requires observance of the Haar condition,
which means that a l l the main minors of the stoichiometric matrix should necessarily
be d i f f e r e n t from zero. This condition, however, is not always v a l i d and that is
why we used the algorithm of Abdelmalek [38], which also holds good f o r the cases
when the Haar condition is not observed. The experiments with greater error give
nonfeasible solutions and thus an additional check on the q u a l i t y o f the experi-
ments is carried out.
In [40] two of the authors of the present paper have studied the problem of the
a p p l i c a b i l i t y of d i f f e r e n t computing procedures f o r the determination of the
reaction rates along independent routes. I t has been shown that in the cases when
the law of error d i s t r i b u t i o n is not known the best r e s u l t is achieved by using
nonlinear programming methods with a minimization c r i t e r i o n :

Wcalc _ wexp
E = minmax i l (8)
wexp
1

When the experimental errors are small the l i n e a r and nonlinear programming give
the same result. That is why we used l i n e a r programming as the f a s t e r c a lc ulat ing
procedure,

NEM Program
By means of the NEM program a k i n e ti c equation best f i t t i n g the experimental
results f o r each route is selected and the values of the preexponents and the
a c t i v a t i o n energies f o r each k i n e t i c constant as well as the reaction orders are
determined. The program makes use of the p a r t i a l pressures (determined by CHROM)
and of the rates along routes (determined by LINF). I t is based on a nonlinear
programming method and in p a r t i c u l a r the Nelder-Mead algorithm [33]. In the
 93

calculations the f o l l o w i n g minimization c r i t e r i a were used:

N (RCalc Rexp)2 (9)

El = Z .. - -.
i=I Ij 1J

corresponding to a normal error d i s t r i b u t i o n and:

N (RCalc exp 2 Rexp)2. (10)

E2 = Z Ij - Ri~j ) / ( i j
i=I

corresponding to a normal r e l a t i v e e r r o r d i s t r i b u t i o n . Here N is the t o t a l number

of experiments, taking into account d i f f e r e n t temperatures; j = 1,2 is the route
number; R~ Ic is the theoretical rate along route, calculated on the basis of the
]J
k i n e t i c model" R~ p is the experimental rate along route, i . e . the one already
' lJ
determined by LINFo
The NEM program calculates also the model deviation f o r each tested equation
by the formula:

N
D: Ic - Rexpi.1OO/R xP).I/, (11)
i=I
Ij J J

The k i n e t i c constants were also calculated by the Marquardt procedure [41]. The
values were the same as those calculated by NEM. The confidence i n t e r v a l s of the
estimates were computed only by the Marquardt procedure.

RESULTS
Figure 2 shows the concentrations of a l l the reactants as a function of the
contact time f o r one of the experimental series: the one at 264°C and feedstock
composition C2H4:O2:Ar = 1:1:1. I t can be seen from the f i g u r e that the product
concentrations gradually increase with the increase of the contact time, while the
reactant concentrations decrease with the contact time. Oxygen concentration
decrease is more rapid than that of ethylene, as could be expected from the s t o i -
chiometry of the reaction.
The dependence of the rates along routes R(1) and R(2) on the ethylene p a r t i a l
pressure f o r the series: (240°C, C2H4:O2:Ar = 1:1:1) is shown in Figure 3. Both
rates increase w i t h the increase of ethylene p a r t i a l pressure Pe at the e x i t of
the reactor. At one and the same ethylene content in the feedstock the smaller
the contact time is the greater is the ethylene p a r t i a l pressure at the reactor
e x i t . At t h i s comparatively low temperature (240°C) the epoxidation rate (R(1)
is higher than that of complete o x i d a t i o n R(2). But at the higher temperatures
( f o r example 292°C, Figure 4) the rate of complete combustion is already much
higher than the epoxidation rate. This means that the a c t i v a t i o n energy of the
complete o x i d a t i o n reaction is higher than that of the epoxidation and that is
why the combustion rate rises more speedily with the temperature.
S e l e c t i v i t y decreases with the increase of temperature (Figure 5) as could be
94

Io 60

O ,,.-------.~ c02''H20

"ZOO 300 500 700 900 1100

CONTACT rlME W / Fo(g-c~.hP.mo/e-t)

FIGURE 2 Concentrations of the reagents versus contact time at 264°C and feedstock
composition: 33.3% C2H4, 33.3% 02 , 33,3% Ar.

