Catalysis Today 381 (2021) 200–208

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Catalysis Today
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Kinetics of dibenzothiophene hydrodesulfurization reactions using CoMoP/

Al2O3 and NiMoP/Al2O3
Idia G. Nascimento a, William de R. Locatel a, Bruno C. Magalhães a, Leonardo Travalloni a,
José L. Zotin b, Mônica A.P. da Silva a, *
a
Escola de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, 21949-900, Brazil
b
PETROBRAS S.A. – CENPES, Rio de Janeiro, 21949-190, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Over the last decades, the regulatory agencies, aiming to limit vehicle emissions, established more stringent fuel
Dibenzothiophene specifications, including ultra-low sulfur contents in diesel and gasoline. In such way, hydrodesulfurization
CoMoP/Al2O3 (HDS) is a key process in the oil refining scheme for producing low sulfur fuels. The evaluation of the HDS
NiMoP/Al2O3
reaction kinetics of refractory compounds, as dibenzothiophene (DBT), is an important tool in the search for
Kinetic modeling
improving the activity of usual industrial catalysts. In this context, the main objective of this work was the
Statistical analysis
Deep hydrodesulfurization estimation of kinetic parameters of DBT HDS reactions using CoMoP/Al2O3 and NiMoP/Al2O3 catalysts at
operational conditions which provide a wide range of DBT conversions. The estimation results were evaluated
using statistical tests as t-Student and chi-square. Good fits to the evaluated experimental data were provided by
two power-law models with different levels of detail: one considering the global DBT conversion only and the
other considering a reactional scheme with two parallel routes (direct desulfurization to biphenyl and hydro­
genation to cyclohexylbenzene). The apparent activation energies found were of the order of 90 to 100 kJ mol− 1.
Regarding the biphenyl hydrogenation to cyclohexylbenzene, the parameter estimation was hindered because
this reaction is expected to be significant at conditions with high DBT conversions only.

1. Introduction
Despite the continued increase in energy production from renewable
sources, in many countries, the demand for fossil fuels is still increasing
[1]. Approximately 60 % of crude oil derived from petroleum is used as
transport fuel, and the liquid fuels produced in refineries provide
roughly 95 % of transport energy worldwide, of which diesel oil is one of
the most used fuels [2]. According to the World Energy Outlook [3], in
2018, the production of diesel corresponded to 30 % of oil derived
products. A similar scenario is projected to 2025 and 2030.
Due to the presence of contaminants such as sulfur, the combustion
of diesel oil causes the emission of toxic gases (SOx) and particulate
matter [4]. Moreover, low sulfur fuels are required for proper operation
of catalytic converters dedicated to emissions abatement. In this context,
legislation around the world has required reducing the sulfur content of
diesel oil. In this way, refineries are being impelled to find ways to meet
these demands.
A gradual restriction on the sulfur level in fuels has been observed in
different countries since 1996 [5]. This concentration reduction was
more pronounced in most developed countries, achieving 50 mg kg− 1 or
lower. Nevertheless, many countries with low and middle incomes still
employ fuels with a high sulfur amount, reaching 500 mg kg− 1 and even
5000 mg kg− 1 [6]. According to UNEP analysis [6], the limit of 50 mg
kg− 1 of sulfur would be adopted by most countries by 2025, while the
limit of 10 mg kg− 1 (so-called ultra-low sulfur diesel - ULSD) would be
phased in most countries by 2030.
Deep hydrodesulfurization (HDS) is responsible for obtaining ULSD
(i.e. diesel with sulfur content between 10 and 15 mg kg− 1) [4]. Given
the emergent concerns about environmental impact, the demand for
ULSD is increasing. Simultaneously, the quality of oil feedstock available
for the refining process is declining [7–9]. The sulfur mass concentra­
tions in petroleum medium distillates (boiling interval from 200 to 370
◦
C) are typically between 1 and 3 % (10.000 and 30.000 mg kg− 1),
demanding from refineries the production of higher quality fuels from
lower quality raw material, with a significant impact on refinery struc­
ture and operational conditions for these processes [4,10–13].

