Accepted Manuscript

The Effect of Calcination Temperature on the Activity of Hydrodesulphurization

Catalysts Supported on Mesoporous Activated Carbon

Umar A. Cheche, Khalid R. Alhooshani, Sagir Adamu, Jameel Al Thagfi, Tawfik A.

Saleh

PII: S0959-6526(18)33580-7

DOI: 10.1016/j.jclepro.2018.11.177

Reference: JCLP 14936

To appear in: Journal of Cleaner Production

Received Date: 06 May 2018

Accepted Date: 19 November 2018

Please cite this article as: Umar A. Cheche, Khalid R. Alhooshani, Sagir Adamu, Jameel Al Thagfi,
Tawfik A. Saleh, The Effect of Calcination Temperature on the Activity of Hydrodesulphurization
Catalysts Supported on Mesoporous Activated Carbon, Journal of Cleaner Production (2018), doi:
10.1016/j.jclepro.2018.11.177

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT

The Effect of Calcination Temperature on the Activity of

Hydrodesulphurization Catalysts Supported on Mesoporous Activated
Carbon
Umar A. Cheche 1, Khalid R. Alhooshani 1, Sagir Adamu 2, Jameel Al Thagfi 1,
Tawfik A. Saleh *1

1 Chemistry Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi
Arabia
2 Chemical Engineering Department, King Fahd University of Petroleum & Minerals, Dhahran

31261, Saudi Arabia

*Correspondence to: e-mail: [email protected] ; [email protected]

Home Page: http://faculty.kfupm.edu.sa/CHEM/tawfik/

Abstract

The removal of sulfur compounds from petroleum is increasingly important because sulfur
compounds poison catalysts (i.e. reduce the activity of the catalysts in oil refinery processes) and
are a source of environmental pollution. On the other side, waste rubber tires contribute to
environmental pollution. Here, the motive is the utilization of activated carbon (AC) from the
waste tires as a support for bimetallic catalysts. Therefore, NiMo catalysts supported on waste
tire-derived AC were prepared through an excessive wetness co-impregnation method and
subjected to calcination at temperatures of 100, 200, 300 and 400 °C for hydrodesulfurization
(HDS). A surface area analyzer, Fourier-transform infrared spectroscope, scanning electron
microscope, and Raman spectroscope were used to characterize the prepared catalysts. The HDS
reactions with the prepared catalysts were performed in a high-pressure reactor using a model
fuel containing 1000 ppm dibenzothiophene at different reaction times. The results showed that
the catalyst that is calcined at 300 °C (i.e. NiMo/AC300) is the most active for HDS as compared
to the catalysts calcined at other temperatures (i.e. 100, 200 and 400 °C). This catalyst (i.e.
NiMo/AC300) has a surface area of 352 m2/g, a 6 nm average pore diameter, a total acidity of
0.26 mmol ammonia/g and exhibits a moderate activation energy for NH3 desorption (i.e. Ea =

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102 kJ/mol). The developed catalysts show promising results with the advantage of having a dual
benefit – eliminating waste tire disposal problem and producing valuable supports for HDS
catalysts to yield sulfur-free fuels.

Keywords: Nanotechnology; Oil refinery; Petrochemicals upgrading; Hydrodesulphurization;

calcination; Kinetics

1. Introduction
Crude oil undergoes multiple treatments during the refining process. The removal of sulfur (S) is
one important step since the combustion products of S compounds are the main reason for
environmental pollution. In addition, S is also a catalyst poison. SulSfur compounds are present
in crude oil in a wide range of both aliphatic and aromatic forms including thiophenes.
Hydrodesulfurization (HDS) is a catalytic chemical process widely used to remove S from
natural gas and from refined petroleum products, such as gasoline or petrol, jet fuel, kerosene,
and diesel fuel. The development of catalysts with suitable supports to be used in HDS is one
area of research that has continued to generate tremendous interest [1]. The supports are needed
for the catalysts to prevent the agglomeration of the catalyst particles, thus maintaining their
efficiency in HDS. Suitable supports improve the performance of catalysts through enhanced
stability caused by the interaction between the catalysts and the support, dispersion of the active
phase of the catalyst on the support and complementary interactions between the catalyst and the
support. The performance of catalysts is measured using a high-pressure reactor in the fuel.

It has long been established that the support materials play crucial roles in industrial processes
such as hydrodesulfurization that involves the use of metal catalysts such as molybdenum (Mo),
platinum (Pt), nickel (Ni), and cobalt (Co) [2]. Studies on the effects of different supports on the
catalytic HDS activity have shown that some catalysts exhibit a higher activity when removing
the S as it is loaded on carbon supports (such as activated carbon (AC), graphene and carbon
nanotube) by the hydrothermal method, compared to the other popular support materials [3]. For
example Mo, Co and Ni sulfides showed higher levels of activity on carbon supports as
compared to alumina or silica [4]. In fact, CoMo/Al2O3 was found to be less effective in the
hydrodesulfurization (HDS) of dibenzothiophene (DBT) and diesel fuel when compared to Co-
Mo/C catalysts under the same experimental conditions [5]. The enhanced HDS activity of these
catalysts when supported on carbonaceous supports have been attributed to the minimal catalyst-

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support interactions which become stronger when the same catalysts are supported on metal
oxide supports [6, 7].

