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where k is the rate constant of the rate-determining step and KT, KH2
KH2S are the adsorption constants of thiophene, H2 and H2S,
respectively. Figure 1 shows that the experimental data measured at
constant thiophene and H2S partial pressures and varying the H2
partial pressure can be satisfactorily fitted using the L-H equation,
giving an estimation of the adsorption equilibrium constants of
hydrogen at different temperatures. The optimized values indicate
that the adsorption equilibrium constant is statistically non-different
from zero under our experimental conditions. Therefore, the
hydrogen adsorption term in the denominator can be ignored. The
optimized values for the adsorption equilibrium constants at 673 K of
thiophene and H2S are 3.5 0.7 bar-1 and 28.9 1.8, respectively.
The intrinsic kinetic parameters, the activation energy of the rate
determining step and the heat of adsorptions, can be derived by fitting
the kinetic data measured at different temperatures using non-linear
multivariable fittings. Figure 2 shows the quality of this fitting and
the intrinsic parameters are summarized in Table 1.
The estimated value for the heat of adsorption of thiophene and H2S
are 57.8 10.9 kJ/mol and 117.1 11.3 kJ/mol, respectively. A
broad range of values for the heats of adsorption of both thiophene
and H2S have been reported in the literature [11,12]. Theoretical
values vary between -62 and -137 kJ/mol, whereas the values for the
heat of adsorption of H2S vary between 75 and 93 kJ/mol [15].
Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2003, 48(2), 603
thioph.
Ni
/mol *S)
0 .0 8
673 K
0 .0 6
623 K
0 .0 4
0 .0 2
r = k ' .P H 2 / ( 1 + K H 2
0 .6
0 .5
.P H 2
0 .8
0 .5
rds
Eact
(kJ/mol)
83.5
0
Kthioph
(bar-1)
8.7
H S
H ads2
0 .1 0
673 K
138.9
-117.1
623 K
598 K
0 .0 0
0 .0 0 0 .0 2 0 .0 4 0 .0 6 0 .0 8
p th io p h ( % )
Figure 2. Dependence of the rate of thiophene HDS on the thiophene
partial pressure along with a non-linear multi-variable fitting
according to the L-H model. PH2= 90 vol% and PH2S= 0 vol%.
To summarize, the values of the heat of adsorption reported in this
contribution indicate a relatively strong adsorption of both thiophene
and H2S.
The activation energy is about 85 kJ/mol, in line with theoretical
calculations [15], which predict overall reaction enthalpies for C-S
scission and sulfur removal of 70 kJ/mol and 73 kJ/mol, respectively.
It is important to mention that much lower activation energies,
usually obtained from Arrhenius plots, have been reported in the
literature [16-18]. However, the activation energy derived from
Arrhenius plots represents the apparent activation energy and not the
real activation energy of the rate-determining step. Moreover, a
decrease in apparent activation energy with increasing temperature
has been frequently observed [16-18]. Such a decrease of the
apparent activation energy has been often attributed to a decrease of
the surface coverage of the reactants as temperature increases [17,
18]. The relation between apparent and real activation energy is:
H
app
rds
T
Eact
= Eact
+ H ads
+ H ads2
Therefore, a negative apparent activation energy may be obtained
when the adsorption energies of thiophene and hydrogen are large
enough. This then explains the Volcano-type curve recently reported
by Borgna et al. [18].
Conclusion
Planar model catalysts can be applied to obtain intrinsic kinetic
parameters for the relatively simple thiophene hydrodesulfurization
reaction, offering an excellent opportunity to study reaction
mechanism and kinetics without under diffusion-free conditions.
648 K
0 .0 4
0 .0 2
(kJ/mol)
-57.8
0 .0 8
0 .0 6
(kJ/mol)
1 .0
Ni
0.0967
0
KH
(bar-1)
2S
/mol *S)
k 0 (molthioph/molNi*S)
thioph
P H (% )
Thioph
Value
H ads
0 .4
Parameter
H S
app
rds
T
Eact
= Eact
+ (1 T# ) H ads
+ (1 *H ) H ads2 #H S .H ads2
2
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Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2003, 48(2), 604