* Corresponding author.
E-mail addresses: zotin@petrobras.com.br (J.L. Zotin), monica@eq.ufrj.br (M.A.P. da Silva).

https://doi.org/10.1016/j.cattod.2020.07.013
Received 4 March 2020; Received in revised form 7 June 2020; Accepted 7 July 2020
Available online 1 August 2020
0920-5861/© 2020 Elsevier B.V. All rights reserved.
I.G. Nascimento et al.
Fig. 1. Reaction pathway for HDS of DBT [14].
Within the main sulfured contaminants present in the diesel,
dibenzothiophene (DBT) and alkyldibenzothiophenes stand to be
representative of the most refractory compounds. The HDS of DBT oc­
curs through two pathways: direct desulfurization (DDS), responsible for
biphenyl (BPH) formation, which can be later hydrogenated to cyclo­
hexylbenzene (CHB) or hydrogenation (HYD) of a benzene ring of DBT.
This last pathway produces an equilibrium mixture of intermediate
compounds named thetrahydrodibenzothiophene (THDBT) and hex­
ahydrodibenzothiophene (HHDBT), which reacts rapidly, forming CHB.
Finally, the last aromatic ring can be hydrogenated to dicyclohexyl
(DCH) [4,14]. A reactional scheme for HDS of DBT is shown in Fig. 1.
The development of kinetic models for hydrotreating reactions is an
important tool for a better understanding of the process. In fixed-bed
reactors, these reactions occur in triphasic medium with complex phe­
nomena of mass and energy transfer. Aiming to simplify this approach, a
pseudo-homogeneous model is usually assumed, which assemble the
influence of these phenomena into apparent kinetic parameters of the
reactions. Power-law and Langmuir-Hinshelwood models are the most
used for HDT reactions. The use of power-law model is preferred for
representing real feedstocks kinetics due to the compositional and
reactional complexity. On the other hand, Langmuir-Hinshelwood
models take into consideration the adsorption of reactants and prod­
ucts on the catalyst surface. Thus, they can describe the effect of phe­
nomena such as the competition between molecules for the active sites.
The kinetics of DBT reactions using Langmuir-Hinshelwood models
was evaluated by Broderick and Gates [15] and Signhal et al. [16]. The
authors reported that the best model was a global one, considering
adsorption of DBT and H2S on one type of catalytic site and
non-dissociative adsorption of hydrogen on another type of site. Sub­
sequently, Vanrysselberghe and Froment [17] detailed the reaction
mechanism for HDS of DBT. In this work, the reaction rates for all
components were considered. The authors assumed two different types
of active sites, one for hydrogenolysis and another for hydrogenation,
with dissociative adsorption of hydrogen on both types of sites.
Competition between DBT, H2, BPH, and H2S compounds was also
considered for the respective catalytic sites. Morales-Valencia et al. [18]
assumed that all products (BPH, CHB, and H2S) contributed to kinetic
inhibition by competitive adsorption with DBT.
Topsøe et al. [19] evaluated several rate-limiting steps (from the
adsorption of reactants to desorption of products) and the best data
fittings were obtained considering that the rate-limiting step was the
addition of the first or the second hydrogen atom to the reactant
molecule (DBT). Uner et al. [20] corroborated this observation,
affirming that the rate-limiting step of the HDS process is generally the
reaction between the adsorbed organosulfur species and hydrogen.
Egorova and Prins [21] studied the HDS of DBT over NiMo and CoMo
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Catalysis Today 381 (2021) 200–208
catalysts. They reported that hydrogenation of the first phenyl ring
(HYD route) was the rate-limiting step for both catalysts. In contrast, the
next step, the removal of sulfur from the partially hydrogenated in­
