A

ELSEVIER Applied Catalysis A: General 113 (1994) 89-102

Intrinsic kinetics and industrial reactors modelling

for the dehydrogenation of ethylbenzene to styrene
on promoted iron oxide catalysts
B.K. Abdalla”, S.S.E.H. Elnashaie&*, S. Alkhowaite?,
S.S. Elshishinib
“Chemical Reaction Engineering Group (CREG), Chemical Engineering Department King Saud University,
P. 0. Box 800, Riyadh 11421. Saudi Arabia
%Zhemistry Department, Faculty of Science, King Saud University, Riyaa%, Saudi Arabia

(Received 3 February 1994)

Abstract

In this preliminary investigation two approaches are used to obtain intrinsic kinetics for the catalytic
dehydrogenation of ethylbenzene to styrene on different promoted iron oxide catalysts: ( 1) A rigorous
heterogeneous model based on the dusty gas model for the catalyst pellets is used to extract intrinsic
kinetics from the data of an industrial reactor. (2) A pseudohomogeneous model is used to extract
intrinsic kinetics from the results of a laboratory fixed bed reactor packed with in-house prepared
powder catalysts with negligible diffusional resistances. The extracted intrinsic kinetics were used in
the heterogeneous model to simulate the industrial reactor and the results for the three in-house
prepared catalysts are compared with those of the industrial reactor.

Keywords: Dehydrogenation; Ethylbenzene; Intrinsic kinetics; Iron-oxide., Promoters; Styrene

1. Introduction

Despite the industrial importance of the catalytic dehydrogenation of the ethyl-

benzene to styrene no studies are reported in the literature regarding the develop-
ment of a kinetic model for the intrinsic kinetics of this multiple reaction system.
All kinetic models reported in the literature are effective rates obtained from indus-
trial reactors where diffusional resistances strongly affect the rates of reaction
[l-8].

*Corresponding author. Fax. ( + 966- 1) 4633563, e-mail F45KOO6@SAKSIJOO.BITNET.

0926-860X/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved

SSDIO926-860X (94)00028-P
90 B.K. Aba!alla et al. /Applied Catalysis A: General 113 (1994) 89-102

In 1973 Lee [ 91 published an interesting review paper on this industrially impor-

tant reaction and discussed many important catalysis aspects of this reaction. How-
ever, Lee [9] did not present a kinetic model for the reaction. Sheel and Crowe
[ 81 investigated this reaction and suggested taking six independent reactions into
consideration. They fitted their kinetic model to industrial data using a pseudohom-
ogeneous model and therefore the kinetic parameters they obtained are obviously
not intrinsic. A rigorous heterogeneous model is used in this investigation to extract
intrinsic kinetics. Furthermore a laboratory reactor with fine catalyst pellets with
negligible diffusional resistances was constructed and operated over a wide range
of parameters and for different catalysts. A one-dimensional pseudohomogeneous
model (v’s = 1) is used to obtain intrinsic kinetics parameters from the results of
this laboratory reactor. In both cases the simple kinetic model of Sheel and Crowe
[ 81 was used in the investigations.

2. Derivation of mathematical model

The six reactions taken into consideration are [ 81:

C6 H5CH, CH, + C6H5CHCH2 + H2 (1)
C6H5CH2 CH3 + C6H6 + C2H4 (2)
C6HSCH:!CH, + H2 -+ C6H5CH3 + CH, (3)
2H20+C2H_, -+2CO+4H, (4)
H20+CH4 +CO+3Hz (5)
H20+CO-+COa+Hz (6)
The rate equations are given by:
R, =k,(p,, -PST PHJ Km > R2 = k2 PEB R, = k PEB PHZ (7)
R4 =~PH~oP% R5 =~PH~OPMET& =MPTIT~)PH~oPco (8)
the rate constants of these reactions are given by:
ki =exp[A; - (Ei/RT)] (9)
The model equations of the catalyst pellets and of the reactor are given by:
the mass balance equations of the components for the catalyst pellets are expressed
as follow:
dNi/dZ=&ri (10)
where ri is the rate of disappearance of component i, and the boundary condition
is,
at Z=O, Ni=O
 B. K. Abdalla et al. /Applied Catalysis A: General 113 (I 994) 89-102 91

the dusty gas model equations for the intraparticle multicomponent diffusion of the
components are given by [ lo] :