Several studies have demonstrated that there is a strong correlation between the support types
and the performance of HDS catalysts. Some of the salient factors include: composition,
morphology, surface acidity and stability of the support material [8]. For instance, despite the
numerous desirable characteristics of alumina, its strong interactions with metallic oxide
catalysts impedes sulfidation and leads to some undesirable transformations [9,10]. Besides the
minimal catalysts-support interactions, studies have shown that carbon supports possess certain
unique advantages over alumina and other metal oxide supports. These advantages include
higher surface areas than alumina, as well as the ease of recovering the active Mo particles from
the spent or used catalysts [7].

Tremendous effort has been devoted to the formulation of more robust catalysts and the
modification of the existing ones for enhanced activity and efficiency. In this regards, we
reported previously that HNO3-treated AC at 90 °C exhibited the best performance for adsorptive
HDS as compared to other AC based supports treated at lower temperatures in HNO3 or NaOH
[11]. In most cases, the target is to increase the proportion and stability of the most active phase
of the catalysts [12,13] or to increase the dispersion of support materials through the use of
chelating agents [14,15]. Carbon has been noted to possess desirable properties that allow for the
dispersion of the active phase of the catalysts [16,17]. The inherent high surface area and low
surface acidity are some of the key attributes that have made carbon attractive as a potential
alternative support for catalysts used in various applications, especially the HDS of fuels [8,18].
In fact, numerous studies related to the utilization of carbon material as support for various HDS
catalyst have been reported [11,18]. Recent developments include the preparation of mesoporous
carbon supports using a different approach to achieve a specific morphology and other desirable
characteristics that will improve the performance of the supported catalyst [19,20]. Doping
carbon supports with heteroatoms and the extension of the applications of the supported catalysts
to simultaneous HDS and hydrodenitrogenation (HDN) have also been reported [21].

It has been established that the type of the active species (metal catalysts like Mo) and the extent
of their dispersion in the support is related to the type of support materials and the calcination
temperature after the usual impregnation, along with the subsequent drying [18]. Even the degree

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of presulfidation of Mo dispersed in various support materials was shown to be affected by the

calcination temperature [22]. Although there are numerous sources of carbon, including biochar
[23, 24, 25], the conversion of waste rubber tires into AC has a dual advantage: it overcomes the
problems of disposal and offers useful support for catalysts.

To the best of our knowledge, no reports have been published with a focus on the calcination
effect of NiMo particles supported on AC. The hypothesis is that the calcination temperature of
the prepared catalysts has an effect on the HDS. Therefore, in this study, we investigated the role
of calcination temperature on the performance of an NiMo catalyst supported on AC sourced
from waste rubber tires. From the results, we can easily determine whether or not these
pretreatment steps are necessary for the optimal performance of the supported catalysts.

2. Experimental Section
2.1. Materials
Ammonium molybdate [(NH4)6Mo7O24.4H2O] molecular weight 1235.86 g/mol, and nickel
acetate [Ni(C2H3O2)2.4H2O] molecular weight 248.8366 g/mol, are of A.C.S certified analytical
grades from the Fisher Scientific Company, USA. Analytical grade reagents helped in improved
optimization of the study. Decahydronaphthalene (decalin) [C10H18] (99%), and
dibenzothiophene (DBT) [C12H8S] (98%) were obtained from Sigma Aldrich, USA.

2.2. Catalysts Preparation

The materials used are AC derived from waste rubber tires [11]. In brief, the waste rubber tires

were cut and the iron wires were removed. The rubber pieces were cleaned and thermally treated

at 573 K. The obtained char was carbonized at 773 K. Then, the obtained carbon black was

activated with 4 M nitric acid at 363 K under a reflux condenser. Next, AC was separated and

dried for the preparation of catalysts.

The catalysts were prepared through excessive wetness impregnation of the AC with an Mo
atomic weight of 95.95 g/mol (13 wt.%) and an Ni atomic weight of 58.69 g/mol (3 wt.%) using
aqueous solutions containing the appropriate amounts of their metal salts, as depicted in Fig. 1.
Around 6 g of the AC was added to aqueous solutions containing 1.435g ammonium molybdate
(0.78 g Mo) and 0.762g nickel acetate (0.18g Ni). The misxture was stirred, then, the solution

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was allowed to evaporate at 70 °C and subjected to further drying at 100 °C for 24 h. Three of the
samples were calcined at temperatures of 200, 300 and 400 °C. This range was selected as per
the literature and to avoid the side effect on C if the temperature increased. The calcination lasted
for 3 h under a continuous flow of nitrogen (N2 flow rate was maintained at 20 mL/min and a
temperature ramp of 10 °C min-1). The samples were labeled NiMo/AC100, NiMo/AC200,
NiMo/AC300 and NiMo/AC400, depending on the calcination temperature. The four prepared
catalysts were characterized and evaluated for HDS activity.

Fig. 1. Preparation of NiMo/AC by excessive wetness impregnation

2.3. Catalyst Characterization

X-ray diffraction (XRD) of the sample was performed using a Bruker D8 focus diffractometer,
with Cu Kα radiation at 40 kV and 40 mA. Diffractograms of the catalysts in powder form were
recorded at 12 °min-1 scanning speed over 10° ≤ 2θ ≤ 90°. The surface areas were measured to
obtain the N2 physisorption pore volume, and the pore size distributions were determined via the
BET and BJH methods using a Micromeritics ASAP-2010 instrument. The catalysts were
degassed at 150 °C for 3 h prior to the physisorption experiments at 77 K. The adsorption
isotherms for nitrogen were measured at 77 K.