termediates, is faster than the reaction of hydrogen addition. Likewise,
Rabarihoela-Rakotovao et al. [22] evaluated HDS of DBT over CoMoP
and NiMoP catalysts. They reported that the rate-limiting step for DDS
pathway is the beta-elimination of H2S from the hydrogenated inter­
mediate of this reaction.
Solvent can also affect the reaction rate. In the literature, it has been
reported that an inert hydrocarbon does not affect the kinetic constant.
On the other hand, it may compete for adsorption on the active sites,
affecting the reaction rate, especially when the solvent has a high molar
mass, such as n-hexadecane [23–25].
Due to a difficulty in estimating adsorption parameters, some authors
simplified Langmuir-Hinshelwood to power-law models, which satis­
factorily described the experimental data under the employed condi­
tions [21,26–29]. Besides, Ali et al. [30] estimated rate constants of a
kinetic model based on Langmuir-Hinshelwood mechanism for simul­
taneous HDS of DBT and alkyldibenzothiophenes. These rate constants
showed trends similar to those obtained for a pseudo-first-order kinetic
reported in previous work [31].
It is known that every experimental observation is subject to fluc­
tuations in a certain degree of incertitude and, consequently, there is no
perfect mathematical model. Such models are used to make predictions
and the uncertainties associated with the estimation of its parameters
should be considered. In this way, some statistical tests can be used to
evaluate the quality of the model and its estimated parameters [32].
However, few works reporting these tests have been found in the liter­
ature on the kinetic evaluation of hydrotreatment reactions, especially
in continuous reactors [17,33,34].
The objective of this work was the estimation of kinetic parameters
of HDS reactions of DBT employing CoMoP/Al2O3 and NiMoP/Al2O3 as
catalysts in an upflow fixed-bed reactor. For evaluation of the model
fitting quality, the chi-square test and the determination coefficient were
used. The quality of the parameters was measured by t-Student test and
parameter correlation.
2. Experimental
2.1. Catalyst preparation and characterization
The catalysts CoMoP/Al2O3 and NiMoP/Al2O3 (CoMoP and NiMoP)
were prepared by incipient wetness impregnation method, aiming to
obtain the following concentrations: 20 wt.% of MoO3, 4 wt.% of P2O5
and 4.5 wt.% of CoO or NiO. In order to obtain higher levels of mo­
lybdenum, a solution with 30 vol% ammonium peroxide is used as
solvent, which favors the solubility of the precursor [35]. These con­
centrations resulted in an atomic ratio of Ni/(Ni + Mo) equal to 0.3, and
the ratio P/Mo equal to 0.4. Phosphoric acid (85 % - VETEC), nickel
nitrate (97 % - VETEC), cobalt nitrate (97 % - VETEC) and ammonium
heptamolybdate (99 % - VETEC) were used as precursors. The pH of the
final solution was adjusted to 3. After the impregnation step, the catalyst
was dried and calcined (calcination in two stages: 300 ◦ C for 1 h and 450
◦
C for 1 h). The catalysts were characterized by X-ray fluorescence
(XRF), inductively coupled plasma - atomic emission spectrometry
(ICP-AES), N2 adsorption, X-ray diffraction (XRD) and thermogravi­
metric analysis (TGA). The particle size used for the reactions was in the
range of 0.250 to 0.150 mm.
2.2. Catalytic tests
Before the tests, the catalysts were sulfided in situ in two steps using a
solution containing 4 wt% of CS2 and n-hexane (0.10 mL min− 1). HDS of
DBT (98 % - BOC Sciences) was performed in a fixed-bed reactor (PID
Eng & Tech) operated in upflow mode. The initial concentration present
on feed was 3500 mg kg− 1 of S using a mixture of n-paraffins between
I.G. Nascimento et al. Catalysis Today 381 (2021) 200–208

