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Intrinsic kinetics of thiophene HDS over a NiMo/SiO2 model catalyst

Article · September 2003

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 INTRINSIC KINETICS OF THIOPHENE HDS
OVER A NiMo/SiO2 MODEL CATALYST
A. Borgna, E.J.M. Hensen, J.A.R. van Veen
and J.W. Niemantsverdriet
Schuit Institute of Catalysis, Eindhoven University of Technology,
PO Box 513, 5600 MB Eindhoven, The Netherlands
Introduction
Supported mixed transition metal sulfide catalysts play a pivotal role
in refineries for the production of clean motor fuels. They are
employed not only to hydrotreat the final products like gasoline and
diesel, but also to pretreat fluid catalytic cracking or reformer feed
[1]. Furthermore, they provide the hydrogenation functionality in
most hydrocracking catalysts that upgrade vacuum residue to more
valuable products. Two major drivers for the development of more
active hydrotreating catalysts are (i) dwindling oil supplies forcing
refiners to use heavier feedstock and (ii) ever-tightening motor fuel
specifications (for instance, the EU Auto Oil programme II [2]).
Noteworthy is that mostly the use of an improved catalyst is more
economic than modifications to the process.
While research on hydrotreating catalysts has been extensive over the
last 50 years [3-5], it has proven very difficult to relate catalyst
structure to catalyst activity and selectivity on the molecular level. In
recent years, we have employed the model catalyst approach to
heterogeneous catalysis. The essential point is to prepare planar
model catalysts by spin-coating which mimics the industrial pore
volume impregnation method. In this way, realistic models can be
obtained which are easily amenable to high-resolution spectroscopic
studies. We have shown before [6,7] that the strong tandem-mix of
characterization and reactivity evaluation enables detailed insight into
the influence of active phase formation on the activity. Here, we will
show how these well-defined models can be used to obtain intrinsic
kinetics of thiophene hydrodesulfurization.
Experimental
Model catalyst preparation NiMo/SiO2 planar model catalysts
consisting of a Si(100) wafer covered by a thin layer of SiO2 as
support were prepared by spin-coating as extensively described
before [6,7]. Planar SiO2 model supports were prepared by oxidizing
a Si(100) single-crystal wafer in air at 1023 K for 24h. After
calcination the wafers were cleaned in a H2O2/NH4OH solution at
338 K. Subsequently, the surface was hydroxylated in boiling water
for 20-30 min. As a typical example, we describe here the preparation
of NiMo/SiO2. A model silica support was spin-coated in nitrogen
atmosphere at 2800 rpm with an aqueous solution containing
Ni(NO3)2.6H2O (Merck, p.a.) and (NH4)6Mo7O24.4H2O (Merck,
purity >97%) with an atomic ratio of 1:3, respectively. The
concentration of the precursor solution was adjusted to result in the
required metal loadings (2 Ni at/nm2 and 6 Mo at/nm2). Prior to
characterization or catalytic testing, a model catalyst was sulfided at a
rate of 5 K/min to 673 K + 1 h in a mixture of 10 vol.% H2S in H2.
Reactivity evaluation. Atmospheric thiophene HDS reactions
were carried out in a batch-type reactor. After sulfidation, the reactor
was flushed with the reactant mixture for 5 min at the desired
reaction temperature. The reaction was then carried out in batch
mode by closing the reactor inlet and outlet. This was marked as zero
reaction time. After a reaction time of 1 h a gas-phase sample was
taken from the reactor using a precision sampling gas syringe which
was injected on a DB-1 column to analyze the main products: 1-
butene, n-butane, trans-2-butene, cis-2-butene, thiophene and small
Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2003, 48(2), 603
amounts of C1-C3 hydrocarbons. The HDS activities are expressed as
thiophene conversion after 1 h of reaction time and per 5 cm2 of
model catalyst. These values were corrected for blank thiophene
conversion measured using an empty reactor. Between two
experiments the catalyst was resulfided at 673 K for 1 h.
Results and Discussion
Because diffusion limitations are absent, the use of planar model
catalysts offers great advantages in kinetic studies. Catalytic data
were obtained at different temperatures varying the partial pressures
of hydrogen, thiophene and H2S, respectively. The kinetic data were
analyzed considering both power-law and Langmuir-Hinshelwood
(L-H) kinetics Between 573 and 673 K, positive orders in thiophene
and hydrogen and moderately negative orders in H2S were obtained.
Moreover, while the reaction order in thiophene significantly
decreased as the reaction temperature decreases, the order in
hydrogen was nearly constant and close to 1. The lower reaction
order of thiophene as compared to the reaction order in hydrogen
clearly indicates that thiophene adsorbs much stronger than
hydrogen. The negative order in H2S indicates that the HDS reaction
is inhibited by H2S, probably due to competition with thiophene for
sulfur-defect sites. The trends in the reaction orders are in agreement
with the literature [8,9]. Heats of adsorption and activation energies
can be derived once a kinetic model has been adopted. Several
mechanisms and associated kinetic models for the
hydrodesulfurization of thiophene have been proposed in the
literature [10-14].
Although the precise mechanism of thiophene HDS reaction is still
under debate, we have chosen an often-used simplified reaction
network consisting of elementary steps, in which thiophene
exclusively adsorbs on sulfur vacancies and H2 adsorbs dissociatively
on different sites to form butadiene (B) and H2S. Assuming that the
surface reaction between adsorbed thiophene and H2 is the rate-
limiting step and the H2S adsorption takes place on sulfur vacancies
exclusively, in competition with thiophene adsorption, the following
Langmuir-Hinshelwood rate expression can be obtained:
k KT K H 2 pT pH 2
r =
(1 + KT pT + K H S pH 2 S / pH 2 ) (1 + K 1H/ 2 p1H/ 2 ) 2
2 2 2
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].
 0 .0 8 Table 1: Intrinsic kinetic parameters obtained from non-linear