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2.4. Catalyst Testing

The HDS activity test was conducted in a high-pressure batch reactor (model: Parr 4576B)
operated at 350 oC and under a pressure of 50 MPa with rotation. About 0.3 g of NiMO/AC was
introduced to 0.1 L of the fuel which contained DBT (1000 ppm-S) using dodecane as a solvent.
The tests were performed at various reaction times. The S content was analyzed by gas
chromatography sulfur chemiluminescence.

3. Results and Discussion

3.1 Catalyst identification

The FTIR spectra presented in Fig. 2 reveals some of the functional groups present in the AC-

based supported catalysts. The most conspicuous are the bands centered around 3400, 2350,

1600 and 1300 -100 cm−1, which are peculiar to some of the common functional groups often

associated with AC. The broad band centered at 3400 cm−1 is due to the stretching vibrations of

O–H while the bands at 2350, 1600 and 1300 -100 cm−1 are due to C≡C stretching vibration of

the alkyne group, (C═O) stretching vibrations of carboxylic and carbonyl compounds. This is a

clear indication of the presence of acidic oxygen groups that can serve as adsorption sites on the

surface of the catalysts. IR bands can be attributed to the Mo-O-Mo stretching vibrations found

at 620 and 850 cm-1. The strength of these acidic sites was investigated via ammonia temperature

programmed desorption (TPD). Moreover, ammonia desorption studies also help in correlating

the activity with the accessibility of the active sites, especially those located on the micropores

possessing similar diameters to reactants and/or intermediates [26].

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Fig. 2. IR Spectra of the prepared catalysts: NiMo/AC100, NiMo/AC200, NiMo/AC300 and NiMo/AC400

The powder X-ray diffractograms of the catalysts NiMo/AC100, NiMo/AC200, NiMo/AC300

and NiMo/AC400 are presented in Fig. 3. In all cases, there are three major broad diffraction
peaks at 2θ values of 25, 37 and 54 °. However, the peaks for NiMo/AC300 and NiMo/AC400
are more intense when compared to NiMo/AC100 and NiMo/AC200. The appearance of these
peaks can be attributed to the presence of Mo species and the varying degree of intensity of the
peaks is a result of the difference in the degree of crystallinity. This is an indication that
calcination at high temperature affects the degree of crystallinity of the nanoparticles
incorporated into the AC. The diffraction peak at around 2θ value of 25 ° can be attributed to the
graphite or to hexagonal MoO3 [27–29]. Diffraction peaks at 2θ of 20 – 30° (002) 40 – 50 °
(101) have been reported for the graphite phase of AC [20,30,31]. The additional peaks can be
attributed to other forms like MoO3 or even MoO2. Therefore, the presence of these peaks can be
taken as additional evidence of the successful impregnation of the AC with the metal catalyst.
There are no visible and peculiar peaks that indicate the presence of Ni due to its presence as a
promoter on Mo or its low concentration as compared to the proportion of Mo [32].

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Fig. 3. X-Ray diffraction spectra of catalysts; NiMo/AC100, NiMo/AC200, NiMo/AC300 and NiMo/AC400

The scanning electron microscopy (SEM) images in Fig. 4 show the surface morphology and

textural characteristics of selected catalysts. It is important to note that the nanoparticles of NiMo

are well distributed on the AC sheets as a catalyst support [33]. The SEM image indicates the

pores on the surface of the AC support, as well as metal particles on the surface. This is an

indication that some of the metals were deposited onto the surface of the AC while some might

have been trapped in the pores. The energy dispersive x-ray (EDX) spectra provide both

qualitative and quantitative information about the surface composition of the prepared catalysts.

The identified elements present are C, O, Mo, and Ni. It was not unexpected that C was found to

have the most intense peak because C represents over sixty percent of the elements in the

sample. The peaks related to O and Mo are conspicuous and account for approximately nine

percent and seven percent, respectively.

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(a) (b)

(c) (d)

Fig. 4. SEM images of (a) NiMo/AC100, (b) NiMo/AC200, (c) NiMo/AC300 and (d) NiMo/AC400

The results of the textural properties of the AC support and the various catalysts prepared using
different calcination temperatures are presented in Table 1. The changes in the textural properties
of the support material on loading Ni and Mo are evident when the values of the BET surface
area and the average pore volumes obtained for the support materials are compared to those of
the prepared catalysts, as shown in Fig. 5. In general, the BET surface areas of the new catalysts
were lower than that of the bare AC support material. The observed reduction in the BET surface
area can be attributed to the incorporation of Ni and Mo onto the C-based support material. In
addition, a reduction in the specific surface area of the support after loading with metals was
observed. A similar trend was observed with the pore volumes and the average pore size of the
catalyst although the difference in magnitudes is small compared to the difference in the specific
surfaces areas. Moreover, there is a noticeable difference in the magnitude of the specific surface
area of the catalysts depending on the calcination temperature employed at the preparation stage.
NiMo/AC400 has the largest surface area compared to NiMo/AC300 and NiMo/AC200.

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However, the NiMo/AC400 has a smaller average pore diameter. The observed trend is an
indication that the metals were successfully loaded on the AC support. The solvent and volatile
reagents trapped within the pores are more effectively evacuated at higher temperatures. The
shapes of the adsorption-desorption isotherms obtained for the catalysts calcined at different
temperatures are similar to those of the Type-IV isotherms associated with mesoporous materials
as reported in previous work [19], [34] and [35].