Table 1 vaporization of the reacting mixture was neglected in the kinetic

Experimental conditions for validation of the best model. modeling [15,17,37–39] and the feed DBT concentration was assumed
Catalyst Validation experiment T (◦ C) P (bar) WHSV (h− 1) constant. The limitations of the mass transfer were neglected, as verified
by the Weisz-Prater and Mears criteria [40] and described in Supple­
CoMoP 1 225 45 6
2 255 45 6 mentary Information.
3 240 45 10 The model parameters were estimated using a hybrid numerical
4 240 45 12 procedure that combines a heuristic method of particle swarm optimi­
5 300 60 10 zation (PSO) with a deterministic method (Gauss-Newton) for mini­
NiMoP 6 225 45 6
7 255 45 6
mizing the objective function of weighted least squares [41–43]. The
8 270 60 10 PSO is efficient in minimizing and building the confidence region of
9 270 60 12 parameters. The random searches ensure a higher probability of finding
10 300 60 10 the global minimum of the objective function compared to methods
based on derivatives [42]. For the PSO, it was used 1000 iterations and
100 particles. The parameters that consider the individual and group
C13 and C18 as solvent (0.082 ± 0.003 mol L− 1 of DBT). The experi­
contribution to the speed of each particle were equal to 1.5, and the
ments were performed at temperatures between 210 and 270 ◦ C, H2
factor of inertia was constant and equal to 0.75 [44]. The tolerances
pressure from 30 to 60 bar and weight hourly space velocity (WHSV)
adopted for the step and the objective function were 10− 10 and 10− 8,
between 4 and 8 h− 1. The gas/oil ratio was kept constant at 400 (NL/L).
respectively. The routine of numerical integration of material balance
The progress of reaction was evaluated by gas chromatography (Agilent
equations was the Dassl [45]. The adequacy of the models could be
6890 N). It is noteworthy to mention that the global mass balance was
tested using the coefficient of determination (R2) and chi-square test.
above 95 % for all conditions evaluated for both catalysts. The station­
The confidence intervals of the parameters were obtained through
ary state was obtained on average after 6 h of time on stream on the test
t-Student distribution for a confidence level of 95 % [32]. Also, para­
condition and considering a variation less than 0.2 % in reactant con­
metric correlations were evaluated.
version. It was adopted a factorial design with 3 levels and 3 variables.
The experimental error was evaluated from three replicates obtained at
3. Results and discussion
the central point. Finally, additional experiments were carried out to
validate the best model (Table 1).
3.1. Catalytic tests

2.3. Kinetic modeling
In the molar balance equations, it was considered that the reactions
are irreversible, the hydrogen is in excess, and the catalyst bed is
isothermal. The hydrogen concentration in the liquid phase (Table S.3 in
Supplementary Information) and the maximum vaporization degree of
solvents and DBT were estimated with HYSYS by a flash calculation
using the Soave-Redlich-Kwong equation of state [36] to model all
components in the feed mixture. For 67 % of the employed experimental
conditions (temperatures up to 240 ◦ C), the maximum vaporization
degree ranged from 2 to 10 % for the solvent mixture and from 1 to 6 %
for DBT (on a molar basis). For the other experimental conditions
(temperature of 270 ◦ C), the maximum vaporization degree varied up to
22 % for the solvent mixture and up to 14 % for DBT. Due to the
concomitant vaporization of solvent and DBT, the estimated DBT con­
centrations in the feed liquid phase were very close for all experimental
conditions (variation of 9 % relative to the average value). Thus, the
Through the characterization techniques, it was verified that the
preparation of the catalyst was carried out satisfactorily. The charac­
terization results are provided in Supplementary Information.
The effects of temperature, H2 pressure and WHSV on conversion of
DBT and yield of products (BPH and CHB) were evaluated. At the
employed conditions, it was not possible to observe DCH formation. As
expected, high temperatures, low WHSV values, and high H2 pressure
increase DBT conversion.
For the CoMoP catalyst (Fig. 2a), it is observed that BPH is formed in
greater quantity than CHB, indicating that the DDS pathway was the
main reaction route [17,21,46,47]. However, for NiMoP, the yields of
both products are closer. The nickel catalyst has a higher hydrogenation
power, favoring the HYD route [48,49]. Indeed, in Fig. 2b, it is possible
to observe a reduction in BPH formation and an increase in CHB for­
mation for high conversion values (mainly at high temperatures), which
can be associated with the hydrogenation of BPH forming CHB, as

Fig. 2. Yield as a function of DBT conversion using (a) CoMoP and (b) NiMoP catalysts.

