KINETICS OF CATALYTIC DEHYDROGENATION

OF ETHY'LBENZENE T O STYRENE
SERGIO C A R R A AND LUCIO FORNI
Istituto Chzmica Fisica, Unioersitd di Milano, Milan, Italy

The rate of dehydrogenation of ethylbenzene to styrene has been investigated employing both differential
reactor and integral reactor techniques a t temperatures from 495" to 630" C. and pressures from 1 to 1 1
atm. No influence of the HnO-ethylbenzene ratio on reaction rate has been observed. In a preliminary investigation, the adsorption coefficient of styrene relative to ethylbenzene was found to b e equal to 8.0 and
almost independent of temperature. Experimental data have been interpreted on the basis of a kinetic
model, which itakes into account the chemisorption of ethylbenzene and styrene on the catalyst surface. At
the highest temperature small amounts of cracking by-products (benzene and toluene) were present and
their formation has been kinetically interpreted.

dehydrogenation of ethylbenzene (EtB) is the most important method for the industrial manufacture of styrene
(Sty). The reaction is usually carried out a t temperatures
above 600" C. with a large amount of water as diluent (from
2.5 to 3 parts by weight of water per part of ethylbenzene).
In spite of the importance of the process, few kinetic data have
appeared so far in the literature (2, 6 ) . For this reason process
kinetics have been extensively investigated \vith the aim of
obtaining a kinetic model useful for both technical application
and interpretation of the reaction mechanism. Some data
concerning this research have been published ( 4 ) . Their
interpretation emphasized the competitive adsorption of
ethylbenzene and styrense on the catalyst. Such data have been
reinvestigated no\\'. together with a new series of runs in an
enlarged analysis, from which a more complete model of the
reaction kinetics has been formulated.

THE

Experimental

Materials. EtB was an industrial product, purified by

distillation; its purity was tested by gas chromatography
(>99%).
T h e industrial type Shell 105 catalyst had the
follo\ving composition (per cent by weight) : FenOs93, C r 2 0 35,
KOH 2. This catalyst was ground and mechanically classified; sizes between 10- and 30-mesh were separated and used
throughout.
Equipment and Experimental Procedure. Three stainless
steel reactors (.4,B, and C) of the same size (2-cm. diameter,
30-cm. length) were em.ployed; they differed only in the heating method.
Reactor ,4was immersed in a molten salt bath of the following composition: N a N 0 2 40%, N a x O 3 7 7 , > K N 0 3 537,,',.
The feed mixture \vas preheated in a coiled pipe preheater,
which was immersed in the same bath (internal diameter of
the pipe, 4 mm. ; number of coils, 19 ; diameter of coils? 10 cm.),
Reactor B was identical to A, but immersed in a molten
lead bath.
Reactor C was directly heated by electrical resistance
heaters.
In all three reactors the catalyst was contained in a small
stainless steel basket placed in the middle of the reactor.
The bottom of the basket was formed of metal mesh.
The temperature was controlled by an electronic regulating
device connected with three thermocouples; the first \vas
placed at the feed point., the second immediately above. and
the third immediately beloiv the catalytic bed. T h e tempera-

ture constancy was very good with reactors A and B ( *1 ' C.)
and good with reactor C ( i 3 O C.).
Some experiments \<ere performed without catalyst to
determine Xvhether any conversion \could take place.
Water and ethylbenzene in the desired ratios \vere mixed,
preheated, and successively fed into the reactor. I n some of
the runs, which had been suitably chosen, we verified that
mass-transfer processes did not constitute the rate-limiting
step. Ethylbenzene feed rates \vere between 0.5 and 2.0
grams per minute in all but seven of the 51 runs carried out
(three runs were below 0.5 and four above 2.0 grams per
minute).
To verify the stability of the catalyst, we performed a series
of runs with fresh catalyst, and determined the variation of
per cent conversion us. reaction time. After a small initial
fall during the first 100 minutes starting from the feed, the
conversion remained constant.
As all runs were conducted with fresh catalyst, the samples
for the analysis of reaction products were \vithdrawn 2 hours
after the start of feeding. During reaction at the highest
temperature, some samples of the reaction gases were withdrawn and successively analyzed by gas chromatography.
The chief component of the reaction gases was hydrogen, which
contained small amounts of cracking gases. In Table I a
typical analysis is given.

Table 1.