-dCi/&=NiIDKei + k yiNby”” (11)

j-l e1.J
i+j

and the boundary condition is,

at z=r,, Ci(Tp) =Ci,

the effectiveness factors are computed using the following equations:

re
1
77i= - Ridz (12)
rpRi
0

The heterogeneous model equations are given by:

dXildl= TipcABRif FEeF (13)

where i is for reactions 1, 2 and 3 and Xi is the fractional conversion of the

ethylbenzene.

dX,Idl= vjPcABRjIFH,o, (14)

wherej is for reactions 4,5 and 6 and Xj is the fractional conversion of steam.
The Ergun equation ( 12) is used to compute the pressure profiles along the
reactor.

(1 -•)Co 150(1-E)Po +1
dPld2 = - 1. lo-’ (1%
Dp EPG gc 4

The energy balance equation for adiabatic operation is given by:

dTIdl= 5 ( -AHi)qiRihABI f FjCpj (16)

The pseudohomogeneous model equations are obtained by setting q’s equal to

1.Oin equations ( 13, 14 and 16) ; and using equation ( 15) to compute the pressure
profile along the length of the reactor. For the heterogeneous model the two-point
boundary value differential equations of the catalyst pellets are solved using the
global orthogonal collocation technique [ 111 and the bulk gas phase equations are
solved using an JMSL (Math/PC-Libaray ) integrating subroutine with automatic
step size control (DGEAR) [ 121.
92 B. K. Abahlla et al. /Applied Catalysis A: General 113 (1994) 89-102

3. Experimental

3.1. Industrial catalyst and reactor data

The characteristics of the industrial reactor are given in Table 1.

The initial guesses for the pre-exponential factors and activation energies for the
effective reaction rates were taken from the work of Sheel and Crowe [ 81 and
Crowe [ 141 and the equilibrium constant is given in refs. [ 10,161.
The heterogeneous model can be used to extract the intrinsic kinetics constants
from these industrial data using the following simple iterative technique:
The kinetic data of Sheel and Crowe [ 81 and Crowe [ 141 are used in the
heterogeneous model. The results obtained give low conversions compared to those
of the industrial reactor. The conversions of the six reactions obtained from the
industrial reactor are divided by the corresponding ones obtained from the hetero-
geneous model. Multiplying factors are obtained for the six reactions. The rate
equations are then multiplied by the corresponding factors and the program is rerun.
The results obtained are again compared with the industrial ones and new multi-
plying factors are obtained. The above procedure is iterated until the results obtained
are very close to the industrial ones. The kinetic parameters of the intrinsic rate
constants obtained are given in the second and third column of Table 7. The
heterogeneous model with the obtained intrinsic kinetics gives results which are
very close to the results of the industrial reactor as shown in Table 2.

Table I
Industrial reactor specification, catalyst properties and feed conditions [ 8I

Symbol Value Dimension

Reactor diameter I .95 m

Catalyst bed depth 1.70 m
Catalyst density 2146.27 kg/m’
Catalyst diameter 4.7 mm
Catalyst pore radius 2400 .A
Catalyst porosity 0.35
Catalyst tortousity 4.0
Inlet pressure 2.0 bar
Inlet temperature 922.59” K

Inlet gas molarflow-rates

Ethylbenzene EB 36.87 kmol EB/h
Styrene ST 0.67 kmol ST/h
Benzene BZ 0.11 kmol BZ/ h
Toluene TOL 0.88 kmol TOL/h
Steam Hz0 453.10 kmol H,O/ h
Total molar feed TMF 491.63 kmol/h
Total mass flow TMFR 12238.79 kg/h

“Corrected by Crowe [ 131.

