150

Kinetic Study for Oxidation of Ethylene over

Silver Catalyst under Stationary State*

by Akimi Ayame**,Hisao Kano**, TakatsuguKanazuka** and HiromuBaba***

Summary : A kineticstudyfor oxidationof ethylenewas carriedout using an integral reactorand

a silver catalystpromotedby potassium sulfate under stationary state. Measurementswere made
under ordinary and higher pressures. Empirical rate equations werefound to be:
rC2H4O=k1P0.33Cc2H4Co21/2-k3P0.24Cc2H4oCH2o-1/2
rCO2=k2P0.32Cc2H4Co2,
whereP is the total pressure,and ki and Ci are the rate constantand molefraction for component
i, respectively.

In the present investigation, an attempt was

1 Introduction
made to establish accurate rate equations under
In our earlier work1)∼5), it was found that a such a stationary state in which the change in
gradual decline in the activity of a silver catalyst the activity of silver catalyst could be neglected.
for ethylene oxidation could be attributed to
2 Experimental
the following factors; sintering of the silver, the
formation of some oxidized state of silver and 2.1 Catalyst
the formation of surface residues. Surface re- The catalyst used in this experiment had the
sidues, silver glycoxide and its polymer, were following composition;Ag2O:K2SO4:Al2O3=
recognized as being important not only in the 15g:75mg:50g. It was reduced in a stream
earlier part of the reaction but also in the sta- of hydrogen for 30∼50 hours at 50∼60℃. Al2O3

tionary state. was fused alumina beads (5∼6mmφ), supplied

The formation of surface residues was retarded Norton Co.. The method of preparation of the
in the presence of water, carbon dioxide and catalyst is described in detail in the preceding
excess oxygen, and water was most effective. paper1).
The amount of surface residues was quantitatively 2.2 Preparation of Mixed Gas (Feed Gas)
determined by the oxidative desorption technique.
Ethylene was supplied by Japan Petrochemical
Consequently, the stationary activity can be re-
Co., air by Hokkai-Sanso Co.. They were mixed
garded as being attained through a competition in a cylinder. The mixture contained 2.5±0.1
between deactivation by ethylene oxide and re-
per cent ethylene.
tardation of deactivation by water, carbon dioxide
2.3 Apparatus
and oxygen. When the equilibrium is established
A flow diagram is shown in Fig. 1. The
between these two opposing influences, a sta-
reactor consisted of 40mmφ stainless steel pipe
tionary state for ethylene oxidation results .
700mm long and settled in a salt bath (KNO3-
For such a catalytic reaction system , since
NaNO2-NaNO3). An alumel-chromel thermo-
the variation in the concentration of reactants
and products causes the change in the stationary couple was inserted through the center of the
reactor tube. The catalyst bed was located at
activity of the catalyst, kinetics will be complicat-
ed considerably, and it will be important to the height of 300mm from the bottom of the
examine the effects of reactants and products tube. 50g of the catalyst was placed on top
of a layer of about 20mm of 8mmφ｢  alundum
on kinetics under each stationary state.
beads (Macroport, Norton Co.) on the support.
* Received June 9, 1973. The net catalyst bed was about 35mm in height.
** Department of Industrial Chemistr
I y, Muroran Since a considerable temperature difference
nstitute of Technology (Mizumoto-cho , Muroran,
050) through the catalyst bed resulted in the case of
*** Department of Mechanical Engineering a higher pressure operation, the average tem-
I , Kitami
nstitute of Technology(Koen-cho , Kitami, 090)
perature was assumed to be the same as the
Bulletin of The Japan Petroleum Institute
 Ayame, Kano, kanazuka and Baba: kinetic Study for Oxidation of Ethylene over Silver Catalyst 151

Fig. 1 Flow Diagram

Fig. 2 Results of Conditioningand Check Runs

predetermined value of the control heater. The

pressure and flow rate of feed gas were precisely
controlled using regulating valves located at
the inlet and outlet of the reactor. The pressure
drop across the bed was negligible in the gauge
pressure range from 0 to 15kg/cm2. Ethylene,
ethylene oxide and carbon dioxide were analyzed
by gaschromatography.

