Math1 Comput. Modelling, Vol. 14, pp. 263-267, 1990 0895-7177/W 53.08 + 0.

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Printed in Great Britain Pergamon Press plc
SIMULATION AND OPTIMIZATION OF THREE EXISTING ETHYLBENZENE
DEHYDROGENATION REACTORS IN SERIES

I. Onal
Middle East Technical University, Ankara, TURKEY
N. Yalcm, E. Uygun, H. Oztllrk
PETKIM Petrochemicals Research Center Yarimca, TURKEY

Abstract. A computer model was developed to simulate the performance of

three commercial reactors in series for dehydrogenation of ethylbenzene to
styrene. The model can be used to predict the performance of dehydrogenation
catalysts in the commercial reactors. In the model program, flow of the reactant
stream through the catalyst bed is treated as one-dimensional plug flow. The
kinetic rate parameters were obtained by using the Conjugate Direction method
as a multivariable search technique so as to minimize the sum of squares of
differences between predicted and actual conversions. The predicted conversions
were found by numerically solving the differential equations for pressure gradient,
energy, and material balances for the main reaction and five side reactions.
The resultsindicate reasonably good simulation of the new plant data as a test of
the model. Various catalyst and reactor combination schemes will later be used
to optimize overall plant performance by means of the computer model developed.

Keywords. Simulation; optimization; search techniques; kinetics

INTRODUCTION of change of catalyst activity is very much

slower than that of the main reaction. After
Styrene is manufactured by dehydrogenation examining various combinations of reactions,
of ethylbenzene over iron-oxide based catalysts. the best set of reactions were:
Conditions of commercial reaction are typically:
550-625 C, I atm. total pressure, and dilution of = 0 C2H3 + H2 (1)
with 6-17 moles steam ’ C2H5
ethylbenzene reactant
per mole of ethylbenzene. Under these conditions, + H2-0 CH3 + CH (2)
0 C2H5 4
conversion to styrene is limited (by equilibrium)
to about 75 % and catalysts in use give 0 C2H5~0 H + C H (3)
selectivities to styrene of 95 %. Major by- 2 4
products are benzene, toluene, and CO . The 0 C2H5 + H2-0 H + C H (4)
overall reaction is strongly endother II?IC and 2 6
the reactors used are typically adiabatic. + 2H20-0 CH3 + CO + 3H ‘5)
’ ‘ZH5 2 2
In Ethylbenzene Dehydrogenation plant, there are 0 C2H5 + 4H20 -0 H + 2C02 + 6H2 !:j
three adiabatic reactors in series. The catalyst
used is Shell-105 (3/16”) for reactor I, and CCI-97
where 0 = C6H5
(l/8”) for reactors 2 and 3. The catalyst is
composed of iron-oxide promoted with potassium
carbonate and chromium oxide. Shell-105 is Only the main reaction was assumed to be
a more active catalyst than CCI-97 which is more reversible. Side-reactions were assumed to
be irreversible.
selective. Superheated steam is added at the
inlet of each reactor. The inlet temperatures
The Reactor Model
of each reactor are 600, 625, and 630 C,
respectively. The operating pressure of the
The The reactor was assumed to be “plug-flow”
reactors is approximately 1.5 atmosphere.
products taken from the third reactor are sent reactor, the flow inside the reactor was radially
uniform, and axial dispersion was ignored. The
to separation columns. The top product of
design equation for a commercial-scale, plug
the ethylbenzene column is recycled to the
flow reactor is given as
inlet of the first reactor. The process flow
sheet is given in Figure I.
dx. -r.
L= J_ (7)
The main objective of this research is to optimize
the reactor and plant operation to increase dw
FO
product yield and profit for dehydrogenation
of ethylbenzene to styrene process.
w = weight of the catalyst
MATHEMATICAL MODEL DEVELOPMENT X. = conversion of ethylbenzene in reaction i
1
i = 1.6
Choice of Reactions reaction rate of ethylbenzene for reaction i
-‘i = i = I,6
In the ethylbenzene dehydrogenation process, 6
reactions were chosen among the 17 possible F. = ethylbenzene feed rate
chemical reactions (Shell 1969, Ralph 1948, Emerson
1973, Sergio 1965), by using the method known as In the model, any limitations of film mass and
delta analysis (Robert 1985). Carbon deposition heat transfer to the catalyst pellet were lumped
and removal were excluded, because the rate into the rate constants. It was found by laboratory