 B.K. Abahlla et al. /Applied Catalysis A: General 113 (1994) 8%102 93

Table 2
Results of the heterogeneous model as compared with the industrial reactor data

Industrial reaCtor Heterogeneous model

Molar flow-rate Conversion and Molar flow-rate Conversion and

(kmol/h) yield (%) (kmol/h) yield (46)

Conversion
EB 19.45 47.26 19.29 47.45
Hz0 -0 -0 447.32 1.26
Yield
ST 15.56 40.37 15.53 40.17
BZ 1.5 3.77 1.64 4.12
TOL 2.03 3.12 2.07 3.17
Exit press. (bar) 2.32 2.83
Exit temp. (K) 850.0 851.10

“Output water is not measured in plant operation [ 81.

3.2. In-house prepared catalysts and laboratory reactor data

Preparation of the catalyst

The catalysts studied were prepared by wet mixing iron oxide (cy-Fe,O,) , potas-
sium carbonate (K&O,) and the corresponding amount of promoter in a rotary
evaporator. Water was removed under vacuum at 70°C until a consistency of a
flowable powder is obtained. The catalysts were dried at 120°C and calcined at
600°C overnight with air flowing at 100 ml/min. Three catalysts of different
compositions were prepared: catalyst (A) 80 wt.-% Fe*O,-20 wt.-% K20 (8OFe-
20K), catalyst (B) 75 wt.-% Fez03-20 wt.-% K@-5 wt.-% CeOz (75Fe-20K-
5Ce) and catalyst (C) 70 wt.-% Fe203-20 wt.-% K@-5 wt.-% CeO,-5 wt.-%
CrzO, (70Fe-20K-5Ce-5Cr). The three catalysts differ considerably in composition
from the industrial catalyst considered in this study which has the following com-
position: 62% Fe,O,, 36% KzC03 and 2% Crz03 (62Fe-36K-2Cr).

Table 3
Surface characteristics of the three in-house prepared catalysts

Catalyst Density x 10-j &TX lo-” v,x 103 rPX lo9

(kg/m?) (m*/kg) (m’/kg) (m)

A 4.54 1 15.333 0.1288 20.7

B 4.920 28.426 0.1838 15.5
C 4.939 34.112 0.1745 12.3

Catalyst A 80% FqOj-20% K20.

Catalyst B 75% Fe*O,-20% K&-5% CeO,.
Catalyst C 70% FezOx-20% K&--5% CeO,-5% Cr,03.
94 B. K. Abdnlla et al. /Applied Catalysis A: General 113 (1994) 89-102

lllll14

1 - AIR O- STEAM GENERATOR

2 - He 0 - EB METERING PUMP
3 - PRESSURE REGULAlOR lo- PREsClRE GAUGE
4 - GAS PUR!FIER 1, - REACTOR TUBE
5 - NEEDLE VALVE 12 - TUBULAR FURNACE
5- ROTAUETER 13 - CONDENSER
,- SHUT-OFF VALVE lb - SAMPLE CONDENSATE
COLLECTOR

Fig. 1. Schematic diagram of the experimental set-up. ( 1) Air; (2) He; ( 3) Pressure Regulator; (4) Gas Purifier;
(5) Needle Valve; (6) Rotameter; (7) Shut-off Valve; (8) Steam Generator; (9) EB Pump; (10) Pressure
Gauge; ( 11) Reactor; ( 12) Furnace; ( 13) Condenser; ( 14) Sample Condensate Collector.

Partial characterization of the catalyst

The surface properties, namely, specific area, total pore volume and mean pore
radius of the three catalysts were determined from nitrogen adsortion isotherms at
77 K using Micromeritics Accusorb 2100 under reduced pressure of 10m5 Torr ( 1
Torr = 133.3 Pa). Prior to measurements the samples were outgassed at 250°C
overnight. Data for the partial characterisation of the three catalysts is shown in
Table 3. The addition of CeO, and CrzO, promoters causes an increase in the
structural density of the catalyst as determined by helium pycnometry. The addition
of CeO, promoter results in an almost two-fold increase in the surface area. A
further increase, although not as notable, results from the addition of, Cr,03 pro-
moter, indicating a substantial effect of CeO, on surface area and a lesser effect of
Cr203.
The total pore volume in Table 3 is calculated from:
v, = 15.88 * lo-“v,, (17)
where V,, is the volume of nitrogen adsorbed at saturation. The total pore volume
increases from 0.1288. low3 m3/kg for the non-promoted catalyst A to
0.1838. 10e3 and 0.1745 - 10e3 m3/kg for the promoted catalysts B and C, respec-
tively.
The mean pore radius is calculated using the relation:
 B.K. Abdalh et al. /Applied Catalysis A: General 113 (1994) 89-102 95