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mentioned in the literature [14,50]. Table 2

Estimation results for CoMoP catalyst.
3.2. Estimation of kinetic parameters Model Parameters of the Kinetic parameters Fobj
reparameterized equations
Four power-law models were evaluated: two global models consid­ a 4.5 ± 1.0 ln (k0) 19.5 ± 8.8
ering only DBT conversion and two more detailed, individual models b 24.0 ± 4.3 E (kJ mol− 1) 85.8 ± 15.5
GPL 23.6
that consider the reaction rate of DBT, BPH and CHB (as mentioned α* 0.4 ± 0.4 α* 0.4 ± 0.4
before, at used experimental conditions DCH concentration was negli­ β* 0.1 ± 0.2 β* 0.1 ± 0.2
gible). Global models have an important role in industrial applications PFO
a − 1.7 ± 0.1 ln (k0) 24.8 ± 4.0
30.3
because the quantification of all contaminants is less precise than b 23.1 ± 2.9 E (kJ mol− 1) 102.2 ± 12.6
a1 − 1.7 ± 0.1 ln (k0,1) 25.5 ± 3.3
assessing the total sulfur content. Furthermore, the kinetic treatment of b1 23.8 ± 2.6 E1 (kJ mol− 1) 106.0 ± 11.5
all sulfured compounds simultaneously can be relatively complex. a2 − 2.0 ± 0.4 ln (k0,2) 19.2 ± 15.3
IPL 81.0
The first model tested was a global power-law (GPL) model with b2 17.1 ± 5.5 E2 (kJ mol− 1) 79.5 ± 25.6
adjustable reaction orders for DBT and H2, as described by the following a3 − 1.1 ± 0.9 ln (k0,3)* 24.1 ± 2645.6
b3* 23.0 ± 72.7 E3 (kJ mol− 1)* 103.0 ± 325.9
equation:
a1 − 1.5 ± 0.1 ln (k0,1) 24.1 ± 2.6
dCDBT b1 22.7 ± 2.3 E1 (kJ mol− 1) 100.3 ± 10.2
α
CHβ 2 (1) PIPL 89.9
− = kHDS CDBT a2 − 1.7 ± 0.1 ln (k0,2) 24.4 ± 4.3
ρd τ b2 22.7 ± 2.9 E2 (kJ mol− 1) 101.4 ± 13.1