Table 1. The obtained textural features of catalysts

Catalysts BET Surface External Micropore Total pore Average pore

Area (m²/g) Surface Area Area (m²/g) volume of diameter (Å)
(m²/g) pores (cm³/g)
AC 583.37 350.16 233.20 0.98 52.32
NiMo/AC100 323.03 220.07 102.96 0.53 65.58
NiMo/AC200 356.70 229.13 127.56 0.55 61.53
NiMo/AC300 352.11 230.78 121.33 0.53 60.25
NiMo/AC400 434.53 259.60 174.94 0.60 54.83

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Fig. 5. N2 Adsorption-desorption Isotherms of the carbon support and catalysts where p/p0 is the relative
pressure, P is the pressure and P0 is the saturation pressure of adsorbate at the temperature of adsorption

3.2 Temperature Programmed Desorption and Kinetic Modeling

Temperature programmed desorption of NH3 from the surface of the catalysts was used to

determine the surface acidity of the prepared catalyst after calcination at the stated temperatures

(i.e. 100, 200, 300 and 400 °C). It is evident from the results presented in Fig. 6 that both the

weak and strong acid sites are present although the latter is significantly more abundant in all

cases.

The peak desorption temperatures recorded for the catalysts at around 150 °C are for the weak

acid sites while the more intense peaks at 620-660 and 726 °C are due to the desorption of NH3

from the strong acid sites [36]. Table 2 shows the results of the acidity and kinetics of NH3

desorption from the prepared AC based catalysts. The desorption kinetics was carried out by

applying the following equation [37].

) ( ( ))
𝑑𝑉𝑑𝑒𝑠 𝑘𝑑𝑒𝑠
(
𝑉𝑑𝑒𝑠 𝐸𝑑𝑒𝑠 1 1
𝑑𝑇
= 𝛽
1‒ 𝑉𝑚
exp ‒ 𝑅 𝑇 𝑇𝑐
‒ (1)

Where, Vdes/Vm is the fractional volume of NH3 desorbed, Tc is the centering temperature, β is the

heating rate, kdes is the first order rate constant, and Edes is the activation energy.

The model was solved in Mathematica using a nonlinear model which applies the 4th order

Runge Kutta. The regression was achieved by applying a Levenberg-Marquardt algorithm

(Mathematica’s NonLinearModelFit function). This minimizes the sum of the square errors

between the observed and predicted values. It can be observed in Table 2 that all the samples

show high coefficients of determination, R2 > 0.99. To further evaluate the goodness of the fit,

we have illustrated the parity plot (Fig. 7) of the experimental versus the model predicted

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fractional amounts of ammonia desorbed from the samples. Each of these samples was initially

saturated with ammonia at 120 °C. The data points were close to the 45° line, with random

deviations of the data above and below the equality line. Therefore, we deduce that the first order

desorption model adequately satisfies the experimental desorption process from the four samples.

In general, the activation energies are of the same order, with comparable rate constants.

NiMo/AC400 exhibits the highest activation energy (i.e. 135.36 kJ/mol), with a fast rate constant
‒3 ‒1
of 17.5𝑥10 𝑚𝑖𝑛 . This indicates a relatively stronger affinity of the support for basic

reactants/adsorbents, as compared to the other supports. Moreover, the fact that it desorbed the

highest amount of NH3 (i.e. 0.276 mmol/g) suggests that it contains a greater number of acidic

sites than the other catalysts. However, it is important to note the correlation between the surface

area of the catalysts and the acidity of the catalysts calcined at the different temperatures.

NiMo/A300 exhibits two desorption peaks suggesting the existence of stronger acid sites (in

addition to the common acid sites observed at around 656 °C for the rest of the catalysts). The

lowest value of the average desorption energy from the varying acid sites of NiMo/AC300 is

102.60 kJ/mol.

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Fig. 6. Ammonia TPD (concentration versus temperature) profiles of the freshly prepared samples

Fig. 7: Parity plot of the experimental and predicted fractional amounts of ammonia desorbed
from the samples, initially saturated with ammonia at 120 °C.

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Table 2. NH3 desorption data and results of kinetic modeling

Sample BET Acidity Peak Rate constant, kdes Activation R2
Surface area (mmol NH3/g) desorption (min-1) energy, Ea
(m2/g) Temperature, (kJ/mol)
Tp (°C)
NiMo/AC100 323.03 0.204 646.17 0.0152 ± 0.00058 114.89 ± 2.30 0.998

NiMo/AC200 356.70 0.240 656.43 0.0123 ± 0.00074 119.27 ± 3.45 0.997

NiMo/AC300 352.11 0.260 620, 726.34 0.0197 ± 0.00085 102.60 ± 3.74 0.997

NiMo/AC400 434.53 0.276 631.06 0.0175 ± 0.00053 135.36 ± 1.26 0.998

3.3 Catalyst performance

The performance of NiMo catalysts supported on AC was evaluated for the conversion of DBT
at different reaction times, Table 3. The experiments were performed by measuring the amounts
of DBT present in the aliquots taken from the batch reactor at intervals of 1 h. Throughout the
reaction time, higher conversions were achieved by increasing the reaction time using the
catalysts calcined at different temperatures. However, catalysts calcined at high temperatures
performed better after long reaction times. The difference in DBT conversions becomes
significant, especially when the reaction is allowed to proceed beyond 2 h. Among the prepared
catalysts, NiMo/AC300 gave the best performance. A comparison of NiMo/AC(200) and
NiMo/AC(400) at the 4 h shows differences of more than 10%, Fig. 8. This is a clear indication
that the supported catalyst calcined at 300 oC was more effective in the HDS of DBT. The peak
desorption temperature in TPD plot for the NiMo/AC400 is higher than that of NiMo/AC300
which indicates that it is more difficult for molecules to desorb from the surface. This could be
the reason why the performance of NiMo/AC400 is less than that of the material calcined at 300
oC (i.e. NiMo/AC300). This is supported by the high NH3 desorption activation energy, Ea of
135 kJ/mol for the NiMo/AC400 as compared to 103 kJ/mol for NiMo/AC300. Also, the

