*

, .

.
.
, ,
.
Langmuir -Hinshelwood ,
.
.

(3) .

,
,
. ,
, , Twigg9), Orzechowski 8),
Nault Bolme 7) 5) .
. Twigg9) . ,
,2
(1) , 1 . 1
(2) 1 ,
(3) . 2 ,

.
(1 ) Orzechowski 8) Cambron 1) ,

, . ,
(2 ) 1

1 ,

(3 )
.
(2) (3) (1) ,
Nault Bolme 7) ,
. ,


,
, ,
,
.
5
.
mol% ,
,
.


*
376 1- 5- 1 .

90

 Fig . 1 Experimental apparatus

5)

Fig . 2 Relationship between conversion of ethylene,

yield of ethylene oxide and W/F in the fixed bed
, integral reactor
. ,

.
,
. , ,

3)

. 200 250,

, W/F( ,F

, ) 4.07 23.04 [9-catsec/cm3] ,

. 1 5vol% .

1. 2 .

1 1 2 1
10% 10% w
, 25.09 , F ,

. }V/F

250 . .

200 ,

. ,250 .

. Fig.2 . ,

100250mesh ,
70%
. , 15 .
. ,Fig.2
1 2 ,
Fig.1 .
, .

. (3) .
25mm, 450mm

. , ,

. Langmuir-

Hlnshel wood .
, r1,

, r2
PEG550 . r3 .

5 1 (1979) 91
 (1 ) (2 )
Fig . 3 Relationship between r1, r2 and C1 in the fixed bed differential reactor

(7 )

(8 )

(9 )

Ci/72, Cllr2, C3/ 73

, ,
Fig . 4 Relationship between r3 and C3 in the fixed bed
.
differential reactor

Fig.5

(4 ) . Fig. 5-1 C1r1 , Fig.5- 2 C1/ r2

C1 . Fig. 6

(5 )

, C3 C3/ r3
(6 ) . Eqs. (7), (8), (9)

2 2

Eqs. (1), (2), (3) .

Eqs. (4), (5), (6) Fig.5-1,Fig.5-2 Fig.6

. , .

, ,

Fig.7Fig.8 .Fi9.7

, . ,Fig.8 .

Fig.3Fig.4 . Fig.3

, Fig. 3-1 .

, Fig. 3-2

.Fig.4

.
, Eqs. ,

(4), (5), (6) angmuir- Hinshel wood

. , , .
2 3
, K1'= 1A2C2, 2'= 2A2CG, 1(3'= 3A2CG

92
 (1 ) (2 )
Fig . 5 Relationship between Cl/ r1,C1/ r2 and C1

Fig . 7 The effect of operating temperature

upon the reaction rate constants

Fig . 6 Relationship between C3/73 and C3

,
.

, .

(10 )

(11)

(12 )

(13)

Eqs.( 10), (11), (12), (13) Rung- Kutta

. ,

(14)
Fig . 8 The effect of operating temperature upon adsorp-
(15) tion constants

Fig.9 Fig.10
3.
.Fig.9 , Fig. 10

. ,
Table1
. Table1
. ,

5 1 (1979) 93
 Fig . 9 Experimental conversion vs. calculated one Fig . 10 Experimental yield vs. calculated one

Table 1 Comparison of activation energies obtained by the other investigators

with those obtained by this experiment

Table 2 Comparison of adsorption ,

constants obtained by the
other investigator with those
.
obtained by this experiment

,
Langmuir .Hinshel wood

Nomenclature

.
Al = adsorption constant of ethylene [crn3/ mol ]
KIAIA2, K2AIA2 A2 = adsorption constant of oxygen
K3A2A3 [cm3/mol]
Tabier . A3 = adsorption constant of ethylene oxide
[cm3/ mol]

A, adsorption constant of carbon
Nault Bolme 7) dioxide [crn3/mol ]
Table2 . , Table 2 C1 = concentration of ethylene [mol/ cm3]
Clo = concentration of ethylene at ttie
200 .
inlet of reactor [mol /cm3]
, .
G2 = concentration of oxygen [mol /cm3 ]
Kurilenko 6) C3 = concentration of ethylene