6-
.

X
~4"
9")

0 I I I I I I I l : ~,
,59 41 4,5 4,5 47 49 ^
C2H4 PARTIAL PRES.SURE,P
E × IO-ZATM

FIGURE 3 Computed rates along routes versus ethylene partial pressure at 240°C
and feedstock composition: 50.0% C2H4, 25.0% 02, 25.0% Ar.

expected from the comparison of figures 3 and 4. Another factor which turned out
to exert influence on the s e l e c t i v i t y is the feedstock composition (Figure 6):
this result is interesting and somewhat unexpected. As can be seen from the figure,
the selectivity drops with the decrease of oxygen content in the feedstock. A
mathematical expression for the s e l e c t i v i t y that reflects both factors (see Sm
on Figures 5 and 6) is derived from our kinetic equations and w i l l be discussed
later. Figures 5 and 6 i l l u s t r a t e the model deviation graphically.
 95

%j 0

~22tf

R(2)

1 2!0 J2 '2'4 '26 '2~ Jo\

C21"-I4 PARTIAL PRE,S,SURE,PEX'IO-WATM

FIGURE 4 Computed rates along routes versus ethylene partial pressure at 292°C
and feedstock composition: 33.3% C2H4, 33.3% 02 , 33.3% Ar.

,o6o

(J~ I I I I | I I I ! --~
200 220 260 280240 300
TEMPERATURE ~ P C

FIGURE 5 Selectivity S versus temperature at feedstock composition: 50.0% C2H4,

25.0% 02 , 25.0% Ar ( 0 - model s e l e c t i v i t y Sm, 0 - experimental s e l e c t i v i t y Se).

The degree of conversion of ethylene AXe does not affect the s e l e c t i v i t y con-
siderably as follows from Figure 7. This fact may be considered as evidence in
favour of the parallel scheme of reaction, rather than the parallel-consecutive
scheme.
96

80

°"~6 0

2of
' ~ ' ~ ' ' 4. . . . 5
FEED RATIO C2H4 : 02

FIGURE 6 Selectivity S versus feedstock composition at 292°C ( 0 - model selec-

t i v i t y Sm, 0 - experimental selectivity Se).

~'lO-
I I I I I I I I 1 -'-
0 0 qO 30 50 70 90
DEGREE OF CQIVVERSION
z~xc,,.. %

FIGURE 7 Selectivity S versus degree of conversion of ethylene ~Xe at 264°C and

feedstock compositions:/~60% C2H4, 20% 02 , 20% Ar;033.3% C2H4, 33.3% 02 , 33.3%
Ar;025% C2H4, 50% 02 , 25.0% Ar.
 97

Kinetic analysis
Various published k i n e t i c equations f o r ethylene e p o x i d a t i o n , corresponding to
a Rideal-Eley or a Langmuir-Hinshelwood type of mechanism, and also other equations
possible from a physical p o i n t of view, were tested to f i t our experimental r e s u l t s .
We d i s c r i m i n a t e d between these r i v a l models not only on the basis of the m i n i m i z a t i o n
c r i t e r i o n and the model d e v i a t i o n . We rejected models w i t h i m p l a u s i b l e a c t i v a t i o n
energy values (below 5 kcal mole -I or well over 60 kcal mole - I ) and also models
w i t h systematic e r r o r of the model rates along routes. The r a t e equations f i t t i n g
our experimental data best ( i . e . , g i v i n g values of the model rates along routes
nearest to those of the experimental rates) are the f o l l o w i n g :

KI.Po.P e
R(1) = (12)
I + K3.Po + K4.Pe

K2.P .P
o e
R(2) = (13)
I + K3.P o + K4.P e

where P is the oxygen p a r t i a l pressure and P is the ethylene p a r t i a l pressure.