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average pore diameter (Å) for the NiMo/AC400 is 55 as compared to 60 for NiMo/AC300,
indicating that the material which calcined at 300 oC possesses a more suitable pore size than that
calcined at 400 oC. The reason could be that some metal nanoparticles blocked some of the pores
of the materials that calcined at 400 oC to a greater extent than in the case of the material which
calcined at 300 oC. Thus, the obtained results indicated that the prepared catalyst can be used on
an industrial scale since the reactor usually works at around 300 oC for the industrial
desulfurization process. Previous studies reported on the preparation of HDS catalysts with a
calcination effect where the sequential impregnation method is used. The calcination is often
repeated after the incorporation of each of the active species [38]. The reported catalysts showed
a comparable performance to those reported in the literature, as shown in Table 4. However, the
reported catalysts in this study are inexpensive from a financial point of view since the AC was
derived from waste tires.

Table 3. Concentrations of sulfur in aliquot taken from the reactor at 1 h intervals

Concentration of DBT in of products taken at intervals (ppm)

Catalysts
Set point (0 h) 1h 2h 3h

NiMo/AC100 713 430 271 36

NiMo/AC200 747 216 122 49

NiMo/AC300 707 228 132 12

NiMo/AC400 840 691 366 153

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Fig. 8. Graphical representation of the performance of NiMo/AC, NiMo/AC/200, NiMo/AC300

and NiMo/AC400

Table 4. Comparing between the AlMoCoB5% catalysts and others reported in the
literature.

Sulfur Sulfur Removal

Catalysts Reference
Concentration (ppm) %
FeMoS/Carbon 1000 30% [39]

NiMo/graphene 1300 ppm-DBT 99 % [40]

P and Ni–Al2O3
supported Mo 520 50% [41]
oxycarbide
CoMo/SBA-15 2160 77% [42]
CoMoS and
340 97% [43]
NiMoS
NiMo/–Al2O3 740 90% [44]

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3.4 Kinetics studies

The activity of the catalysts towards the HDS of DBT was measured by calculating the kinetic
rate constants for each catalyst, assuming a pseudo first order kinetics. The calculations were
based on the changes in the concentration of sulfur present in the aliquots taken from the reactors
at intervals of 1 h starting when the temperature of the reactor reaches 350 °C. The values of the
rate constants for all the catalysts are presented in Table 5. Analysis of the results shows that the
catalysts calcined at lower temperatures were more active than the catalysts calcined at higher
temperatures. The value of the rate constant for NiMo/AC300 is higher that of NiMo/AC400,
even though its R2 value is larger in magnitudes. The values obtained for the rate constants are
similar to those reported for HDS catalysts supported on AC, and even other porous materials
[5], [31] and [32]. Moreover, the R2 values for all the catalysts indicate that results fit well with
the pseudo-first-order- kinetics proposed for the HDS of DBT.

Table 5. Pseudo-first-order kinetics for NiMo/AC, NiMo/AC200, NiMo/AC300 and

NiMo/AC400

Catalysts Average Products Distribution (%)

BP PC

NiMo/AC100 88 11
NiMo/AC200 83 16
NiMo/AC300 82 17
CoMo/AC400 79 18

The HDS rate constants k (s-1), ks-1g-1cat. R2 values were calculated for all the prepared catalysts,

NiMo/AC100, NiMo/AC200 and NiMo/AC300 and NiMo/AC400, and the results are presented

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in Table 6. The pseudo 1st order rate constant calculated for NiMo/AC100, NiMo/AC200,

NiMo/AC300 and NiMo/AC400 are 2.0 × 10-4s-1, 1.9 × 10-4 s-1, 8.8 × 10-5 s-1 and 8.9 × 10-5 s-1

respectively. The decrease in the magnitude of the rate constant as the calcination temperature

increases is a clear indication that calcination at higher temperatures reduces the activity of the

catalyst. Moreover, the magnitude of the R2 values range from 0.850 to 0.989, which suggests

that the reactions involving all of the tested catalysts agree well with the proposed pseudo-first

order kinetics for the desulfurization process using supported Mo-based catalysts. Calculations

for the nth order rates yielded lower R2 values. The slope of the lines from the kinetics plots

presented in Fig. 9 further illustrates how the thermal treatment enhanced the HDS of the DBT.

While NiMo/AC100, NiMo/AC200, and NiMo/AC300 have a slope of approximately 0.0002,

NiMo/AC400 has a slope of 0.0001 which suggests that the HDS reaction is slower when

NiMo/AC400 is used as a catalyst. The observed phenomenon can be attributed to the

differences in the extent of the dispersion of the metal catalysts on the support and the higher

degree of NiMo/AC300 crystallinity of the active phase evident in the XRD spectra, Fig. 3.