7kcal/ mo1 oxide [mol/ cm3 ]

C4 = concentration of carbon dioxide
, , 5>
[mol/ cm3]
, 13.1 kcal/ moi = activation energy for the reaction
E1
. from ethylene to ethylene

, oxide [ kcal/ mol ]

94
E2 = activation energy for the reaction W = catalyst weight [g]
from ethylene to carbon X = conversion of ethylene [ -]
dioxide [ kcal/ mol ]

E3 = activation energy for the reaction 8 = bulk density of silver catalyst [g/cm3 ]
from ethylene oxide to carbon = yield of Ethylene oxide [ -]
dioxide [kcal/mol]

F total volumetric gas flow rate at a Literature cited

reaction temperature [ cm3/ sec ]

K1 = chemical reaction rate constant 1) Cambron, A. and F. L. W. Mckim: U. S. Pat. 2562857

(1951), Can. Pat. 475366 (1951)
from ethylene to ethylene
2) Kano, H. and T. Kanazuka: J. Chem. Soc. (Japan) (Ind.
oxide [mol/g-catEsec] Eng. Section), 61, 1157 (1958)
K2 = chemical reaction rate constant from 3) Kimura, S.: Jap. Pat. 16606 (1961)
4) Kiryu, T., M. Tabata and F. Yoshida: J. Chem. Soc.
ethylene to carbon dioxide
(Japan) (Ind. Eng. Section), 63, 268 (1960)
[mol/ g- catE sec] 5) Kobayashi, H., S. Arai, M. Kobayashi, T. Hoshikuma and
K3 = chemical reaction rate constant J. Mikami: J. Chem. Soc. (Japan) (Ind. Eng. Section),
from ethylene oxide to carbon 69, 597 (1966)
dioxide [ mol/ g- catE sec] 6) Kurilenko, A. I., N. V. Kul'kova, N. A. Rybabova and
M. I. Temkin: Zhur. Fiz. Khim., 32, 797 (1958)
r1 = reaction rate from ethylene to
7) Nault, L. G., B. W. Bolme and L. N. Johanson: Ind.
ethylene oxide [mol/ g- catE sec]
Eng. Chem. Process and Development, 1, 285 (1962)
r2 E reaction rate from ethylene to 8) Orzechowski, A. and K. E. MacCormack: Can. J. Chem.,
carbon dioxide [mol/ g- catE sec] 32, 388 (1954)
r3 = reaction rate from ethylene oxide 9) Twigg, G. H.: Trans. Faraday Soc., 42, 284 (1946)

to carbon dioxide [mol/ g- catE sec]

(197712 19 ; 10 (
R = gas constant [cal / KE mol] ,197610) )
T = absolute temperature [ K]

Reaction Kinetics for the Synthesis of Ethylene Oxide

from Ethylene on Silver Catalyst

Kunio Kato, Kiyomi Amada and Sachizo Ehara

Dept. of Chem. Eng., Gunma Univ., Kiryu 376

Silver catalyst prepared by the thermal decomposition of silver succinic acid in a nitrogen
atmosphere has not only high selectivity to ethylene oxide in the synthesis of ethylene oxide from
ethylene, but also very steady catalyst activity. In this study, the reaction kinetics for the
oxidation of ethylene was investigated with a differential reactor.
Catalytic oxidation of ethylene consists of the following three simultaneous successive reac-
tions; the oxidation of ethylene to ethylene oxide, the perfect oxidation of ethylene, and the de-
composition of ethylene oxide to carbon dioxide. The reaction kinetics of these reactions was
analyzed by Langmuir - Hinshel wood kinetic theory with surface reaction rate control, and the
reaction rate equations for these reactions were obtained. The calculated conversion of ethylene
and yield of ethylene oxide with these rate equations agreed well with experimental conversion of
ethylene and selectivity obtained by an isothermal integral reactor.

5 1(1979) 95