rp = 2.5 *104VPISBET (18)

r-decreases from 20.7. lo-’ m (207 A) to 15.5. lo-’ (155 A), 12.3. lo-’ (123
A) by the addition of promoters. This result together with the increase in the total
pore volume and the total surface area with the addition of promoters, suggests that
these promoters open up a large amount of small pores, increasing the total surface
area and the total pore volume.

3.3. Reaction equipment and experimental procedure

Fig. 1 shows a schematic diagram of the experimental equipment used. A stream

of helium at designated flow-rate was metered through a steam generator while
another line served as a carrier of feed as dispensed from a Masterflex liquid
metering pump. A heating tape at 200°C placed before the reactor prevented con-
densation of the ethylbenzene. The catalyst bed is composed of a catalyst mixture
( 1.Og catalyst/ 1.Og ceramic) situated between two inert ceramic layers inside the
Table 4
Feed conditions and experimental results of catalyst A

Temp. He rate Press. EB %C BZ %S TOL %S ST %S

(“C) (ml/min) (bar)

EB feed= 0.145 mUmin. Hz0 feed = 0.362 mUmin

500 330 1.468 2.03 1.23 98.77
530 330 1.468 3.02 2.46 97.54
560 330 1.463 3.80 1.84 98.16
590 330 1.463 5.96 2.03 97.97
620 330 1.433 11.01 2.54 97.46
650 330 1.363 19.89 3.55 0.45 96.00
680 330 1.313 32.01 4.6 1 I .57 93.82
710 330 1.263 38.66 6.35 2.76 90.89
740 330 1.313 5 I 46 8.09 5.86 86.05

EB feed = 0. I53 ml/min, Hz0 feed = 0.4833 ml/min

620 950 I .393 4.30 2.41 97.59
620 750 1.363 4.46 3.41 96.59
620 550 1.333 4.46 3.80 96.20
620 350 1.288 5.00 5.07 94.93
620 150 1.213 4.99 6.90 93.16

EB feed= 0.151 ml/mitt. Hz0 feed = 0.4875 mhin

620 400 1.263 17.57 2.20 97.80
620 400 1.263 9.52 3.12 96.88
620 400 1.263 6.09 3.98 96.02
620 400 1.263 4.89 4.76 95.24
620 400 1.263 4.57 5.19 - 94.81
620 400 I .264 4.61 4.73 - 95.27
620 400 I.264 4.34 4.74 95.76

-: Value was too small to be detected.

96 B.K. Abahlla et al. /Applied Catalysis A: General 113 (1994) 89-102

65 cm long and 0.75 cm I.D. stainless steel reactor tube. The reactor set-up is heated
by a temperature-controlled tubular furnace. Products and unreacted feed are passed
through a condenser and sample condensates are collected for analysis.
prior to the experimental determinations, the bed was first heated overnight at
600°C under a stream of air to remove contamination. Both feed and product were
analysed by a Varian Aerograph model 940 gas chromatograph using a flame
ionization detector (FID) . The column used was a 10 ft. X l/8 in. stainless steel
tube packed with 20% DC-200 on Chromosorb W. The catalyst performance was
expressed by the following formulae:
Ethylbenzene conversion, %C = (ST + BZ + TOL + EB (outlet) ) /EB (inlet)
. 100; styrene selectivity, %S = ST/(ST + BZ + TOL) ’ 100. The results for
catalysts (A), (B) and (C) are shown in Tables 4-6.