3 Results Fig. 3 Typical Temperature Distribution Curves

through Catalyst Bed
3.1 Change of Catalyst Activity due to
Changes in Reaction Conditions activity remained unchanged over a considerably
As standard conditions, Tm=200℃, F'= length of time.
12.8l/hr and P=1.0atm have been chosen, It has already been shown for the identical
where Tm is the average temperature, F' is catalyst in a glasstubing reactor that if the tem-
the flow rate of mixed reactant gas and P refers perature or flow rate is altered, the extent of
to the total pressure. conversion becomes steady within 2∼3 hours8).

Under these conditions, the catalyst activity On the other hand, when the operating pres-
was examined frequently for 1,600 hours (Fig. 2). sure is raised at constant temperature and flow
It was apparent that at least 30 hours were re- rate, the total conversion increases gradually
and a constant conversion is attained within
quired for stabilization, and that the catalyst
Volume 15, No. 2, November 1973
 152 Ayame, kano, kanazuka and Baba: Kinetic Study for Oxidation

Table 1 Experimental Values under Ordinary and Higher Pressure

4 or 5 hours. Reverse results occur when pres- longitudinal temperature profiles in the bed are
sure levels are reduced. From these facts, the shown in Fig. 3, where Tb is the temperature of
conversion data corresponding to one set of salt bath (℃) and F is the feed rate (g-mol-
reaction conditions were determined at about C2H4/hr). Therefore, the average temperature
5 hours after alternating the pressure levels . at the center of the catalyst bed was considered
However, the variation in the total conversion as the reaction temperature (Tm) .
mentioned above was found to be of the same 3.3 Kinetic Data
order of magnitude as the experimental errors . Table 1 shows the results of the several kinetic
3.2 Temperature Distribution in the Ca- runs made during the intervals indicated in
talyst Bed Fig. 2 (A, B and C). For period A the temper-
Because of the large heat of reaction ature level was fixed at 200℃ and conversions
, due
particularly to the combustion of ethylene, a were measured at various pressures and contact
longitudinal temperature gradient was observed times (W/F). For periods B and C, the temper-
especially under high pressures . Some typical ature levels were kept constant at 240 and 265℃,

Bulletin of The Japan Petroleum Institute

 of Ethylene over Silver Catalyst under Stationary
Fig. 4 AgreementbetweenCalculatedValuesby Eqs.
(1)-(2) or Eqs. (3)-(4) and ObservedValues
over Ag-KieselguhrCatalyst7)
respectively. Frequent checks indicated almost
constant conversions within experimental errors,
and hence the surface was assumed to be of the
same state as that of the reference. The ap-
parent rates of reactions (rC2H4Oand rCO2)were
determined at each contact time by graphical
differentiation9) of x or y versus W/F plots (for
example, dotted curves in Fig. 5 and 6). Mole
fraction Ci (i=C2H4, O2, etc.) was calculated
from the equations established in a previous
paper6). The calculated values of x and y, based
on some set of rate equations were obtained by
use of a modified Euler's method11).
3.4 Rate Equations
Rate Eqs. (1) and (2), reported previously
by Kano et al.6),7), are in good agreement with
the kinetic data obtained for Ag-Kieselguhr ca-
talyst at low conversion levels, but the agreement
is poor at high conversion levels (Fig. 4, dotted
line).
rC2H4O=k1pC2H4pO21/2-k3pC2H4O
rCO2=k2pC2H4pO2+k3pC2H4O
where k1, k2 and k3 are rate constants.
When Eqs. (1) and (2) were applied to the
kinetic data in Table 1, the data did not coincide
with the equations; in particular, deviations of
y were larger than those of x.
Some modification was made on these equations
based on the experimental data. As a result,
it was found that the following rate equations
well represented the observed data (solid curves
Volume 15, No. 2, November 1973
State 153
Table 2 Rate Constants in Eqs. (3) and (4)
Table 3 Rate Constants in Eqs. (5) and (6)
at P=1atm in Fig. 5, 6, 7 and 8) and those of
Ag-Kieselguhr catalyst7) (Fig. 4, solid line).
rC2H4O=k1pC2H4pO21/2-k3pC2H4O/pH2O1/2 (3)
rCO2=k2pC2H4pO2 (4)
k1 in Eqs. (3) and (4) was also estimated from
the kinetic data under high total pressure (P) in
Table 1, and it was found to decrease as P in-
creased (Table 2). It is, therefore, impossible
to represent the data under different pressures
by the same rate equations, although good agre-
ement was observed at each pressure level.
The authors have attempted to represent their
data with the following equations, assuming that
the rate constant involves a term in total pressure.
rC2H4O=(k1)1PlCC2H4CO21/2-(k3)1PnCC2H4O/CH2O1/2
(5)
rCO2=(k2)1PmCC2H4CO2 (6)
(k1)P=(k1)1Pl, (k2)P=(k2)1Pm, (k3)P=(k3)1Pn (7)
where (k1)1, (k2)1 and (k3)1 are rate constants
at one atm pressure, and l, m and n are constants.
(k1)P, (k2)P, and (k3)P are rate constants at a
(1) fixed temperature and pressure. (ki)P was deter-
(2) mined from the kinetic data and was tabulated
in Table 3. l, m and n were determined from
Eq. (7), (Table 3).
Fig. 5, 6, 7 and 8 show the agreement between
the observed and the calculated values by Eqs .
(5) and (6) using (ki)1. It is evident that these
equations give better agreement with the data ,
and the rates under high pressures can be es-
timated from the kinetic data available under
ordinary pressure.
154 Ayame, Kano, Kanazuka and Baba: Kinetic Study for Oxidation