Typical Run Analysis

Temperature, " C .
Pressure, atm.
Feed rate of EtB, g./min.
Outgoing gas flow, literslmin. (S.C.)
HZO/EtB ratio (weight)
Coniwsion. sc
To Sty
To benzene
To toluene
Selectix ity, 7c
Analvsis of gases. Yc
Hz
Air
CH4
COZ

CH z=CH
CO
CHa-CHa

VOL. 4

630
1

246
0 20
3.00
33.25
1 50
1 13
92 50
88 29
0.70
2.56
6.19
1 83
0 19
0 24

NO. 3 J U L Y 1 9 6 5

281

10

8
L

s
'

3
40

80

c
Figure 1 .
tion rate

(mm)

Effect of ethylbenzene partial pressure on reac-

Temp., 495' C.

10

% s t y Feed

Three analytical methods have been tested : titration of

styrene double bond by mercuric derivative formation (5);
refractometry; and gas chromatography by means of Fractovap. Model B,'f, C. Erba apparatus.
In the last method a stainless steel column? 6 mm. in diameter and 2 meters long, filled with 207, didecylphthalate on 30to 60-mesh Celite was employed. Column temperature :
110' C.; carrier gas: hydrogen; retention time ratios: benzene 1 , toluene 2, EtB 3.75, Sty 5.38.
Calibration factors equal to unity resulted for all the substances. The three methods agreed with a maximum difference of 1%. Consequently the refractometric method )vas
employed, because of its rapidity, for low temperature runs
when no cracking products were present in the reaction
products. At higher temperatures gas chromatography was
employed to detect benzene and toluene together with ethylbenzene and styrene.

Figure 2. Effect of styrene percentage in feed mixture on reaction rate

0

495' C.

505' C.

kbEPE

7 =

+ c biPi

(1)

T h e results shown in Figure 1 clearly show that: at a total

pressure of 1 atm., reaction rate is independent of both the
H20,'EtB ratio and the partial pressure of ethylbenzene.

0.4
x

0,2

80

40

W/F
Relation of conversion and contact time

0 565' C.
A 595'C.
0 630'C.
Calculated from Equation 7 and at 630' C. from Equations 7 and 14

I & E C PROCESS D E S I G N A N D DEVELOPMENT

5 1 5 ' C.

Catalytic dehydrogenation reactions may be interpreted ( 7 )

employing a kinetic model in which it is assumed that the
reaction is unimolecular on the catalytic surface. Far from
equilibrium conditions, the following rate law corresponds to
the model:

0.6

Figure 3.

Reaction Kinetics

Runs were carried out in reactor A at 495', 505', 510', and

515' C. with a differential reactor technique. T h e degree of
reaction of ethylbenzene u-as kept below 37,.
A first set of runs \vas performed a t 495' C. with different
values of the H 2 0 'EtB ratio, in order to investigate the influence of steam on the reaction rate. A second set of runs
\vas made at different temperatures with a HZOtEtB ratio
equal to 5 and different amounts of styrene in the feed mixture.

510' C.

The results are reported in Figures 1 and 2 . In reactor 3

experiments were carried out at 565' and 595' C. lvith a
H20,'EtB ratio of 5.
Graphical plots of the integral conversion data are given in
Figure 3. In reactor C reactions were carried out at 630' C..
working bvith a H20,'EtB ratio of 3 ; three series of runs were
made working at 1. 6, and 11 atm.. respectively.
Results are reported graphically in Figures 3 and 4 ; contact
time 7 = Tt:'F is expressed as grams of catalyst per mole of
ethylbenzene per hour.

Experimental Results

282

30

20

Analysis

120

40

20
W/ F

Figure 4.

10

Relation of conversion and contact time

20

30

W/F

Calculated from Equations 1 4 and 1 5

0 sty
0 By-products
Temp., 6 3 0 ' C.
Press., 1 atm.

Figure

5.

Relation of conversion and contact time

Calculated from Equations 1 4 and 1 5

0
Sty
0
products Temp.,

T h e partial pressure of ethylbenzene has only a small influence on reaction rate, as shown by runs at 630' C. under a
total pressure above 1 atm. (Figures 4, 5. and 6). An increase
in pressure from 1 to 11 atm. gives an increase in reaction
rate \\ith a factor slightly less than 2 . O n the other hand. as
pointed out in Figure 2. the amount of styrene in the feeding
mixture strongly affects the reaction rate. Because of the high
operating temperature,;. the equilibrium adsorption constant
of hydrogen should have a considerably lower value than the
corresponding constanis for hydrocarbons. \%:e may assume
that. far from equi1ib:rium conditions at atmospheric pressure. the folloiving simplified equation expresses the rate of reaction adequately:

6 3 0 ' C.

10

Press.,

6 atm.