Table 5
Feed conditions and experimental results of catalyst B

Temp. He rate Press. EB %C BZ %S TOL %S ST %S

(“0 (mUmin) (bar)

EB feed = 0. I39 mUmin, H,O feed = 0.3348 mUmin

500 460 1.113 0.09 1.73 98.27
530 460 1.113 1.52 2.54 _ 97.46
560 460 1.113 2.88 2.01 _ 97.99
590 460 1.113 5.59 1.96 _ 98.04
620 460 1.113 10.53 2.33 91.67
650 460 1.113 14.92 3.88 _ 96.12
680 460 1.113 26.11 3.99 1.01 95.00
710 460 1.113 40.91 4.69 1.96 93.35
740 460 1.113 53.14 6.57 4.05 89.38

EB feed = : 0. I36 ml/min. Hz0 feed = 0.338 ml/min

620 2875 1.113 14.76 2.44 97.56
620 1393 1.113 9.96 2.34 97.66
620 697 1.113 8.46 2.73 91.27
620 460 1.113 7.44 2.97 97.03
620 230 1.113 6.24 3.30 96.70
620 153 1.113 6.08 3.22 96.78
620 115 1.113 5.71 3.24 96.76
620 92 1.113 5.80 3.19 96.81
620 77 1.113 5.39 3.33 96.67
620 71 1.113 5.13 3.25 96.75

EB feed = 0.126 mhin, Hz0 feed = 0.306 mWmin

620 1050 1.113 22.98 1.26 _ 98.74
620 850 1.113 20.25 1.47 _ 98.53
620 650 1.113 18.54 1.89 98.11
620 450 1.063 17.77 2.37 0.31 91.32
620 250 1.063 16.30 3.44 1.75 94.81
620 150 1.063 17.08 4.32 3.20 92.48

-: Value was too small to be detected

 B.K. Abahlla et al. /Applied Catalysis A: General 113 (1994) 89-102 91

Table 6
Feed conditions and experimental results of catalyst C

Temp. He rate Press. EB %C BZ %S TOL 96s ST %S

PC) (mUmin) (bar)

EBfeed= 0.1452 mUmin,Hz0 feed = 0.362 mUmin

600 171 I .455 47.95 4.12 2.56 93.32
600 267 1.557 50.76 3.18 2.51 94.31
600 345 1.624 53.68 2.37 2.21 95.42
600 480 1.760 53.98 1.83 2.07 96.11
600 618 1.828 52.95 I .31 I .53 97.10

EBfeed = 0.1498 mUmin, Hz0 feed = 0.3348 mUmin

502 450 1.624 9.07 2.23 97.17
520 450 I .624 12.30 2.17 - 97.83
540 450 1.624 15.79 2.50 97.50
560 450 1.624 19.53 2.65 91.35
580 450 1.624 30.68 3.66 0.83 95.51
600 450 1.624 36.73 4.19 1.09 94.72
620 450 1.624 43.94 5.01 I .83 93.15
645 450 1.624 52.70 6.37 2.86 90.17
660 450 I.624 55.02 8.16 4.29 87.54
690 450 I .692 63.01 11.0 8.39 80.61
710 450 I.692 67.09 14.46 12.40 73.14

EB feed = 0.1595 mUmin. Hz0 feed = 0.3345 mumin

500 600 1.760 3.58 3.11 96.89
530 600 I .760 5.82 3.32 96.68
560 600 1.760 9.71 3.68 96.32
590 600 1.760 18.03 4.38 95.62
620 600 1.794 31.77 5.09 2.43 92.48

-: Value was too small to be detected.

