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9183
A set of intrinsic rate equations based on the HougensWatson formalism was derived for the dehydrogenation
of ethylbenzene into styrene on a commercial potassium-promoted iron catalyst. The model discrimination
and parameter estimation was based on an extensive set of experiments that were conducted in a tubular
reactor. Experimental data were obtained for a range of temperatures, space times, and feed molar ratios of
steam to ethylbenzene, styrene to ethylbenzene, and hydrogen to ethylbenzene. All the estimated parameters
satisfied the statistical tests and physicochemical criteria, and the kinetic model yielded an excellent fit of the
experimental data. The model was applied in the simulation of the dehydrogenation in industrial multibed
adiabatic reactors with either axial or radial flow and accounting also for thermal radical-type reactions, internal
diffusion limitations, coke formation, and gasification.
1. Introduction
Styrene (ST) is one of the most important monomers in the
chemical industry. More than 2.5 107 MT/year of styrene
monomer is produced worldwide.1 The dehydrogenation of
ethylbenzene (EB) on iron oxide catalysts promoted by potassium accounts for 85% of the commercial production.2 Benzene
(BZ), toluene (TO), methane, and ethylene are the main
byproducts.3 The dehydrogenation of EB is an endothermic and
reversible reaction with an increase in the number of moles, so
that high conversion requires high temperatures and a low EB
partial pressure.
Potassium promotes the catalyst activity and enhances the
selectivity to ST. The role of potassium is attributed to the
existence of an active phase, potassium ferrite (KFeO2).410
Potassium also promotes the gasification of the carbonaceous
deposits on the catalyst and would maintain the catalyst activity,
even at relatively low steam-to-hydrocarbon ratios (i.e., below
a molar ratio of 11.8:1).5,11,12
High steam-to-hydrocarbon ratios favor the selectivity to ST
but also the lifetime and stability of the catalyst by decreasing
the undesired carbon production. Devoldere and Froment13
studied the influence of the formation of coke on the catalyst
and of its gasification by steam on the operation of ST plants
and introduced the notion of a dynamic equilibrium coke
content.
The kinetics of EB dehydrogenation have been widely
investigated1418 but seldom in a fundamental way, generating
empirical polynomial correlations for the optimization of the
commercial unit.1921 Furthermore, the reaction rates reported
in most of the papers are not intrinsic, but rather are effective
(i.e., including the effects of diffusional limitations).14,16,22
Recently, however, Schule et al.23 derived a mechanistic model
using a single-crystal unpromoted iron oxide film. It includes
EB dehydrogenation into ST, but it does not consider BZ and
TO formation and thermal reactions. The redox reactions on
the catalyst and coke formation were included in the model that
contains 31 parameters, 13 of which were estimated from overall
kinetic measurements, whereas the others (such as adsorption
* To whom correspondence should be addressed. Tel.: +1-979-8453361. Fax: +1-979-845-6446. E-mail: g.froment@che.tamu.edu.
9184 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
of the reactor, and its bed depth varied between 3 and 5 cm,
depending on the amount of catalyst. The upper and lower
sections of the reactor were filled with R-Al2O3 beads to serve
two functions: preheating and mixing of reactants and decreasing
the free volume in the reactor.
A small fraction of the exit gas was sent to a Shimadzu 17A
gas chromatograph with a thermal conductivity detector (TCD),
followed by a HewlettsPackard (HP) 5890 gas chromatograph
with a flame ionization detector (FID) for online analysis. Two
gas chromatographs were connected in series, and helium was
used as a carrier gas. The Shimadzu 17A gas chromatograph
was equipped with two valves to inject the gaseous products
and switched the valves by means of a timing program stored
in the gas chromatograph. The oven temperature programs of
the Shimadzu 17A and HP 5890 gas chromatographs and valve
switching timing program were matched to accomplish the
desired separation of all compounds. Three capillary columns
were used: HP PLOT Molecular Sieve 5A column (Agilent,
0.53 mm ID 25 m 15 m), for the separation of H2 and
N2; GS-Q capillary column (J&W, 0.53 mm ID 30 m), for
the separation of N2, CO, CO2, CH4, C2H4, and H2O; and a
HP-5 capillary column (Agilent, 0.53 mm ID 1.5 m
30 m), for the separation of aromatic compounds.
N2 was used as a primary internal standard for the TCD
analysis. EB was chosen as a secondary internal standard,
because it appeared on both TCD and FID as one of the major
compounds and could be used to tie the analyses on the two
detectors.