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Fig. 9. Plots for (A) NiMo/AC (B) NiMo/AC200, (C) NiMo/AC300 and (D) NiMo/AC400
suggest pseudo-first-order reaction

3.5. Proposed mechanism

The composition of the aliquots taken from the reactor at an interval of 1 h was determined by
GC-MS and the results are presented in Table 6. Biphenyl (BP), and phenylcyclohexane (PC) are
the main products identified from the HDS of DBT for all of the catalysts used under the same
reaction conditions. In all cases, BP was present in larger amounts when compared to PC
depending on the catalyst used. The results show that the catalysts calcined at lower temperatures

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are more selective towards the formation of BP. The distribution of products after the HDS
reaction is one of the factors that is often taken into consideration in order to determine the
selectivity of the catalysts involved, as well as the HDS reaction pathway. The proposed
mechanism is illustrated in Fig. 10. It should be noted that BP and PC are the main products of
DBT HDS which result from the direct desulfurization and hydrogenolysis of the substrate.
Various types of catalysts have been tested and the impact of the synthesis routes or preparation
conditions on product distribution investigated by various research groups have shown that the
products of the HDS reactions involving DBT are mainly BP and PC [8].

Table 6. Products distribution for NiMo/AC, NiMo/AC200, NiMo/AC300 and NiMo/AC400

Catalysts Average Products Distribution (%)

BP PC

NiMo/AC100 88 11
NiMo/AC200 83 16
NiMo/AC300 82 17
CoMo/AC400 79 18

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Fig. 10. Proposed mechanism for the HDS of DBT over the prepared catalyst

4. Conclusions
The scientific hypothesis was confirmed: the calcination temperature of the NiMo/AC catalysts,
prepared by excessive wetness impregnation of the AC support, has an effect on the HDS. The
catalysts were calcined at temperatures of 200-400 °C under N2 atmosphere after drying at 100
°C and their performance assessment reveals that the calcination temperature plays a role in the
HDS performance of the catalyst. Subtle variations in the properties of the catalysts were
observed from the results of the characterization by TGA, FT-IR, SEM-EDX, and XRD. The
results show that the catalyst calcined at 300 °C was more effective in the HDS of DBT than the
other catalysts calcined at different temperatures. The differences in the performance of the
catalysts can be attributed to the degree of dispersion and crystallinity of the active phase. The
realistic outstanding performance of NiMo/AC300 is related to its favorable structural and
textural properties, as well as its moderate metal-support interaction as evidenced by its low

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activation energy for NH3 desorption as compared to other catalysts. The utilization of waste
rubber tires as a source for AC production involves a dual cleaning process: solving the tires’
disposal issues and converting tires to useful materials; thus, it has dual benefits for both the
environment and industry. From an economic point of view, the reported catalysts are applicable
on a commercial scale as the support is obtained from waste.

Acknowledgements
The authors acknowledge the support provided by King Fahd University of Petroleum &
Minerals (KFUPM) – Saudi Arabia for funding this work through project No. DSR NUS15105.

References
[1] H. Ge, Z. Qiu, Z. Ge, W. Han, Improvement of Hydrodesulfurization Catalysts Based on Insight of
Nano Structures and Reaction Mechanisms, 2018. doi:10.1007/978-3-319-60630-9_4.
[2] T.A. Saleh, Applying Nanotechnology to the Desulfurization Process in Petroleum Engineering,
1st ed., IGI Global, 2016.
[3] S.K. Maity, L. Flores, J. Ancheyta, H. Fukuyama, Carbon-Modified Alumina and Alumina -
Carbon-Supported Hydrotreating Catalysts, Ind. Eng. Chem. Res. 48 (2009) 1190–1195.
[4] J. Matos, J.L. Brito, J. Laine, Activated carbon supported Ni-Mo: effects of pretreatment and
composition on catalyst reducibility and on ethylene conversion, Appl. Catal. A Gen. 152 (1997)
27–42. doi:10.1016/S0926-860X(96)00334-1.
[5] H. Farag, D.D. Whitehurst, K. Sakanishi, I. Mochida, Carbon versus Alumina as a Support for Co-
Mo Catalysts Reactivity towards HDS of Dibenzothiophenes and Diesel Fuel, Catal. Today. 50
(1999) 9–17. doi:10.1016/S0920-5861(98)00476-3.
[6] Y. V. Joshi, P. Ghosh, M. Daage, W.N. Delgass, Support effects in HDS catalysts: DFT analysis
of thiolysis and hydrolysis energies of metal-support linkages, J. Catal. 257 (2008) 71–80.
doi:10.1016/j.jcat.2008.04.011.
[7] H. Farag, Synthesis of CoMo-based carbon hydrodesulfurization catalysts: Influence of the order
of metal impregnations on the activity, Appl. Catal. B Environ. 84 (2008) 1–8.
doi:10.1016/j.apcatb.2008.02.026.
[8] M.S. Shafeeyan, W.M.A.W. Daud, A. Houshmand, A. Shamiri, A review on surface modification
of activated carbon for carbon dioxide adsorption, J. Anal. Appl. Pyrolysis. 89 (2010) 143–151.
doi:10.1016/j.jaap.2010.07.006.
[9] P.A. Nikulshin, V.A. Salnikov, A. V. Mozhaev, P.P. Minaev, V.M. Kogan, A.A. Pimerzin,
Relationship between active phase morphology and catalytic properties of the carbon-alumina-
supported Co(Ni)Mo catalysts in HDS and HYD reactions, J. Catal. 309 (2014) 386–396.
doi:10.1016/j.jcat.2013.10.020.
[10] M.M. Hossain, K.E. Sedor, H.I. de Lasa, Co–Ni/Al2O3 oxygen carrier for fluidized bed chemical-
looping combustion: Desorption kinetics and metal–support interaction, Chem. Eng. Sci. 62
(2007) 5464–5472. doi:10.1016/j.ces.2006.12.066.