where Ci is the molar concentration of compound i (mol L− 1), τ is the

*
Parameter statistically non-significant from the t-Student test considering
space-time (h), ρ is the density of feedstock (kg L− 1), kj is the rate significance level of 95 %.
constant of reaction j (mol1-α-β Lα+β kg−cat1 h− 1) and α and β are reaction
order related to DBT and H2, respectively. ( ) Ej
A simpler approach of Eq. 1 widely cited in literature can be used aj = ln k0,j − (10)
R Tref
[14,28,34,51–57]. The pseudo-first-order kinetic model (PFO) considers
that hydrogen concentration does not influence HDS activity because Ej
the main route for this reaction is DDS [28,34]. bj = (11)
R Tref
dCDBT
− = kHDS CDBT (2) where aj and bj are the fitting parameters, T is the temperature (K), Tref
ρd τ
is the reference temperature (K), k0,j is the pre-exponential factor for
The third and fourth models consider the kinetics of each reaction reaction j, Ej is the activation energy for reaction j (kJ mol− 1) and R is
pathway in order to model the product distribution for each catalyst. A the universal gas constant (kJ mol− 1 K− 1). When the model contains
simple pseudo-first-order kinetics was considered for the reaction steps. more than one rate constant (models IPL and PIPL), the correlation
The third model considers a series-parallel reaction scheme, with DDS between parameters aj and bj for each reaction should be minimized by
and HYD reaction being parallel steps and BPH being hydrogenated to optimizing the reference temperatures. This optimization was per­
CHB, as described in reference [50]. For the last model, only the parallel formed through the minimization of the sum of the squares of all
steps were considered [58]. The order related to H2 was assumed as zero parameter correlations [60], using the package “scipy.optimize” of Py­
for DDS pathway and first order for HYD [34]. thon. The optimized reference temperatures are available in Supple­
For the third model (individual power-law - IPL), the equations are mentary Information (see Tables S.8 to S.11).
presented below: A model of the Langmuir-Hinshelwood type for reagent consumption
dCDBT was also evaluated. However, the adsorption equilibrium constant of
− = k1 CDBT + k2 CDBT CH2 (3) DBT did not present statistical significance. These results are available in
ρd τ
Supplementary Information.
dCBPH The parameter estimation for CoMoP catalyst is presented in Table 2,
= k1 CDBT − k3 CBPH CH2 (4) where Fobj is the minimized value of objective function. The errors of the
ρd τ
kinetic parameters were calculated by linear propagation of the errors
dCCHB obtained for the estimation of aj and bj.
= k2 CDBT CH2 + k3 CBPH CH2 (5)
ρd τ The order regarding hydrogen concentration was not statistically
significant. This result was expected given that direct desulfurization
For the fourth model (parallel-individual power-law – PIPL), the
was the preferential pathway for HDS of DBT. However, the estimated
equations can be described as follows:
order regarding DBT concentration was also non-significant, which in­
dCDBT dicates a numerical difficulty in adjusting such order together with the
− = k1 CDBT + k2 CDBT CH2 (6)
ρd τ non-significant order of hydrogen.
Only in the PFO and PIPL models, all parameters were statistically
dCBPH significant. For model PIPL, the apparent activation energy for DDS
= k1 CDBT (7)
ρd τ route (E1) obtained is lower than values found in the literature [46,53].
These authors reported apparent activation energy between 130 and
dCCHB
= k2 CDBT CH2 (8) 146 (kJ mol− 1) for DDS route and values between 92 and 99 (kJ mol− 1)
ρd τ for HYD route (E2). For model PFO, the global activation energy was
However, there is a high parametric correlation between the pre- consistently close to the energies obtained for the individual routes in
exponential factor and the apparent activation energy during param­ model PIPL and corroborated the literature [28,31].
eter estimation. In order to minimize this effect, a reparameterized form In model IPL, the non-significant parameter was b3, which gives the
of the Arrhenius equation was used [59], shown below: temperature dependence of the rate constant of the BPH hydrogenation
( ( ) ) to CHB (Eq. 9). Thus, this dependence could not be quantified from the
kj = exp aj + bj
T − Tref
(9) available experimental data, probably due to the low number of
T experimental points in the range of high DBT conversion (Fig. 2a), where

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I.G. Nascimento et al. Catalysis Today 381 (2021) 200–208

Fig. 3. Predicted versus observed concentrations using CoMoP for model (a) GPL, (b) PFO, (c) IPL and (d) PIPL.