20
W/F

Figure 6. Relation of conversion and

contact time

I n this equation the approximation (1

biP,)
1

I
I( c b , P , )

is

Calculated from Equations 1 4 and 1 5

0 Sty
0 By-products Temp.,
Press., 1 1 atm.

justified by the independence of the reaction rate from the

ethylbenzene partial pressure. as \ve found \\.hen only ethylbenzene and ivater \?ere fed.
I t follo\vs also that the relative adsorption constant. 2 . of
hydrogen. relative to :styrene. can be neglected. Let X indicate the degree of Conversion of ethylbenzene to styrene, and
.\ the ratio of moles of styrene to moles of ethvlbenzene in the
feed mixture; Equation 2 becomes

dX dT

(1 - X ) k

(1

- X) + z ( X

+ ,V)

(3)

630" C.

4 L

By integration between 0 and X \ve obtain

2 .

'v

using the approximation --In (1 - X)'V X.which is justified

by the lo\\ conversions obtained in a differential reactor.
Equation 4 has been ,applied to the runs in \\hich pure ethylbenzene \%asfed (LV = O), uhile temperatures of 495'. 505'.
510'. and 515' C. were steadily maintained in the reactor.
L-alues of the constant k thus obtained are given in Table 11.
expressed as moles per minute per gram of catalyst.

1.o

0.5

1.5
1 /M

Figure
0

495OC.

7.

Relation of

k / r to 1 / M

Experimental values
505'C.
0 510C.

VOL. 4

NO.

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1 9 6 5

283

Table II.

494
505
510.5
514
565
595
630

Reaction Rate Constants

T h e integral. I. \\as calculated for all the experimental conversions. taking z = 8.03 (average of 8 08 and 7.98). previously
determined in the differential reactor runs.
L'alues of k l for the t u 0 temperatures of 565' and 595' C.
were determined by least squares, minimizing the function

0.53

0.72
0.89
1.08

5.57
13.53
100.00

1.33

T h e z constant was determined kinetically Lvhen reaction

product (Sty) was fed together \vith reagent (EtB). Because
the additional substance combined with a part of the catalytically active surface, a decreased reaction rate was observed.
Let M indicate the mole percentage of ethylbenzene in the
feed mixture of ethylbenzene and styrene; Equation 2 may
then be written as
r

M
z+M(l

-2)

(5)

and, rearranged, as

From this equation, plotting k / r against l , ; M , a straight line

should be obtained. the slope of Xvhich yields t, and the intercept (1 - 2 ) . T h e experimental data are sh0Lz.n in Figure 7,
which confirms the validity of Equation 6. Examination of
the figure shows no significant influence of temperature on z .
T h e best straight line, evaluated by least squares, gives the
folloning values for z :
8.08

where ( T I ' F ) , is the experimental value of contact time corresponding to conversion A'. and the sum is extended over all
experimental data at a given temperature T h e result is

c IJ2
T h e values of k l : obtained from Equation 12. are given in
Table 11. Calculated data are compared in Figure 3.
'Io interpret the runs at 630' C. and atmospheric presiure
it is necessary to consider the side reactions and consequently
to give a suitable form to \Ir(PE) in Equation 8. T\vo hypotheses were considered. T h e first assumes that the reaction
is pseudo-first-order; the second that the reaction is unimolecular heterogeneous with an adsorption on the catalyst
of the same kind as for the main reaction. In the first case
\Ir(P,) takes the form:
\ I r ( P E ) = P,q

(1 3 )

in the second:

from intercept

7.98 from slope

In the previous work ( 3 ) . z was calculated by a different
method? which gave a slightly different value.
In the interpretation of runs using the integral reactor technique, the reverse reaction, assumed to be second-order,
must also be taken into account because of the relatively high
degree of conversion.
T h e general kinetic scheme must also consider side reactions,
because of by-product formation at 630' C.
In formulating this scheme, an over-all degree of conversion,
Y,of ethylbenzene into benzene plus toluene has been used.
assuming that the course of the side reactions should be parallel
to that of the main reaction. T h e kinetics of the process were
described by means of the following system of differential
equations,

In Equation 14 the adsorption of benzene and toluene has been

neglected, because they Lvere present only in small amounts.
T o choose between the t\vo kinetic models, a preliminary
approximate calculation \vas performed. Equation 8 \vas
integrated substituting Equations 13 and 14: respectively
(t = 8.03). and using values of PE ( = P - Ps - Px - PB -

T h e equilibrium constant has been calculated by the following

equation ( 3 ):

1.1

temperatures of 565' and 595' C.. since appreciable

amounts of by-products \vere not found, we can neglect Equation 8 and integrate Equation 7 directly,

At

284

I & E C PROCESS D E S I G N A N D D E V E L O P M E N T

1.3

1.2
1 O?/T

Figure

8. Arrhenius plot

Table 111.