EB conversion, conversions of EB to product j, and selectivities to product j were calculated using the following definitions:
EB conversion (%) ) 100
F0EB - FEB
F0EB
Fj - F0j
F0EB
Fj - F0j
F0EB - FEB
3. Experimental Results
Experimental data were collected by injecting the exit sample
6-10 times into the online GC setup under the same reaction
conditions. The data plotted in the following figures are averages
of those values. The standard deviation of each point is 1%
of the average value.
For all the temperatures, the EB conversion did not increase
appreciably when the space times exceeded 70 g-cat h/(mol EB),
because the reactions approach equilibrium at high space time.
The solid lines in the following figures are drawn to fit the data.
Figure 1 shows the effect of temperature on the EB conversion
to ST for a molar steam-to-EB ratio of 11. The rate of formation
of ST from EB decreased as the space time increased. The
calculated equilibrium conversions of EB to ST are 80.4%,
85.0%, and 88.8% at T ) 600, 620, and 640 C, respectively.
0
The corresponding experimental values at W/FEB
) 62 g-cat
h/mol shown in Figure 1 were 60.0%, 71.6%, and 79.1%,
respectively, i.e., well below the equilibrium values. Figure 2
shows the ST selectivity as a function of the EB conversion for
the complete temperature range. The ST selectivity evolves in
an opposite way to the EB conversion. The ST selectivity has
a tendency to decrease as the temperature increases, because
the competitive reactions that produce byproducts become
pronounced with increasing temperature. Figures 3 and 4 show
the BZ and TO selectivity, as a function of EB conversion. The
rate of BZ formation is only slightly affected by the EB
conversion (or space time), but the rate of TO formation is
significantly enhanced as the EB conversion (or space time)
increases.
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9185
Figure 6. Effect of ST-to-EB feed ratio on (a) the EB conversion and (b)
the ST selectivity for T ) 620 C; PT ) 1.04 bar; H2O-to-EB molar ratio
) 11; H2-to-EB molar ratio ) 0.
results at 600 and 640 C are not included. The increase in the
H2O-to-EB feed ratio did not result in an increase of the EB
0
conversion or the ST selectivity for W/FEB
< 30 g-cat h/mol.
0
Even for W/FEB > 30 g-cat h/mol, the effect of increasing the
H2O-to-EB feed ratio on the EB conversion was insignificant.
The effect of the H2O-to-EB feed ratio on the styrene selectivity,
however, becomes pronounced as the EB conversion increases.
Effect of the Styrene-to-Ethylbenzene Feed Ratio. Figure
6 shows the effect of the ST-to-EB feed ratio on the EB
conversion and the ST selectivity at 620 C. As the ST-to-EB
ratio in the feed increases, the EB conversion decreases, because
of the competitive adsorption of ST and the approach to
equilibrium. Furthermore, the adsorbed ST on the surface
changes to a carbonaceous deposit, which causes catalyst
deactivation. As the ST-to-EB feed ratio increased, the ST
selectivity decreased.
Effect of Hydrogen-to-Ethylbenzene Feed Ratio. Figure 7
shows the effect of hydrogen addition on the EB conversion
and the ST and TO selectivity at 600 C. Hydrogen is involved
in the formation of TO from ST, so that when the H2-to-EB
feed ratio is increased, the TO selectivity is favored, while the
ST selectivity suffers from side reactions. The addition of
hydrogen further reduces the iron catalyst from hematite (Fe2O3)
to magnetite (Fe3O4), which has a lower activity.
4. Reaction Scheme and Rate Equations
Figure 5. Effect of H2O-to-EB feed ratio on (a) the EB conversion and (b)
the ST selectivity for T ) 620 C; PT ) 1.04 bar; ST-to-EB molar ratio )
0; H2-to-EB molar ratio ) 0.
9186 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
kt1
PSTPH2
Keq
kt2
rc1 )
(1 + KEBPEB + KH PH
2
(1)
+ KSTPST)2
k2KEBPEB
(1 + KEBPEB + KH2PH2 + KSTPST)2
rc2 )
(2)
k3KEBPEBKH2PH2
rc3 )
(1 + KEBPEB + KH PH
2
(3)
+ KSTPST)2
k4KSTPSTKH2PH2
rc4 )
(1 + KEBPEB + KH PH
2
(4)
+ KSTPST)2
d(
Figure 7. Effect of H2-to-EB feed ratio on (a) the EB conversion, (b) the
ST selectivity, and (c) the TO selectivity for T ) 600 C; PT ) 1.04 bar;
H2O-to-EB molar ratio ) 11; ST-to-EB molar ratio ) 0.