263
 Proc. 7th Int. Conf: on Mathematical and Computer Modelling

F0(l-x,-~2-~3-~4-~5-~6)
dX2
_=- k2
pT
dw F.
FT

* Fo(eE+~I-~2-~4+3x5+6x6)
(16)
pT
FT

FO(I-x,-~2-~3-~4-~5-~6)
dx3
-=- k3
(17)
pT
dw F.
FT

dx4 k4 F0(l-xl-~2-~3-~4-~5-x6)
_=-
pT
dw F.
FT

* FO(eE+x,-x2-x4+3x5+6x6)
(18)
Fig.1. Reactor System pT
FT
experiments that the main reaction (I) was
limited by pore diffusion resistance. The rate F0(1-xl-~2-~3-~4-~5-x6)
dx5
_= -k5
of styrene reaction was therefore found by 09)
pT
multiplying the intrinsic rate with an effective- dw F.
FT
ness factor. The rate equations for the main
and five side reactions were:
FO(I-xI-~2-~3-~4-~5-x6)
dx6
-=- k6
pT
(20)
dw F.
r, = k 1 [I+-] (8) FT
K
eq where;

‘2 = k2 ‘EB ‘HP (9) n = effectiveness factor of the catalyst pellet

PT = total pressure
‘3 = k3 ‘EB (10) FT = total number of moles at any time
= total number of moles initially
‘4 = k4 ‘EB ‘H2 (II) FO
8B = Initial moles of styrene
Initial moles of ethylbenzene
‘5 = k5 ‘EB (12)
(D = Initial moles of hydrogen
E Imtial moles of ethylbenzene
‘6 = k6 ‘EB (13)

and In writing the energy balance equation, it was

assumed that the reactor was nonadiabatic
ki = exp [ Fi - r = I,6 (14) and the radial temperature gradient was negligible.
The energy balance equation was:
6 dx.
where _dT = __=__- (Ts_ T) _- FO ,Z --L AH, (21)
dw pBr F C FTCp ‘=I dw
k. = reaction rate constant for reaction i TP
P. = partial pressure of reactant j
KJ = equilibrium constant where;
Ff” optimization variable for reaction i
T = gas phase temperature
AE,= activation energy for reaction i = bed radius
LB = catalyst bed density
Reaction rate equations were expressed in terms
Cp = average heat capacity of gaseous reactants
of ethylbenzene conversions. The differential
and products
material balance equations for six reactions
were: Ts = temperature of surroundings
U = heat transfer coefficient
dxl k, F0(l-xl-~2-~3-~4-~5-x6) AHi = enthalpy of reaction i
-= l-l--
pT The enthalpies of the reactions were used as
dw F.
FT linear functions of temperature; the heat
capacities were used in the form of quadratic
F 2P 2(e +x )(e +x -x -x +3x5+6x6) functions of temperature (Carl 1976). The
_OTBlEl25
n (15) pressure drop along the reactor was assumed
K to be linear and expressed with the following
eq FTL equation:

P = Pin‘ (Pin- Pout) * -J- (22)

WTOT
 Proc. 7th Int. Conf. on Mathematical and Computer Modelling 265

Fitting the Kinetic Parameters to the Plant Data at fixed activity of catalyst and it can give
insight into the interplay of variables. Catalyst
The activation energies of reactions 1 to 4 were deactivation can be incorporated into the model,
found from literature (Shell 1969, Ralph 1948, but it requires more plant data.
Sergio 1965), and activation energies of the last
two reactions were estimated. During optimization, REFERENCES
the estimated activation energies were taken as
constant and the reaction rate constants were Carl Y.Yaves (1976). Correlation constants
found by adjusting frequency factors F. in the for chemical compounds. Chemical
Arrhenius equation. The change in activation Engineering, 9, 79-87.
energies did not change the values of reaction Charles N. Satterfield (1970). Diffusion. Mass
rate constants of reactions. Transfer in Heterogeneous Catalysis, 1-77,
David M. Himmelblau (1972). Unconstrained
The six material balances were solved Simultaneously nonlinear programming methods. Applied
with the semi-implicit Runge-Kutta Method of Nonlinear Programming, 63-184.
integration (William 1986, Himmelblau 1972). Emerson H.Lee (1973). Iron oxide catalysts
Conjugate Direction Method (William 1986) was for dehydrogenation of ethylbenzene in
used as a multivariable search technique to the presence of steam. Catalysis Reviews,
minimize the sum of the squares of differences 8(2), 285-305.
between the predicted and actual conversions. Ralph R. Wenner and Ernest C. Dybdal (1948).
As a result of this optimization routine, the Catalytic dehydrogenation of ethlybenzene.
kinetic rate parameters F. were obtained. Data Chemical Engineering Progress, 4, 275-286.
for 20 days were available. For each day, the Robert W. Wansbrough (1985). Modelling chemical
optimization was performed and frequency factors r aactors. Chemical Engineering, August
were obtained for each reactor. The arithmetic 5. 95-102.
average of these frequency factors were calculated Sergio Carra and Lucia Farni (1965). Kinetics
and the reaction rate constant equations were of catalytic dehydrogenation of ethyl-
obtained for each reactor. benzene in the presence of steam. Catalysis
Reviews, 8(2), 281-285.
Because Shell-105 (1/8”)/CCI-97 (l/8”) mixture Shell I.P.G. and Crowe C.M. (19691. Simulation
was loaded in the third reactor, a different and optimization of an existing ethylbenzene
method was applied for the examination of the dehydrogenation reactor. The Canadion
third reactor. Third reactor was assumed to Journal of Chemical Engineering, 47,
consist of two reactors. In reactor 3-A, the 183-187.
kinetic parameters of first reactor were used William H. Press, et.al. (1986). Minimization
so that the inlet data for reactor 3-B were or maximization of functions. Numerical
obtained. The kinetic parameters were optimized Recipes, 274-326.
in reactor 3-B for CCI-97(1/8”) such that the
error coming from the use of parameters of
Reactor 1 in Reactor 3-A, was lumped into the
kinetic parameters obtained for Reactor 3-B.
The kinetic parameter estimation results are
listed in Table 1.