4. Discussion

Using the pseudohomogeneous model and fitting the kinetic parameters to the
experimental results, the values of the pre-exponential factors and activation ener-
gies that minimizes the mean square of the difference between the model predictions
and the experimental results are given in Table 7.
From Table 7 we notice that for the three catalysts the activation energy for the
first reaction is lowest for catalyst (C) and is highest for catalyst (A). The activation
energies for the three catalysts are lower than those of the industrial catalyst.
Reaction ( 1) is the main reaction and is the one responsible for the production of
styrene. For reactions 4, 5 and 6 the activation energies for the industrial catalyst
and the three in-house prepared catalysts are almost the same. For reaction 2 the
activation energy is highest for catalyst (A) and is lowest for catalyst (B) and they
are lower than that of the industrial catalyst. For reaction 3 the activation energies
of catalysts (A) and (B) are very close to that of industrial catalyst, but catalyst
(C) has a much smaller activation energy.
98 B.K. Abdalla et al. /Applied Catalysis A: General 113 (1994) 8+102

Table I
Intrinsic kinetics parameters for industrial catalyst and catalysts, (A), (B) and C)

Reaction Industrial catalyst Catalyst (A) Catalyst (B) catalyst (C)

AT E?‘* A; Ei A; E; Ai Ei

1 0.85 I 9089 1 0.30 87820 0.43 86565 0.75 83357

2 14.00 207989 13.25 193515 13.35 187992 12.19 188630
3 0.56 91515 -0.38 102668 0.81 97334 0.77 100555
4 0.12 103996 0.12 103996 0.12 103996 0.12 103996
5 -3.21 65723 -3.21 65723 -3.21 65723 -3.21 65723
6 21.24 73628 21.24 73628 21.24 73628 21.24 73628

*A,: Pm-exponential factor (dimensionless) [ ki = 3600. exp(A, - EJRTJI.

**E; Activation energy of reaction i (kJ/mol).
***j&u= Exp ( AFdRT), AF,, = a + bT+ CT 2, a= 122725. 157 kJ/kmol, b= - 126.27 kJ/kmol K,
c= -2.194~10-3kJ/kmolK* (161.

One of the main purposes of developing intrinsic kinetics is to use these kinetics
into rigorous design equations (mathematical models) in order to predict the behav-
iour of the industrial reactor. In the present case the most important process after
the intrinsic kinetic is the intraparticle diffusion which is described rigorously by
the use of the dusty gas model rather than the less rigorous Fickian description.
The change of temperature and pressure along the length of the reactor are also
taken into consideration. The prediction of the model should be therefore reasonably
reliable [ 151. The extracted intrinsic kinetic parameters were used in the hetero-
geneous model for the industrial reactor, to simulate its performance when these
catalysts are used after pelletizing to the same particle size of the industrial catalyst.
The results of the conversions and yields obtained and the exit temperatures are
shown in Table 8 together with those of the industrial reactor with the industrial
catalyst.
From Table 8, which gives the simulation results for the four catalysts when used
in the industrial reactor under the same design and operating conditions, the results
show that the ethylbenzene conversions obtained by two of the three in-house
prepared catalysts (catalysts B and C) are higher than that obtained by the industrial
Table 8
Conversions and yields obtained by using the in-house prepared catalysts in the heterogeneous model

Component Industrial Catalyst A Catalyst B Catalyst C

Conversion (%)
Ethylbenzene 41.25 46.41 52.26 51.26

Yield (o/o)
Styrene 40.4 I 33.07 28.37 44.25
Benzene 3.11 13.08 21.99 5.99
Toluene 3.12 0.32 1.90 1.02