22
 ACCEPTED MANUSCRIPT

[11] T.A. Saleh, G.I. Danmaliki, Influence of acidic and basic treatments of activated carbon derived
from waste rubber tires on adsorptive desulfurization of thiophenes, J. Taiwan Inst. Chem. Eng. 60
(2016) 460–468. doi:10.1016/j.jtice.2015.11.008.
[12] L. Peña, D. Valencia, T. Klimova, CoMo/SBA-15 catalysts prepared with EDTA and citric acid
and their performance in hydrodesulfurization of dibenzothiophene, Appl. Catal. B Environ. 147
(2014) 879–887. doi:10.1016/j.apcatb.2013.10.019.
[13] A.I. Dugulan, J.A.R. van Veen, E.J.M. Hensen, On the structure and hydrotreating performance of
carbon-supported CoMo- and NiMo-sulfides, Appl. Catal. B Environ. 142–143 (2013) 178–186.
doi:10.1016/j.apcatb.2013.05.013.
[14] J.A. Toledo-antonio, J. Navarrete-bola, Applied Catalysis B : Environmental Upgrading HDS
activity of MoS 2 catalysts by chelating thioglycolic acid to MoO x supported on alumina, 213
(2017) 106–117. doi:10.1016/j.apcatb.2017.05.011.
[15] K. Ben Tayeb, C. Lamonier, C. Lancelot, M. Fournier, A. Bonduelle-Skrzypczak, F. Bertoncini,
Active phase genesis of NiW hydrocracking catalysts based on nickel salt heteropolytungstate:
Comparison with reference catalyst, Appl. Catal. B Environ. 126 (2012) 55–63.
doi:10.1016/j.apcatb.2012.06.025.
[16] E. Diaz, A.F. Mohedano, J.A. Casas, L. Calvo, M.A. Gilarranz, J.J. Rodriguez, Comparison of
activated carbon-supported Pd and Rh catalysts for aqueous-phase hydrodechlorination, Appl.
Catal. B Environ. 106 (2011) 469–475. doi:10.1016/j.apcatb.2011.06.005.
[17] R.G. Rao, R. Blume, T.W. Hansen, E. Fuentes, K. Dreyer, S. Moldovan, et al., Interfacial charge
distributions in carbon-supported palladium catalysts, Nat. Commun. 8 (2017).
doi:10.1038/s41467-017-00421-x.
[18] J.J. Lee, S. Han, H. Kim, J.H. Koh, T. Hyeon, S.H. Moon, Performance of CoMoS catalysts
supported on nanoporous carbon in the hydrodesulfurization of dibenzothiophene and 4,6-
dimethyldibenzothiophene, Catal. Today. 86 (2003) 141–149. doi:10.1016/S0920-5861(03)00408-
5.
[19] T.-Y. Ma, L. Liu, Z.-Y. Yuan, Direct synthesis of ordered mesoporous carbons., Chem. Soc. Rev.
42 (2013) 3977–4003. doi:10.1039/c2cs35301f.
[20] L.J. Konwar, P. Mäki-Arvela, E. Salminen, N. Kumar, A.J. Thakur, J.P. Mikkola, et al., Towards
carbon efficient biorefining: Multifunctional mesoporous solid acids obtained from biodiesel
production wastes for biomass conversion, Appl. Catal. B Environ. 176–177 (2015) 20–35.
doi:10.1016/j.apcatb.2015.03.005.
[21] T.A. Saleh, Nanotechnology in Oil and Gas Industries: Principles and Applications, Springer,
2017.
[22] G.I. Danmaliki, T.A. Saleh, Influence of conversion parameters of waste tires to activated carbon
on adsorption of dibenzothiophene from model fuels, Journal of Cleaner Production 117 (2016)
50-55.
[23] J. Maroušek, M. Vochozka, J. Plachý, J. Žák, Glory and misery of biochar, Clean Technologies and
Environmental Policy, 19 (2017) 311–317.

[24] J Maroušek, Significant breakthrough in biochar cost reduction, Clean Technologies and