o e
These equations have the same denominator: a s i m i l a r r e s u l t has been obtained by
many other authors [14,18,22,34]. This f a c t means t h a t the mechanisms of both
reactions are c l o s e l y r e l a t e d [35]. The average model d e v i a t i o n of our k i n e t i c
equations is about 20%. The values of the preexponents and of the a c t i v a t i o n energies
( c a l c u l a t e d in conformity with the Arrhenius law) as well as the values o f the
corresponding k i n e t i c constants f o r a l l r e a c t i o n temperatures are reported in
Table I. The q u a n t i t i e s are measured in the f o l l o w i n g u n i t s : [ P ] = [Pe ] = atm,
[R(1)] = [ R ( 2 ) ] = mole h- I g-cat - I , [ K I ] = [K2] = mole h-I g-c~t -I atm -2, [K3] =
[K4] = atm - I .
I t should be noted t h a t the denominator does not r e f l e c t i n h i b i t i o n by the
r e a c t i o n products. In f a c t the i n h i b i t i o n of both reactions by the products has
been e s t a b l i s h e d by many i n v e s t i g a t o r s [ 3 , 8 , 2 1 , 3 5 , 3 6 ] . Nevertheless, i t has not
been considered in some other r a t e equations [ 1 8 , 3 4 ] . Probably, under c e r t a i n
r e a c t i o n c o n d i t i o n s or in the presence o f c e r t a i n a d d i t i v e s to the c a t a l y s t , i t
may be compensated and may not show i t s e l f (as in our case).

S e l e c t i v i t y equation
The s e l e c t i v i t y of the r e a c t i o n can be expressed as f o l l o w s :

S - R(1) (14)
R(1) + R(2)

A f t e r s u b s t i t u t i n g R(1) and R(2) w i t h our k i n e t i c equations, we o b t a i n :

98

TABLE I
Values of preexponents, a c t i v a t i o n energies and k i n e t i c constants

Preexponent Ko Ea/cal mole-I 210°C 240°C 264°C 292°C

K1 13.53 8087 0.00297 0.00486 0.00693 0.0101

K2 2253.00 13559 0.00166 0.00378 0.00685 0.0128
K3 0.0004507 7378 0.980 0.625 0.453 0.321
K4 0.0051330 7897 19.2 11.8 8.38 5.81

TABLE 2
90% Confidence i n t e r v a l s f o r preexponents and a c t i v a t i o n energies

Preexponent Ko Ea/cal mole -I

Lower l i m i t Upperl i m i t Lower l i m i t Upper l i m i t

K1 12.98 14.08 7861 8313

K2 2181.00 2315.00 13125 13993
K3 0.0004394 0.000462 7194 7562
K4 0.005011 0.005255 7621 8173

S = KI___1___ (15)
KI + K2

According to this expression, s e l e c t i v i t y depends only on the temperature, as KI

and K2 are functions only of the temperature. The values of the s e l e c t i v i t y
according to (15) f o r the different reaction temperatures are as follows: 64.1%
(210°C), 56.2% (240°C), 50.3% (264°C) and 44.1% (292°C). R(1) and R(2) are the
approximate solution of the system (6), so i t is to be expected that the values
of the s e l e c t i v i t y , calculated d i r e c t l y from the experimental data, w i l l be some-
what different. In fact the s e l e c t i v i t i e s (16-18), although not quite different
from those of (15) show dependence also on the feedstock composition. So we were
faced with the problem to derive from our kinetic model an expression describing
the dependence of s e l e c t i v i t y on both factors - temperature and feedstock compo-
sition. Several formulae for the calculation of s e l e c t i v i t y from experimental data
were used (16-18).

aCeo.lO0
$I - (16)
ACe

ACeo.lO0
$2 = (17)
ACeo + 0.5ACc
 99

6ACeo. 100
$3 - (18)
5ACeo + 2ACo

where ACi is the d i f f e r e n c e between the concentrations of the corresponding reagent

i in the converted gas mixture and in the feedstock. The index e denotes ethylene,
eo is ethylene o x i d e , o means oxygen and c is carbon d i o x i d e .
We can express the degree of conversion AXi of each substance i from ( I ) . For
example:

W .W
eo (19)
AXe° = f
e

Then f o r AC we o b t a i n :
eo

ACeo = AXeo.100 = Weo.W. IOO/Fe (20)

In the same way we can derive expressions f o r each ACi . I f we s u b s t i t u t e the

corresponding expressions f o r ACeo and AC° in (18) we o b t a i n :

6W
S3 = eo (21)
5Weo + 2Wo.(Fe/F o)

We can use (6) to s u b s t i t u t e the absolute values of Wo and Weo with R(1) and
R(2). Then we use (12) and (13) to s u b s t i t u t e R(1) and R(2). In the end we have:

$3 = I (22)
0.83 + (0.17 + K2/KI).Fe/Fo

This is our s e l e c t i v i t y equation, derived from our k i n e t i c model, which describes

both f a c t o r s i n f l u e n c i n g the s e l e c t i v i t y , the temperature (through the K2/KI term)
and the feedstock composition (through the Fe/F ° term). In Figures 5 and 6, Se is
the experimental s e l e c t i v i t y and Sm is the model s e l e c t i v i t y , c a l c u l a t e d from (22).
We can judge the accuracy and adequacy o f our model from them.

Mechanism
Now we can make use of our k i n e t i c model (12-13) to draw some conclusions about
the mechanism o f both reactions. Temkin [37] has deduced a general equation f o r
the r a t e of a steady state r e a c t i o n accounting f o r the r e a c t i o n proceeding along
d i f f e r e n t pathways:
i00

~Sl
(N) r (N) r o (N) r r ...r
+ -SlaS2 + , , . + r-s1 - s 2 " " sm -s I -s 2 -s m
Z r(N) = I - (23)
n r s l r s 2 " ' " r sm r r ...r
rs I rs I rs 2 s I s2 sm

where s I , s~ s are the step numbers, r s_ and r_ s are the rates of the correspon-
z"" m m m (N)
ding step in the forward and reverse d i r e c t i o n , ~s- is the s t o i c h i o m e t r i c
number of the sm step p a r t i c i p a t i n g in the route N andmr £NJ'' is the r a t e along
route N.
This equation allows us to derive k i n e t i c models d i r e c t l y from the presumed
mechanism. The unique mechanism, which leads to our k i n e t i c model, is represented
by the r e a c t i o n scheme (24).
Steps 2) and 4) are i r r e v e r s i b l e . Step 4) o b v i o u s l y combines several f a s t
consecutive steps. The mechanism assumes both n o n d i s s o c i a t i v e and d i s s o c i a t i v e
adsorption of oxygen on the s i l v e r surface, r e s u l t i n g in adsorbed molecular as
well as atomic oxygen. Adsorbed molecular oxygen produces ethylene o x i d e , whereas
the atomic oxygen is responsible f o r the complete o x i d a t i o n r e a c t i o n . I t is im-
possible to make an assumption about the nature of the a c t i v e s i t e Z only on the
basis of our k i n e t i c study.

I II

1) Z + 02 ÷ ZO2 2 0
2) ZO2 + C2H4 ÷ ZO + C2H40 2 0
(24)
3) 2 ZO ÷ 2 Z + 02 1 -3
4) C2H4 + 6 ZO ÷ 2 CO2 + 2 H20 + 6Z 0 I

I) 2 C2H4 + 02 = 2 C2H40
I I ) C2H4 + 3 02 = 2C02 + 2 H20

Temkin assumes t h a t Z is a molecule of the surface compound AgO2. The ZO and ZO2
are also surface oxides, r e s p e c t i v e l y Ag202 and Ag203 [ 1 4 , 1 5 ] . In t h i s way our
k i n e t i c study supports a s i n g l e s i t e R i d e a l - E l e y t y p e o f mechanism w i t h the
ethylene molecule p a r t i c i p a t i n g from the gas phase.
Any o f the f o u r steps (24) may be considered as the f i r s t one in the sequence.
In t h i s way , beginning each time with a d i f f e r e n t step, we obtained f o u r d i f f e r e n t
equations from equation (23). Now we can s u b s t i t u t e the step rates rsm with the
corresponding expressions from the Law o f Mass Action. We have:

rsl = k 1 . [ Z ] . P o and r_s I = k~1.[Z02]

rs2 = k2.[ZO2].P e and r_s 2 = 0 (25)

 i01

= =
rs3 k3.[ZO]2 and r_s 3 k_3.[Z]2.p °

rs4 k4.[ZO]~P e and r s4 = 0

Thus we obtained a system of four equations with f i v e unknowns - the surface

concentrations [ Z ] , [ZO] and [ZO 2] plus R(1) and R(2). We need a f i f t h equation
to solve the system. I f [ Z ] , [ZO] and [Z02] are measured in mole f r a c t i o n s then:

[Z] + [ZO] + [Z02] = I (26)

In t h i s way we have the f o l l o w i n g system:

R(1).(2.k2.P e + 2 . k _ I )
= [Z]
kl.k2.Po.P e

2.R(1)/k2.P e = [Z02]

R(1).k4.Pe.[ZO]6 + R(2).k_3.Po.[Z]2 - 3.R(2).k4.Pe.[ZO]6

= [ZO] 8 (27)
k3.k4.P e

!R 2L1,16 = [zo]
k4" Pe~

[ ~ + [ZO] + [Z02] = I

We can solve the system i n t r o d u c i n g some approximations. The values of R(1)

and R(2) are of the order of n x 10-5 mole h -I g-cat - I . Therefore R. 2 are of the
order of i0-I0 and we can assume t h a t Ri2 = O. The same holds t r u e , of course, f o r
1

the terms Ri3, Ri4 etc. I t is apparent from (26) t h a t , f o r instance, [ZO] < I so
we can assume in the t h i r d equation of the system (27) the term [ZO] 8 = O.
F i n a l l y we o b t a i n :

a,P .P O,33a.Po.Pe
R(1) = o e and R(2) = (28)
I + b.P ° + c.P e I + b.P ° + c.P e

where

k1"k 2 kl.k 2 + 36.kl.k 4 k2

a = - - b = and c - (29)
12.k_ I 36.k 1.k 4 k_1
102

Unfortunately, the expressions (29) do not offer the p o s s i b i l i t y of determining

the rate constants of the steps kI , k_1, k2 and k4. The equations (29) i l l u s t r a t e
the complex nature of our kinetic constants in (12-13). The ratio KI/K2 of the
constants in the numerators of our kinetic equations (12-13) is not equal to 3,
as follows from (28), in the whole experimental temperature i n t e r v a l . Our kinetic
constants KI and K2 change independently from each other with the change in tem-
perature. Nevertheless, we think that our kinetic equations support the mechanism
(24) because as a result of (28) a r e a l i s t i c value for the s e l e c t i v i t y , 75%, is
obtained, which is achieved i n d u s t r i a l l y .

CONCLUSIONS
As a result of a steady-state kinetic study of ethylene epoxidation over a
supported s i l v e r catalyst at atmospheric pressure and in the temperature interval
210 - 292°C, a kinetic model of the process is proposed. The model consists of
two equations for the partial and for the complete oxidation reactions. The
equations have the same denominator due to the closely related mechanisms of the
two reactions. No i n h i b i t i o n by products is reflected in these equations: probably
under these reaction conditions i t is compensated in some way. The equations
correspond to a single site Rideal-Eley type of mechanism with the ethylene mole-
cule participating from the gas phase. Adsorbed molecular oxygen interacts with
ethylene to produce ethylene oxide, while the atomic oxygen is the precursor of
carbon dioxide and water. Selectivity depends on two factors, temperature and
feedstock composition, and this is described by a model s e l e c t i v i t y equation,
derived from the kinetic model.

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