The comparison of the results predicted by the

model with actual plant data in terms of styrene
yield and selectivity as well as outlet temperature
for each reactor is shown in Table 2. Table
3 gives the extent of deviation from the
mathematical model prediction for each day
of operation examined. The predictive capability
of the model is reasonably good. The reasons
for the deviations shown are complex, ranging
from errors in flowmeter readings and sample
analysis techniques to the necessary simplicity
of the mathematical model itself.

CONCLUSIONS

Steady-state simulation of three existing plant

reactors for dehydrogenation of ethylbenzene
to styrene is described. The predicted model
results in terms of styrene yield, selectivity,
and outlet temperature are good considering
the limitations of simulating actual plant reactor
data. Conjugate Direction Method as a multivariable
search technique was a useful method for seeking
optimum operating conditions for these reactor
systems involving 6 or sometimes 7 decision
variables. Computer time for each optimization
was about 15 minutes. The model will be
confirmed and further developed in terms of
kinetic parameters such as activation energies
by laboratory reactor tests. The model can
be used for reactor and later for plant optimization
266 Proc. 7th Int. Co& on Mathematical and Computer Modelling

TABLE 1 Kinetic Parameter Estimation Results

Reaction No. u

1 2 3 4 5 6 (cal/hr-cc-K)
------
REACTOR I
CATALYST: SHELL-105
AVERAGE F 8.555 7.391 18.826 5.888 2.504 7.616 2.05
STANDARD DEVIATION FOR F 0.123 0.282 0.445 0.659 0.542 0.207
ACTIVATION ENERGY 21372 21857 49575 22500 19500 27500
(cal/gmol)

REACTOR 2
CATALYST: Ccl-97
AVERAGE F 6.549 7.309 19.113 5.805 2.680 7.842 11.1
STANDARD DEVIATION FOR F 0.206 0.447 0.372 0.830 0.697 0.461
ACTIVATION ENERGY 16462 21857 49575 22500 19500 27500
(cal/gmol)

REACTOR 3-A
CATALYST: SHELL-105
AVERAGE F 8.555 7.391 18.826 5.888 2.504 7.616 28.0
STANDARD DEVIATION FOR F 0.123 0.282 0.445 0.659 0.542 0.207
ACTIVATION ENERGY 21372 21857 49575 22500 19500 27500
(caI/gmol)

REACTOR 3-B
CATALYST: Ccl-97
AVERAGE F 10.877 9.802 20.686 7.199 5.428 9.578 28.0
STANDARD DEVIATION FOR F 0.252 0.576 0.457 1.216 0.314 0.605
ACTIVATION ENERGY 16462 21857 49575 22500 19500 27500
(caI/gmol)

TABLE 2 Comparison of Model vs Actual Results

REACTOR OUTLET TEMPERATURE (K)