23
 ACCEPTED MANUSCRIPT

Environmental Policy 16 (2014), 1821-1825

[25] J Maroušek, Economically oriented process optimization in waste management, Environmental
Science and Pollution Research 21 (2014) 7400-7402.
[26] A. Le Valant, N. Bion, F. Can, D. Duprez, F. Epron, Preparation and characterization of bimetallic
Rh-Ni/Y2O3-Al2O3 for hydrogen production by raw bioethanol steam reforming: influence of the
addition of nickel on the catalyst performances and stability, Appl. Catal. B Environ. 97 (2010)
72–81. doi:10.1016/j.apcatb.2010.03.025.
[27] C. Fontaine, Y. Romero, A. Daudin, E. Devers, C. Bouchy, S. Brunet, Insight into sulphur
compounds and promoter effects on Molybdenum-based catalysts for selective HDS of FCC
gasoline, Appl. Catal. A Gen. 388 (2010) 188–195. doi:10.1016/j.apcata.2010.08.049.
[28] A. Tougerti, E. Berrier, A.S. Mamede, C. La Fontaine, V. Briois, Y. Joly, et al., Synergy between
XANES Spectroscopy and DFT to Elucidate the Amorphous Structure of Heterogeneous
Catalysts: TiO2-Supported Molybdenum Oxide Catalysts, Angew. Chemie - Int. Ed. 52 (2013)
6440–6444. doi:10.1002/anie.201300538.
[29] T. Bhaskar, K.R. Reddy, C.P. Kumar, M.R.V.S. Murthy, K.V.R. Chary, Characterization and
reactivity of molybdenum oxide catalysts supported on zirconia, Appl. Catal. A Gen. 211 (2001)
189–201. doi:10.1016/S0926-860X(00)00874-7.
[30] S. Kang, J. Ye, J. Chang, Recent Advances in Carbon-Based Sulfonated Catalyst:Preparation and
Application, Int. Rev. Chem. Eng. 5 (2013) 133–144. doi:10.15866/ireche.v5i2.6912.
[31] J. Chen, H. Yang, Z. Ring, HDS kinetics study of dibenzothiophenic compounds in LCO, in:
Catal. Today, 2004: pp. 227–233. doi:10.1016/j.cattod.2004.07.036.
[32] T.C. Ho, Deep HDS of diesel fuel: Chemistry and catalysis, in: Catal. Today, 2004: pp. 3–18.
doi:10.1016/j.cattod.2004.07.048.
[33] Y. Wang, R.T. Yang, Desulfurization of liquid fuels by adsorption on carbon-based sorbents and
ultrasound-assisted sorbent regeneration, Langmuir. 23 (2007) 3825–3831.
doi:10.1021/la063364z.
[34] D. Valencia, T. Klimova, Citric acid loading for MoS2-based catalysts supported on SBA-15. New
catalytic materials with high hydrogenolysis ability in hydrodesulfurization, Appl. Catal. B
Environ. 129 (2013) 137–145. doi:10.1016/j.apcatb.2012.09.006.
[35] R. Huirache-Acuña, T.A. Zepeda, E.M. Rivera-Muñoz, R. Nava, C. V. Loricera, B. Pawelec,
Characterization and HDS performance of sulfided CoMoW catalysts supported on mesoporous
Al-SBA-16 substrates, Fuel. 149 (2015) 149–161. doi:10.1016/j.fuel.2014.08.045.
[36] M.A. Alvarez-Merino, J.P. Joly, F. Carrasco-Marín, C. Moreno-Castilla, Application of ammonia
intermittent temperature-programmed desorption to evaluate surface acidity of tungsten oxide
supported on activated carbon, J. Colloid Interface Sci. 260 (2003) 449–453. doi:10.1016/S0021-
9797(02)00253-9.
[37] S. Adamu, M.Y. Khan, S.A. Razzak, M.M. Hossain, Ceria-stabilized meso-Al2O3: synthesis,
characterization and desorption kinetics, J. Porous Mater. 24 (2017) 1343–1352.
doi:10.1007/s10934-017-0376-3.
[38] S.L. Amaya, G. Alonso-Núñez, T.A. Zepeda, S. Fuentes, A. Echavarría, Effect of the divalent
metal and the activation temperature of NiMoW and CoMoW on the dibenzothiophene

24
 ACCEPTED MANUSCRIPT

hydrodesulfurization reaction, Appl. Catal. B Environ. 148–149 (2014) 221–230.

doi:10.1016/j.apcatb.2013.10.057.
[39] R. Hubaut, J. Altafulla, A. Rives, C. Scott, Characterization and HDS activities of mixed Fe – Mo
sulphides supported on alumina and carbon, Fuel. 86 (2007) 743–749.
doi:10.1016/j.fuel.2006.09.012
[40] H. Wang, B. Xiao, X. Cheng, C. Wang, L. Zhao, Y. Zhu, J. Zhu, X. Lu, NiMo catalysts supported on
graphene-modified mesoporous TiO2 toward highly efficient hydrodesulfurization of
dibenzothiophene, Appl. Catal. A Gen. 502 (2015) 157–165. doi:10.1016/j.apcata.2015.05.028
[41] P. Da Costa, J. Manoli, C. Potvin, Deep HDS on doped molybdenum carbides : From probe
molecules to real feedstocks, Catal. Today. 108 (2005) 520–530. doi:10.1016/j.cattod.2005.07.166
[42] L. Peña, D. Valencia, T. Klimova, CoMo/SBA-15 catalysts prepared with EDTA and citric acid and
their performance in hydrodesulfurization of dibenzothiophene, Appl. Catal. B Environ. 147
(2014) 879–887. doi:10.1016/j.apcatb.2013.10.019
[43] N. Kunisada, K.H. Choi, Y. Korai, I. Mochida, Effective supports to moderate H2S inhibition on
cobalt and nickel molybdenum sulfide catalysts in deep desulfurization of gas oil, Appl. Catal. A
Gen. 260 (2004) 185–190. doi:10.1016/j.apcata.2003.10.016
[44] E. Pedernera, R. Reimert, N.L. Nguyen, V. Van Buren, Deep desulfurization of middle distillates:
Process adaptation to oil fractions’ compositions, Catal. Today. 79–80 (2003) 371–381.
doi:10.1016/S0920-5861(03)00066-X

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 ACCEPTED MANUSCRIPT

Highlights

 Activated carbon from waste tires was loaded with Ni and Mo nanoparticles and

calcined at different temperatures

 Prepared catalysts showed excellent performance for HDS of sulfur compounds

 The prepared catalyst calcined at 300 oC showed the highest efficiency