Fig. 5 x vs. W/F and SEL vs. W/F at 240℃

Fig. 7 Agreement between Calculated Values by Eqs.

(3)-(4) or Eqs. (5)-(6) and Observed Values
over Ag-K2SO4-Al2O3 Catalyst

Fig. 6 y vs. W/F and Tt vs. W/F at 240℃

4 Discussion
4.1 Pressure Effect
It has been found that conversion of ethylene
to ethylene oxide (x) and that to carbon dioxide
(y) increase as the pressure increases at a given
W/F, as shown Fig. 5 and 6. Consequently,
at a given S. V. the increase in total pressure Fig. 8 Space-Time-Yield vs. Space-Velocity
gives a higher space-time-yield (S. T. Y.) as shown
in Fig. 8.
4.2 Rate Equations step for its oxidation, (corresponding
and

Shishakov et al.12) and Kagawa et al.13) con- to Oads-in the present work) serves as an active
firmed by means of electron diffraction that both site for the formation of ethylene oxide.
adsorbed atomic oxygen, Oads-, and adsorbed If the intermediates in the combustion of both
molecular oxygen, (O2-)ads, exist on the surface ethylene and ethylene oxide are to be identical,
of the catalyst. Kilty et al.14) supported the e.g. adsorbed ethylene oxide or acetaldehyde10),
above findings by I. R. spectra of adsorbed O the reaction scheme could be represented as
and O2. From these results, they have proposed follows1),4);
the following mechanism; 1) ethylene oxide is k1
formed from gaseous ethylene and (O2-)ads, 2) C2H4+(O2-)ads C2H4O+Oads- (8)
carbon dioxide and water are formed from C2H4+Oads-
k2'
C2H4Oads (9)
gaseous ethylene and Oads-. Kenson et al.15) k3'
C2H4O+e- C2H4Oads (10)
have also suggested that adsorption of ethylene
k4
oxide on the silver surface is the rate-determining C2H4Oads+Oads- 2CH2Oads (11)

Bulletin of The Japan Petroleum Institute

of Ethylene over Silver Catalyst under Stationary State 155

CH2Oads+4Oads-(or 2(O2-)ads) oxidation and the retarding actions to deactivation

(fast)
by ethylene oxide4) are attributable to the same
(CO3-)aas+2OHads+4e-(or 2e-) (12) behaviors of water, carbon dioxide and oxygen
Here, the inhibition effects on adsorption of on the catalyst surface1),2). In the treatment
water, carbon dioxide and oxygen to ethylene of kinetics on this catalytic oxidation, there has,
oxidation are assumed to be negligible. As- however, been no information for interaction be-
suming the adsorbed atomic oxygen to act as an tween the inhibition effect and the retardation
active site in Eq. (8) and the inhibition effects effect of each component. Even if it is possible
of components other than water for adsorption to elucidate experimentally or theoretically some
oxide to be negligibly small because the adsorption problems as described above, its rate equations
is specificially retarded in the presence of will be much more complicated.
water1),2),16) Eq. (3) is derived from Eqs. (8) It seems worthwhile that precise and simple
and (10) as follows: rate equations applying to the kinetic data under