W F0EB
d(
dXBZ
1
2
3
2.2215 10
2.4217
1020
17
3.8224 10
16
W F0EB
d(
Eti [kJ/mol]
dXH2
272.23
352.79
313.06
W F0EB
d(
) 2rc2 + rt2
B
FB
(5b)
B
FB
B
(5a)
FB
(5c)
B
FB
(5d)
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9187
Table 2. Parameter Values and Statistical Tests Derived from the Data at 620 C
95% Confidence Interval
parameter
unit
estimate
standard deviation
t value
lower value
upper value
KEB
KST
KH2
k1
k2
k3
k4
bar-1
bar-1
bar-1
kmol/(kg-cat h)
kmol/(kg-cat h)
kmol/(kg-cat h)
kmol/(kg-cat h)
8.466
34.00
3.091
0.2725
0.00544
0.0184
0.0302
1.01
1.51
0.447
0.0171
0.000504
0.00874
0.00565
8.37
22.6
6.91
15.9
10.8
2.11
5.66
6.460
31.02
2.204
0.2385
0.00444
0.001095
0.0190
10.47
36.99
3.977
0.3065
0.00644
0.03571
0.0413
value
A1
A2
A3
A4
AEB
AST
AH2
Figure 8. Effect of temperature on (a) the rate coefficients ki and (b) the
adsorption equilibrium constants Kj. Symbols represent estimated values
per temperature; lines represent calculated values from estimates at all
temperatures.
175.38
296.29
474.76
213.78
Adsorption Enthalpy [kJ/mol]
-102.22
-104.56
-117.95
Ha,EB
Ha,ST
Ha,H2
Xj ) 0 at
W
)0
F0EB
S() )
[y - f(x , )]
i
98 Min
(6)
i)1
(7)
9188 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
Table 4. Adsorption Entropies and Standard Entropies for
Ethylbenzene (EB), Styrene (ST), and Hydrogen (H2)
component
0
-Sa,j
[J/(mol K)]
0
-Sg,j
[J/(mol K)]a
51 - 0.0014Ha,j
[J/mol]
ethylbenzene, EB
styrene, ST
hydrogen, H2
95.61
87.53
121.5
361.65
346.25
186.1
194.1
197.4
216.1
RgT
1 d 2 dPs,BZ
r
)(F r + srt2)
2 dr
dr
De,BZ s c2
r
(15c)
B
dT
) F0EB -Hr1 1rc1 + rt1
0
F
d(W FEB)
B
j)1
B
B
- Hr3 3rc3 + rt3
- Hr44rc4 (12)
Hr2 2rc2 + rt2
FB
FB
dPt
d(W F0EB)
) fR
usGF0EB
FBdp
RgT
1 d 2 dPs,H2
r
)[Fs(rc1 - rc3 - 2rc4) + s(rt1 - rt3)]
2 dr
dr
D
r
e,H2
(15d)
with boundary conditions
Ps,j ) Pj at r ) R
dPs,j
) 0 at r ) 0
dr
(11)
(14)
(15b)
[ (
) (
(9)
j pj
b(1 - B)
Re
RgT
1 d 2 dPs,ST
r
)[Fs(rc1 - rc4) + src1]
2 dr
dr
D
r
e,ST
m c
a+
(8)
(10)
RgT
1 d 2 dPs,EB
r
)
[F (r + rc2 + rc3) + s(rt1 + rt2 + rt3)]
2 dr
dr
De,EB s c1
r
(15a)
where Sog is the standard entropy of the gas and Soa is the entropy
of the adsorbed molecule. For adsorption, Soa is smaller than Sgo,
because of the translational contribution to Sgo.33 The gas-phase
o
standard entropies of EB, ST, and H2 in Sg,j
can be obtained
36
o
from Stull et al. Sa,j was calculated from the relation
Soa,j ) R ln Aj
B
1 - B
f)
(13)
i )
[rci(Ps,j)Fs + rti(Ps,j)s] dV
[rci(Pj)Fs + rti(Pj)s]V
(16)
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9189
Table 5. Feed Conditions, Reactor Dimensions, and Simulation
Results of a Three-Bed Adiabatic Axial Flow Reactor Using the
Heterogeneous Model
value
parameter
bed 1
bed 2
bed 3
72950
103.18
1.33
36.89
98.49
1.000
0.507
1.25
886
811.36
82020
219.19
1.50
65.78
95.10
1.423
3.480
1.06
898.2
845.71
78330
329.98
1.43
83.76
90.43
1.754
7.809
0.783
897.6
873.6
parameter
inner radius of reactor [m]
feed molar flow rate [kmol/h]
EB
ST
BZ
TO
H2O
total feed molar flow rate [kmol/h]
value
3.50
707
7.104
0.293
4.968
7777
8496.37
Figure 12. Effect of total pressure on (a) the EB conversion and (b) the ST
selectivity in a three-bed adiabatic axial flow reactor using the heterogeneous
model for isobaric conditions and for Tin ) 886, 898, and 897 K; H2O-to0
EB molar ratio ) 11 mol/mol; FEB
) 707 kmol/h.