Exit temp. (K) 850.0 847.54 841.20 842.68

 B.K. Abdalla et al. /Applied Catalysis A: General 113 (1994) 8%102 99

catalyst. The ethylbenzene conversion for catalyst (A) is slightly lower than that
obtained using the industrial catalyst. However, the higher ethylbenzene conver-
sions did not give high styrene yields in the case of catalyst (B), where the obtained
benzene yield is higher than those obtained using the industrial catalyst. Catalyst
(C) gave a higher styrene yield than that of the industrial catalyst. The improvement
in the styrene yield is almost 10% over that of the industrial catalyst. Catalyst (B)
produced almost as much benzene as styrene.
Fig. 2 shows the conversion, yield, temperature and effectiveness factor profiles
along the length of the reactor. For catalyst B the ethylbenzene conversion rises
faster than all other catalysts reaching the highest X,, of 52.24% at the exit.
However, for this catalyst the styrene profile rises slowly giving a low YsT of
28.37% at the exit. The benzene profile for this catalyst rises much faster than for
all other catalysts giving a relatively high exit Yuzof 21.99%. The drop of temper-
ature along the catalyst bed is faster for this catalyst giving an exit temperature of
841.2 K. For catalyst C the X,, profile rises reasonably fast giving a high exit value
of 51.26%, also the YsTprofile rises fast, giving a high exit YsTof 44.25%, on the
other-hand the Y,, profile is suppressed compared with catalyst B giving an exit
value of Ysz equal to 5.99%. The drop of temperature for this catalyst is slightly
more than for catalyst B ( 1 K difference at the exit). For catalyst A the X,, profile
rises along the length of the reactor in a rate comparable to that of the industrial
catalyst, giving an exit X,, which is about 1% lower than that of the industrial
catalyst. However, the rise of the YsTprofile for this catalyst is quite slow (higher
only than that of catalyst B) giving the next lowest to catalyst B, i.e. 33.07%. The
Yuzis reasonably high ( 13.08%)) second only to catalyst B. The drop in temperature
for this catalyst along the length of the reactor is lower than for the other in-house
prepared catalysts B and C. The temperature drop associated with the industrial
catalyst is lower than for catalyst A, although it gives a higher conversion due to
the fact that the YTo,_(which is produced through an exothermic hydrogenation
reaction) is higher for the industrial catalyst (3.12%) than for catalyst A (0.32%).
Therefore the only in-house prepared catalyst that gives a higher YsT than the
industrial catalyst is catalyst C, although both catalysts B and C give higher ethyl-
benzene conversions compared with the industrial catalyst.
Fig. 2 also shows the profiles of the effectiveness factors of EB, ST, BZ and TOL
for the four catalysts. For catalyst B the r)EBrises faster than for all the other
Catalysts, reaching a value of 0.50 at the exit of the reactor. The ,jsT of this catalyst
shows a clear non-monotonic behaviour and goes down to 0.08 at the exit of the
reactor. The TBz and %oL for this catalyst B rise sharply along the length of the
reactor, woL shows a small decrease near the entrance of the reactor but it again
increases sharply. The values of woL are higher than those of 77~~For catalyst C
QB increases very slowly along the reactor giving the lowest values reached by
any of the four catalysts (0.32). Also qsT for this catalyst shows non-monotonic
behaviour and it gives the second lowest value compared with the other catalysts;
while quz increases sharply along the length of the reactor and gives the highest
B.K. Abaklla et al. /Applied Catalysis A: General I13 (1994) 89-102
 B.K. Abdalla et al. /Applied Catalysis A: General 113 (1994) 8WO2 101

value (0.92) as compared to those of the other catalysts. Also %oL shows a small
decrease at the entrance of the reactor then it increases sharply along the length of
the reactor reaching the high value of 0.96 at the exit of the reactor. For catalyst A
the %B increases very slowly along the length of the reactor reaching a value of
0.49; however the qsT shows small non-monotonic behaviour. The 7)~~and woL
increase sharply along the reactor giving the second highest values of 0.84 and
0.88, respectively. The behaviour of the effectiveness factor profiles obtained when
catalyst A is used are very similar to those obtained by the industrial catalyst, only
%oL shows a small reduction at the beginning of the reactor when catalyst A is
used.

5. Conclusion

Intrinsic kinetics of an industrial catalyst for the dehydrogenation of ethylbenzene

to styrene have been extracted from industrial reactor data using a rigorous heter-
ogeneous model based on the Stefan-Maxwell equations for multicomponent dif-
fusion in porous catalyst pellets. Three in-house prepared catalysts with different
compositions have been produced in a powder form and the intrinsic kinetics for
these catalysts have been obtained from the experimental results using a pseudo-
homogeneous model. The possible use of these catalysts in the same industrial
reactor has been simulated using the rigorous heterogeneous model. The results
show that one of the catalysts (catalyst C, with 5% Ce02 and 5% CrZ03) gives
considerably higher ethylbenzene conversion and styrene yield than the industrial
catalyst. Another one of the catalysts (catalyst B, with 5% CeO*) seems to be
almost as much a benzene producer as a styrene producer.