Reaction Rate Constants Evaluated from Equations

13 and 14

Temperature,
W,F
2 25
12 50
27 50
55 00

630 C. Pressure. 1 atm.

k? X 704
k2 X 104
(Eqs. 8 and 73)
(Eqs. 8 and 7 4 )
1.103
15 210
0.986
8 730
1.186
7 546
1.432
6 747

The activation energy determined is particularly high, but

qualitatively confirms the experimental necessity for high
operating temperatures. It is significant that our z parameter
is practically independent of temperature and represents the
equilibrium constant of the reaction

S,

___
d( M -;F)

--.
cy

+ PE + zPS

which includes the smal?. effect of pressure on reaction rate.

Equations 15 and 8 were used to derive the following approximate parameter values:
cy

= l,bE =

k l = 1.5

0.06 atm.

mole min.- g. cat.-

k y = 1.33 X

mole min.- g. cat.?

In Figures 4, 5? and 6 the agreement between evaluated and

experimental data is shown. A comparison ivith Figure 3
shows that replacing
b,P,) by (1
b,Pi) did not sub-

(E
i

stantially improve the interpretation of data at 1 a t m . ; therefore

the approximation introduced in the kinetic model of Equation
2, used for the interpretation of atmospheric pressure runs, is
justified.
In Figure 8 the Arrhenius plot for the k l constant listed in
Table I1 is given. From its slope, the activation energy of the
main reaction (45.8 cal. per mole) has been evaluated.

(16)

where E = EtB. S = Sty. C = an active center of the catalyst.

and g = the substance in the gaseous phase.
The enthalpy change of Reaction 16

PT) taken from curves drawn through experimental data.

The values obtained (Table 111) clearly show that the second
hypothesis represents the kinetics of the process better. Both
constants k , and k ? at 630 C. were calculated by integrating
the system of Equations 7 and 8 by the Runge and Kutta
method and verifying by trial and error the agreement between
experimental and calculated data. This agreement, using the
final values of the parameters, is sho\sn in Figures 4, 5, and 6 .
.4 more general analysis of all the runs at 630 C. was made by
replacing Equation 7 by the kinetic equation

+ EC % E, + SC

AHo

d log z
4.57 T 2 -

dT

will therefore be almost equal to zero? while the corresponding

free energy change will be:
AFO = -4.57

T log z = -4.136 7

(18)

The side reactions seem to be well interpreted by the hypothesis that they take place after adsorption of the reagent on
the catalyst surface, Lvith reaction paths parallel to the main
reaction. The small influence of pressure, Lvhen increased from
1 to 6 and to 11 atm.. may probably be interpreted by a more
complex kinetic model.
Nomenclature

b z , b,? = adsorption coefficients of EtB and Sty

F
= feed rate of reagent: mole,hour
j
= index number of experimental data
k
= reaction rate constant, mole min. g. cat.
K
= equilibrium constant of dehydrogenation reaction.
atm.
= EtB mole percentage in feed mixture
M
;V
= Sty, EtB mole ratio in feed mixture
PE: Ps: P H , PB:PT = partial pressure of EtB? St?: hydrogen:
benzene. toluene, atm.
reaction rate, mole min. g cat.
absolute temperature. OK
catahst weight, g
conversion degree of EtB to Sty
toluene
conversion degree of EtB to benzene

bS
-- =
bE

relative adsorption coefficient

1 =
bE

reciprocal of adsorption coefficient of EtB

L 1

g. cat.
_
mole EtB, hour

= contact time. _

Conclusions

literature Cited

The proposed kinetic model is satisfactory for interpreting

the kinetics of the dehydrogenation of ethylbenzene to styrene.
T h e system of Equations 7 and 8 may therefore constitute the
basis for reactor design. However, an accurate investigation
of reactor performance a t temperatures higher than 630 C .
would require some additional kinetic information about the
influence of the temperature on the rate constant of by-product
formation.

(1) Balandin, A. A , , A d m n . Catalysis 10, 96 (1958).

(2) Balandin. A. A , , Tolstopyatova, A. A . : Zh. Obshch. Khzm. 17,

2182 (1947).
(3) Bogdanova. 0. K., Shcheglova, A . P.: Balandin. A. A,;
Beloniestnykh. I. P.. Petrol. Chem. USSR 1, 1, 120 (1962).
(4) Carrh, S., Chim. Ind. 45, 949 (1963).
(5) Martin, R. LV.. Anal. Chem. 21, 921 (1949).
(6) LVenner, R. R.; Dybal: E. C.? Chem. Eng. Progr. 44, 275 (1948).

RECEIVED
for review December 4. 1964
ACCEPTEDMarch 30. 1965

VOL. 4

NO. 3

JULY

1965

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