9190 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
Table 6. Feed Conditions, Reactor Dimensions, and Simulation
Result of a Three-Bed Adiabatic Radial Flow Reactor Using the
Heterogeneous Model
value
parameter
bed 1
bed 2
bed 3
72 950
103.18
0.614
36.59
98.43
1.01
0.56
1.25
886
812.04
82 020
219.19
0.708
64.18
93.92
1.53
4.54
1.22
898.2
850.26
78 330
329.98
0.681
81.19
83.24
2.12
14.60
1.21
897.6
890.37
parameter
) iRj
value
1.5
7
707
7.104
0.293
4.968
7777
8496.37
(17)
m c
j pj
j)1
dT
) F0EB (-Hri)iri
0
d(W FEB)
i)1
(18)
(19)
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9191
Figure 15. Comparison of simulated (a) temperature profiles and (b) pressure
drop profiles using the heterogeneous model between a three-bed adiabatic
radial flow reactor and a three-bed adiabatic axial flow reactor for Tin )
886, 898, and 897 K; Pin ) 1.25 bar; H2O-to-EB molar ratio ) 11 mol/
0
mol; FEB
) 707 kmol/h.
Figure 16. Effect of feed pressure on simulated (a) EB conversion and (b)
ST selectivity in a three-bed adiabatic radial flow reactor Tin ) 886, 898,
0
and 897 K; H2O-to-EB molar ratio ) 11 mol/mol; FEB
) 707 kmol/h.
9192 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
rs )
dCCP
) rs0Cp )
dt
kEB,pKEBPEB + kST,pKSTPST
(1 - RpCCP)ns(20)
(1 + KEBPEB + KSTPST)ns
dCgr
)
dt
kEB,grPEBnEB + kST,grPSTnST
(1 + KH OPH O PH
2
+ KH2PH2
{(
W F0EB
d(
dXST
W F0EB
d(
dXBZ
W F0EB
d(
dXH2
d(
n3
PH2
1 - RgrCgr)ngr(22)
n2 (
k2PH2O
CtG (23)
(24a)
dCgr
0
) rgr
Ctgrgr - rG ) 0
dt
(24b)
B rc(ST)
FB
8
) 2rc2 + rt2
B
FB
21
Ccn1
B rc(EB)
+
FB
8
(25a)
W F0EB
The values of nEB, nST, n1, n2, n3, ngr, Rgr, kEB,gr, and kST,gr were
estimated by Devoldere and Froment13,41 and are used in the
present work. The intrinsic rate of coke formation, accounting
for the coke precursor formation and coke growth, can be
expressed as the summation of eqs 20 and 22.
8.1.3. Rate Equation for Coke Gasification. The rate
equation for coke gasification was developed under the assumption that the rate-determining step is the irreversible decomposition of an oxidized carbon complex to CO and free carbon.13
Using the pseudo-steady-state approximation for the surface
intermediates, the rate of coke gasification is given by
rG )
dXEB
(21)
(25b)
(25c)
B
+
FB
) (
rc(EB)
rc(ST)
+ 20
(25d)
8
8
{ [ ( )]
( )] [ ( )]
B
dT
) F0EB -Hr1 1rc1 + rt1
0
F
d(W FEB)
B
j)1
B
B
- Hr3 3rc3 + rt3
- Hr44rc4 Hr2 2rc2 + rt2
FB
FB
rc(ST)
rc(EB)
- HC,ST
(26)
HC,EB
8
8
mc
j pj
)}
Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9193
Acknowledgment
The authors are grateful to Dr. R. G. Anthony, Artie McFerrin
Department of Chemical Engineering, Texas A&M, for support
and stimulating discussions.
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