6. Nomenclature

AB Catalyst bed cross-sectional area, m2

Ai Frequency factor of reaction i
Ci, Cis Molar concentration of component i in the gas phase and at the
catalyst surface respectively, kmol/m3
cPi Specific heat capacity of component i, kJ/kmol K
D,.j 9 DK~ Effective molecular and Knudsen diffusivities respectively, m2/h
D,, 4 diameter of the catalyst and the reactor respectively, m
Ei Activation energy of reaction i, kJ/kmol
Fi Molar flow rate of component i, kmol/h
GO Mass velocity of the gas mixture, kg/m2 h
& Gravitational acceleration, m2/h
&i Heat of reaction i, Id/km01
102 B.K. Abdalla et al. /Applied Catalysis A: General 113 (1994) M-102

K EB Equilibrium constant for the ethylbenzene dehydrogenation reaction

to produce styrene, bar
k Reaction i rate constant, kmol/kg h baf (for kl and k2; kmol/kg h
bar, for k3 and kg kmol/kg h ba?, for k4; kmol/kg h bar1.5,for k6;
kmol K3/kg h bar’)
LB Catalyst bed length, m
N Molar flux of component i, kmol/m2 h
pT9 Pi Total pressure and partial pressure of component i respectively, bar
R Universal gas constant ( = 8.314 kJ/kmol K)
Ri Rate of reaction i, kmol/kg h
‘P mean pore radius, m
s BET BET specific surface area, m3/kg
T Temperature of the reactor, K
b Total pore volume, m3/kg
VSt Volume of nitrogen adsorbed at saturation, m3/kg
xi Conversion of reactants
Yi Mole fraction of component i; Dimensionless
Z Thickness of the catalyst slab, m

Greek letters
E Bed voidage fraction, dimensionless
Tli Effectiveness factor of reaction i, dimensionless
Po Viscosity of the gas mixture, kgf h/m2
PO PG Density of the catalyst and the gas mixture respectively, kg/m3

References

[ I] D.E. Clough and W.F. Ramirez, AIChE J., 22 (6) ( 1976) 1097.
[2] B. Davidson and M.J. Shah, IBM J. Res. Dev., 9 (1965) 289.
[3] S. Carraand L. Froni, Ind. Eng. Chem. Process Des. Dev., 4 (3) (1965) 281.
[4] P.J. Heggs and N. Abdullah, Chem. Eng. Res. Des., 64 ( 1986) 258.
[5] L. Petrov, G. Nenov, N. Kirkov and D. Shopov, Kinet. Catal., 25 (1) ( 1984) 106.
[6] D.J. Model, Chem. Eng. Comput., 1 (1972) 100.
[7] F. Abet, M. Maceri and M. Piovan, Quad. Inorg. Chem. Ital., 3 (9) (1967) 154.
[8] J.G.P. SheelandC.M.Crowe,Can. J.Chem.Eng.,47 (1969) 183.
[9] E.H. Lee, Catal. Rev., 8 (1973) 285.
[ 101 S.S.E.H. Elnashaie and B.K. Abdalla, 41st Can. Chem. Eng. Conf., Vancouver, Canada, Oct. 1991.
[ 111 J. Villadsen and M.L. Michelsen, Solution of differential equation models by polynomial approximation,
Prentice Hall, N.Y., 1978.
[ 121A.C. Hindmarsh, Gear: Ordinary Differential Equation System Solver, Lawrence Laboratory, Report UCID-
30001, Revision 3, December 1974.
[ 131 C.M. Crowe, Private communication, McMaster Univ., Aug. 1992.
[ 141 CM. Crowe, Private communication, McMaster Univ., Nov. 1989.
[ 151 S.S.E.H. Elnashaie and S.S. Elshishini, Modelling, Simulation and Optimization of Industrial Fixed Bed
Catalytic Reactors, Gordon and Breach Science Publisher, London ( 1994).
[ 161 R.H. Boundy and R.F. Boyer, Styrene, Its Polymers, Copolymers and Derivatives, Reinhold, New York
(1952).