rC2H4O=k1pC2H4pO21/2-k3'pC2H4O/(1+√KH2OpH2O) ordinary and high pressures have been obtained

in the present investigation.
as 1<√KH2OpH2O is estimated1),

rC2H4O=k1pC2H4pO21/2-k3pC2H4O/pH2O1/2 (13) Acknowledgement

The authors are grateful to Prof. Tatsuya Imoto

where k3=k3'/√KH2O and KH2O is the adsorption
and Dr. Yoshio Harano of Osaka City University
equilibrium constant of water.
and to Prof. Haruo Kobayashi of Hokkaido
The rate equation for the formation of carbon
University for their helpful suggestions.
dioxide is derived assuming that the reaction
rates of Eqs. (9) and (11) are of the same order, References
ｒCO2=(k2'pC2H4pO21/2+k3pC2H4o/pH2O1/2)×k4pO21/2 1) Ayame, A., Numabe, A., Kanazuka, T., Kano, H.,
(14) Bull. Japan Petrol. Inst., 15, (2), 142 (1973).
2) Ayame, A., Kano, H., J. Chem.Soc. Japan, Chem.
Using a set of Eq. (14) and Eq. (3) or Eq. Ind. Chem., 1972, 1819.
(13), the difference between the calculated and 3) Ayame, A., Shibuya, Y., Yoshida, T., Kano, H.,
observed conversions was very large. Con- ibid., 1973, 2063.
4) Ayame, A., Numabe, A., Watanabe, Y., Kano,
sequently, the concentration of C2H4Oads was H., ibid., 1973, 2071.
assumed to be governed by Eq. (9), i. e. 5) Ayame, A., Suzuki, Y., Kano, H., ibid., 1973, 1792.
6) Kano, H., Kanazuka, T., J. Chem.Soc.Japan (Ind.
ｋ2'pC2HpO21/2》k3pC2H4O/pH2O1/2, and then Eq. (4) Chem. Sect.), 61, 1157 (1958).
was obtained from Eq. (14). However, in the 7) Kano, H., Kanazuka, T., ibid., 65, 1 (1962).
course of calculation of conversions based on Eqs. 8) Kano, H., Ayame, A., Memoirsof the Muroran Inst.
of Tech., 4, 871 (1964).
(3) and (4), it was observed that the value of 9) Hougen, O. A., Watson, K. M., Ragatz, R. A.,
"Chemical Process Principles (Second Edition)
k3pC2H4O/pH2O1/2 term was larger than that of ,
Part 1", 7 (1954) John Wiley and Sons, Inc., New
k2'pC2H4pO21/2 term in the large regions of W/F. York.
Reasons for the occurrence of these conflicting 10) Twigg, G. H., Proc. Roy. Soc. (London), A188, 92
results is not evident in the present work. (1946).
11) Lapidus, L., "Digital Computation for Chemical
The stationary activity (or catalyst surface) Engineers", 86 (1962) MacGraw-Hill Book Co.
could be estimated to change with pressure of Inc., New York.
the system, because the constancy of ki in Eqs. 12) Vol, Yu. Ts., Shishakov, N. A., Izv. Akad. Nauk
SSSR, Otd. Khim. Nauk, 1962, 586.
(3) and (4) under different pressures was not 13) Kagawa, Sh., Tokunaga, H., Seiyama, T., J. Chem.
attained. The transformation of Eqs. (3) and Soc. Japan (Ind. Chem.Sect.), 71, 775 (1968).
14) Kilty, P. A., Rol, N. C., Sachtler, W. H. M., 5th
(4) to Eqs. (5) and (6), respectively, seems there- International Congress on Catalysis, Preprint 67
fore, to be required. (1972) Palm Beach, U. S.A.
The inhibition effects of water, carbon dioxide 15) Kenson, R. E., Lapkin, M., J. Phys. Chem., 74,
1493 (1970).
and oxygen for ethylene oxidation have been 16) Ayame, A., Kano, H., Harano, Y., Imoto, T.,
neglected in the present work, because it is es- 9th Kyusyu Meeting of Chem. Soc. Japan, Preprint
72, July, (1972).
timated that inhibiting actions to ethylene

Volume 15, No. 2, November 1973