Only the model IPL presented one non-significant parameter, b3,

Table 3 indicating that the temperature dependence of the BPH hydrogenation
Estimation results for NiMoP catalyst. could not be estimated from the experimental data, similar to what was
Model Parameters of the Kinetic parameters Fobj observed for CoMoP catalyst. Again, this is probably because few
reparameterized equations experimental points referred to high DBT conversions (Fig. 2b).
a 5.0 ± 1.0 ln (k0) 24.7 ± 9.2
For NiMoP catalyst, the reaction order related to sulfur-containing
b 29.6 ± 4.4 E (kJ mol− 1) 97.3 ± 14.6 compound on model GPL was approximately 1, which is usually adop­
GPL 11.6 ted in the literature [52,64,65]. Besides, the order regarding the H2
α 1.2 ± 0.5 α 1.2 ± 0.5
β 0.3 ± 0.2 β 0.3 ± 0.2 concentration (β) obtained was statistically significant, which is
a − 1.6 ± 0.1 ln (k0,1) 22.8 ± 1.7 coherent with the higher hydrogenating behavior exhibited by NiMoP
PFO 1 19.5
b 21.2 ± 1.9 E1 (kJ mol− ) 94.0 ± 8.4 catalyst. The values of the activation energy found by PIPL model are
a1 − 1.4 ± 0.1 ln (k0,1) 20.3 ± 2.9
1 similar to those reported by Mello et al. [34] of 109 ± 2 and 103 ± 5 kJ
b1 18.9 ± 2.4 E1 (kJ mol− ) 84.8 ± 10.7
a2 − 2.2 ± 0.2 ln (k0,2) 27.2 ± 21.9 mol− 1 for the routes DDS and HYD, respectively. As it was observed for
IPL 1 51.8 CoMoP catalyst, the global activation energy in model PFO was very
b2 24.9 ± 6.6 E2 (kJ mol− ) 112.3 ± 29.8
a3 − 2.3 ± 0.4 ln (k0,3)* − 6.0 ± 43.8 close to the energies obtained for the individual routes in model PIPL.
1
b3* − 8.3 ± 9.4 E3 (kJ mol− )* − 36.8 ± 41.3 These apparent activation energies are close to the values 98 and 107 kJ
a1 − 1.0 ± 0.1 ln (k0,1) 21.2 ± 1.2
1 mol− 1, reported by Abid et al. [28] and Gao et al. [65], respectively.
b1 20.2 ± 1.5 E1 (kJ mol− ) 89.80 ± 6.8
PIPL 73.4 The quality of adjustment of each model to the experimental data is
a2 − 2.3 ± 0.1 ln (k0,2) 23.6 ± 1.7
b2 21.3 ± 1.8 E2 (kJ mol− 1
) 95.1 ± 8.1 presented in Fig. 4.
*
Parameter statistically non-significant from the t-Student test considering
Regarding the parametric correlation, models GPL and IPL showed
significance level of 95 %. moderate to strong correlations for both catalysts. In the case of GPL
model, this was expected due to the mathematical structure of powers.
Correlations in the other models were close to zero. All tables of para­
the BPH hydrogenation is expected to be more significant [61–63].
metric correlation and covariance are available in Supplementary
However, parameter a3 was significant, so that a
Information.
temperature-independent rate constant could be assigned to the BPH
Table 4 presents the limit values for the objective functions of the
hydrogenation.
models, considering the chi-square test.
The quality of adjustment of each model to the experimental data is
The test consists in assessing whether the value of the objective
presented in Fig. 3.
function is between the minimum and maximum values that can be
The parameter estimation for NiMoP catalyst is presented in Table 3.
calculated from the chi-square cumulative probability distribution for a

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Fig. 4. Predicted versus observed concentrations using NiMoP for model (a) GPL, (b) PFO, (c) IPL and (d) PIPL.

corroborates the statistical tests mentioned before, which indicate that

Table 4 the model PIPL satisfactorily represents the experimental data.
Limit values for the objective functions of the models considering the chi-square
The parameters estimated considering the PFO and PIPL models
test.
were also used to calculate the rate constants for both catalysts at 300 ◦ C
Fobj,max Fobj and 60 bar of H2, shown in Table 5. It was observed that the NiMoP
Model Degree of freedom Fobj,min
CoMoP NiMoP catalyst presented the higher HYD rate constant, indicating that this
GPL 23 11.7 38.1 23.6 11.6* catalyst is more hydrogenating, as observed experimentally. On the
PFO 25 13.1 40.6 30.3 19.5 other hand, the global rate constant calculated using PFO model was
IPL 75 52.9 100.8 81.0 51.8* higher for catalyst CoMoP. Therefore, for the DBT HDS reaction, the
PIPL 77 54.6 103.2 89.9 73.9 CoMoP catalyst was more efficient.
*
Value out of the range from the chi-square test considering significance level The statistical tests (Tables 2–4, Figs. 3 and 4, and Tables S.9 and
of 95 %. S.11) and the validation experiments (Figs. 5 and 6) reveal that purely
empirical models are capable of achieving a good fit to the experimental
given level of confidence and degree of freedom. Models PFO and PIPL data within the evaluated range of operational conditions.
presented the best performances because they met the evaluated sta­
tistical tests (t-Student and chi-square), as well as high determination 4. Conclusions
coefficients and weak parametric correlations for both catalysts. The
better performance of model PIPL relative to model IPL indicates that Regarding the product distribution, biphenyl was the main product
there was no need to consider the BPH hydrogenation to CHB in the for CoMoP catalyst, corroborating the literature that reports the DDS
kinetic modeling, for the evaluated operational conditions. route as the preferential pathway. In addition, it was observed that the
Besides, five experiments, which were not used in the parameter nickel-promoted catalyst showed the highest hydrogenation behavior
estimation, were compared with the respective simulated values to and, therefore, the smallest difference between the yields in products
validate the PIPL kinetic model. This was considered the best model from DDS and HYD routes.
because it is the more detailed one to present a good performance, given For both catalysts, the kinetic evaluation revealed a good fit for a
the t-Student and chi-square tests (see Tables 2–4) and the low para­ simple power-law model considering the global DBT conversion only
metric correlations (Table S.11). The results are shown in Figs. 5 and 6. (pseudo-first-order model - PFO), as well as for a more detailed model
Figs. 5 and 6 show the overlap of the observed and predicted con­ considering a reactional scheme with the DDS and HYD parallel routes
fidence intervals for 97 % of the evaluated concentrations. Therefore, for (parallel-individual power-law model - PIPL), as indicated by the t-
most experimental conditions, the simulated concentration was statis­ Student and chi-square tests. In both these models, the estimated acti­
tically equal to the respective observed concentration. This simulation vation energies were between 90 and 100 kJ mol− 1 for CoMoP and
NiMoP catalysts. According to the evaluated statistical tests, the