/mol *S)
multivariable fittings on a sulfided NiMo/SiO2 model catalyst.

Ni
673 K Parameter Value

0 .0 6 k 0 (molthioph/molNi*S) 0.0967
thioph.

rds 83.5
Eact (kJ/mol)
Reaction Rate (mol

0 8.7
Kthioph (bar-1)
0 .0 4 623 K
thioph -57.8
− ∆H ads (kJ/mol)
0 138.9
KH (bar-1)
0 .0 2 2S
0 .5 0 .5 2
r = k ' .P H 2 / ( 1 + K H 2 .P H 2 ) H S -117.1
− ∆H ads2 (kJ/mol)
0 .4 0 .6 0 .8 1 .0
P H (% ) At high temperatures, the coverages become lower and in the limit of
2 an empty surface, we find
Figure 1. Dependence of the rate of thiophene HDS on the partial app
Eact rds
= Eact T
+ ∆H ads
H
+ ∆H ads2
pressure of H2 at different temperatures, along with data fit according
to the L-H kinetic model. Pthioph.= 4 vol% and PH2S= 0 vol%. 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
/mol *S)

0 .1 0 by Borgna et al. [18].

673 K
Ni

Conclusion
0 .0 8 648 K Planar model catalysts can be applied to obtain intrinsic kinetic
Thioph

parameters for the relatively simple thiophene hydrodesulfurization

0 .0 6 reaction, offering an excellent opportunity to study reaction
Reaction Rate (mol

623 K mechanism and kinetics without under diffusion-free conditions.

0 .0 4
0 .0 2 598 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:
app rds
Eact = Eact + (1 − ΘT# ) ⋅ ∆H ads
T
+ (1 − Θ*H ) ⋅ ∆H ads2 − Θ #H S .∆H ads2
2
H H S
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Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2003, 48(2), 604

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