STYRENE YIELD Sl-r’RENE SELECTIVITY REACTOR-l REACTOR-2 REACTOR-3

DAY ACTUAL
~__~ MODEL ACTUAL MODEL
- ACTUAL
~--- MODEL ACTUAL MODEL ACTUAL MODEL
15.09.88 49.81 45.40 93.20 92.77 815.00 818.00 851.00 856.00 851.00 853.00
20.10.88 47.17 49.15 92.60 91.43 817.00 819.00 849.00 854.00 854.00 853.00
25.10.88 47.89 48.82 86.65 91.38 818.00 821.00 853.00 853.00 856.00 853.00
27.10.88 46.19 48.03 93.10 91.67 814.00 817.00 852.00 851.00 851.00 853.00
01.11.88 47.90 48.90 92.28 91.33 818.00 819.00 853.00 854.00 856.00 855.00
08.11.88 49.85 48.29 92.26 91.76 814.00 817.00 852.00 852.00 853.00 854.00
10.11.88 49.27 48.39 91.49 91.68 816.00 819.00 854.00 852.00 854.00 855.00
15.11.88 49.61 48.36 90.64 91.63 815.00 817.00 854.00 855.00 855.00 853.00
17.11.88 47.54 47.28 93.04 92.07 813.00 815.00 858.00 852.00 851.00 850.00
22.11.88 46.74 47.76 92.23 91.76 813.00 812.00 859.00 850.00 852.00 853.00
24.11.88 46.81 48.08 91.81 91.77 813.00 814.00 858.00 851.00 851.00 853.00
29.11.88 47.53 47.97 92.20 91.90 813.00 813.00 860.00 852.00 853.00 854.00
01.12.88 48.09 48.40 92.31 91.93 814.00 816.00 853.00 854.00 854.00 853.00
06.12.88 45.92 47.25 92.82 92.11 815.00 813.00 859.00 853.00 852.00 844.00
08.12.88 45.65 47.76 92.50 91.75 815.00 815.00 861.00 853.00 855.00 853.00
20.12.88 47.63 47.83 91.93 92.00 814.00 818.00 855.00 853.00 853.00 854.00
29.12.88 46.94 47.93 92.69 91.72 816.00 815.00 863.00 855.00 853.00 853.00
10.01.89 46.76 48.37 92.07 91.35 817.00 820.00 863.00 859.00 855.00 855.00
12.01.89 47.75 48.34 92.36 91.67 819.00 818.00 853.00 858.00 857.00 858.00
17.01.89 48.79 49.48 91.91 91.10 820.00 819.00 855.00 857.00 859.00 859.00
 Proc. 7th Int. Conf. on Mathematical and Computer Modelling 261

TABLE 3 (+) (-) Deviations for Styrene Plant

(+I!(-) (+)/(-I (+M-1 (+V(-) (+)A-) (+)/(-I

DEVIATION DEVIATION DEVIATION DEVIATION DEVIATION DEVIATION
DATE IN A IN B IN C IN D IN E IN F

15.9.88 - 4.50 - 4.41 - 0.43 3.00 5.00 2.00

20.10.88 2.82 1.98 - 1.17 2.00 5.00 - 1.00
25.10.88 - 1.84 0.93 4.73 3.00 0.00 - 3.00
27.10.88 2.79 1.85 - 1.43 3.00 - 1.00 2.00
01.11.88 1.64 1.01 - 0.94 1.00 1.00 - 1.00
08.11.88 - 1.41 - 1.56 - 0.50 3.00 0.00 1.00
10.11.88 - 1.07 - 0.88 0.19 3.00 - 2.00 1.00
15.11.88 - 1.96 - 1.25 0.99 2.00 1.00 - 2.00
17.11.88 0.26 - 0.26 - 0.97 2.00 - 6.00 - 1.00
22.11.88 1.37 1.02 - 0.47 - 1.00 - 9.00 1.00
24.11.88 1.40 1.27 - 0.03 1.00 - 7.00 2.00
29.11.88 0.64 0.44 - 0.29 0.00 - 8.00 1.00
01.12.88 0.56 0.31 - 0.39 2.00 1.00 - 1.00
06.12.88 1.83 1.33 - 0.72 - 2.00 - 6.00 - 8.00
08.12.88 2.70 2.11 - 0.75 0.00 - 8.00 - 2.00
20.12.88 0.18 0.20 0.08 4.00 - 2.00 1.00
29.12.88 1.61 0.99 - 0.97 - 1.00 - 7.00 0.00
10.01.89 2.16 1.61 - 0.71 3.00 - 4.00 0.00
12.01.89 1.03 0.60 - 0.68 - 1.00 5.00 1.00
17.01.89 1.23 0.69 - 0.81 - 1.00 2.00 0.00

A : TOTAL CONVERSION OF ETHYLBENZENE TO STYRENE AND OTHER BY-PRODUCTS

B : YIELD TO STYRENE
C : SELECTIVITY TO STYRENE
D : EXIT TEMPERATURE FOR REACTOR-l
E : EXIT TEMPERATURE FOR REACTOR-2
F : EXIT TEMPERATURE FOR REACTOR-3

““I 14-J