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Fig. 5. Simulated concentrations from model PIPL and observed concentrations for validation using CoMoP catalyst for (a) DBT, (b) BPH and (c) CHB.

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I.G. Nascimento et al. Catalysis Today 381 (2021) 200–208

Fig. 6. Simulated concentrations from model PIPL and observed concentrations for validation using NiMoP catalyst for (a) DBT, (b) BPH and (c) CHB.

HDS of DBT based on the estimated global rate constant of the PFO
Table 5
model. Nevertheless, NiMoP catalyst exhibited the higher hydrogena­
Rate constants calculated for a reaction at 300 ◦ C and 60 bar of H2.
tion behavior for experiments performed at the same conditions.
1
Model Catalyst Rate constant (L kg− h− 1)

HDS CRediT authorship contribution statement

PFO CoMoP 28.5 ± 6.2
NiMoP 22.7 ± 3.2
DDS
PIPL CoMoP 21.3 ± 4.4
NiMoP 10.8 ± 1.2
*
Normalized by H2 concentration in the liquid phase.
biphenyl hydrogenation to cyclohexylbenzene should not be considered
in the kinetic modeling of HDS of DBT for the employed operational
conditions, since this reaction is expected to be significant only at con­
ditions with high DBT conversions, which were not sufficiently covered
in this work. In order to obtain more information on this reaction, more
experimental points at severe conditions would be necessary (i.e., higher
temperatures and H2 pressures or lower WHSV).
The PIPL model was considered the best model for the obtained
experimental data because it met the statistical tests, presenting all pa­
rameters with significance, low parametric correlations and high
determination coefficients, and it is more detailed compared to the
pseudo-first-order model. In addition, the predictive power of the model
PIPL was tested confronting estimated values and supplementary
experimental data (i.e. conditions that were not used to obtain param­
eter values). For most cases evaluated, the corresponding confidence
intervals of the observed and predicted concentrations overlapped,
validating the kinetic model.
The CoMoP catalyst was considered the most efficient catalyst for the
Idia G. Nascimento: Conceptualization, Methodology, Investiga­
HYD*
tion, Software, Formal analysis, Writing - original draft. William de R.
9.2 ± 1.5 Locatel: Conceptualization, Methodology, Investigation, Writing -
15.7 ± 2.0 original draft. Bruno C. Magalhães: Conceptualization, Methodology,
Investigation, Formal analysis, Writing - original draft. Leonardo
Travalloni: Software, Writing - review & editing. José L. Zotin: Su­
pervision, Writing - review & editing. Mônica A.P. da Silva: Concep­
tualization, Methodology, Supervision, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
To PETROBRAS S.A. for financial support through project
0050.0099615.15.9. To CENPES for support to catalyst preparation and
characterization. Idia G. Nascimento and William de R. Locatel
acknowledge CAPES and CNPq for their financial support.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the

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I.G. Nascimento et al.
online version, at doi:https://doi.org/10.1016/j.cattod.2020.07.013.
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