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Experimental and Kinetics Studies of

Aromatic Hydrogenation in a Two-Stage


Hydrotreating Process using NiMo/Al2O3
and NiW/Al2O3 Catalysts
Abena Owusu-Boakye1, Ajay K. Dalai1*, Deena Ferdous1 and John Adjaye2
1. Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering,
University of Saskatchewan, 57 Campus Drive, Saskatoon, SK, Canada S7N 5A9
2. Syncrude Canada Ltd., Edmonton Research Centre, 942117th Avenue, Edmonton, AB, Canada T6N 1H4

In this work, hydrogenation of aromatic compounds in light gas oil derived from Athabasca bitumen was carried out using a single- and two-stage
hydrotreating processes. Experiments were performed in a trickle-bed reactor using two catalysts namely NiMo/Al2O3 and NiW/Al2O3. NiMo/Al2O3
was used in the first stage for nitrogen and sulphur containing heteroatoms removal whereas NiW/Al2O3 was used in the second stage for satura-
tion of the aromatic rings in the hydrocarbon species. Temperature and liquid hourly space velocity (LHSV) were varied from 350390C and
1.01.5 h1, respectively, while pressure was maintained constant at 11.0 MPa for all experiments. Results from single-stage were compared with
those from two-stage process on the basis of reaction time. Kinetic analysis of the single-stage hydrotreating process showed that HDA and HDS
activities were retarded by the presence of hydrogen sulphide that is produced as a by-product of the HDS process. However, with inter-stage
removal of hydrogen sulphide in the two-stage process, significant improvement of the HDA and HDS activities were observed.

On a ralis dans ce travail lhydrognation de composs aromatiques dans du gasoil lger driv de bitumes dAthabasca laide de procds
dhydrotraitement mono et bi-tag. Des expriences ont t menes dans un racteur lit ruisselant avec deux catalyseurs, savoir NiMo/Al2O3
et NiW/Al2O3. NiMo/Al2O3 a t utilis dans le premier tage pour lazote et le retrait des htroatomes contenant du soufre, tandis que NiW/
Al2O3 a t utilis dans le second tage pour la saturation des anneaux aromatiques dans les espces dhydrocarbures. On a fait varier la
temprature et le volume par volume par heure (LHSV) de 350-390C et de 1,0-1,5 h-1, respectivement, tandis que la pression est maintenue
constante 11,0 MPa pour toutes les expriences. Les rsultats du procd mono-tag sont compars ceux du procd bi-tag sur la base
du temps de raction. Lanalyse cintique du procd dhydrotraitement mono-tag montre que les activits de lHDA et lHDS sont retardes
par la prsence de sulfure dhydrogne qui est produit par le procd HDS. Toutefois, avec le retrait de lhydrogne sulfur entre les deux tages
dans le procd bi-tag, on observe une amlioration importante des activits de lHDA et lHDS.

Keywords: two-stage hydrotreating, aromatic hydrogenation, hydrodesulphurization, hydrodenitrogenation, NiMo/Al2O3,


NiW/Al2O3, kinetic studies

INTRODUCTION diesel and also contributes to the formation of particulate

M
uch attention has been focused on saturation of aromat- emissions in exhaust gases. For example, a typical Western
ics and removal of sulphur and nitrogen compounds in Canada diesel fuel produced from oil sands has the following
light gas oil (LGO) produced from unconventional composition: sulphur: < 500 ppm; aromatics (3040%) and
crude sources. This is because reserves for conventional crudes cetane number (3740) (Environment Canada, 2002). With
are gradually declining (Nishijima et al., 1996; Laherrere, 2003) such composition, the diesel fuel is considered as a poor grade
and with the increasing demand of diesel fuel worldwide on-road fuel.
(Laherrere, 2003; Kamiya, 1991), there is the need to find Studies (Johnson, 1983; Yoes and Asim, 1987; McCulloch et
alternative fuel sources. One of such alternative sources is al., 1987) show that existing middle distillate hydrotreaters
synthetic crude produced from coal and oil sands. designed to reduce sulphur levels are capable of reducing the
Synthetic crude can be distilled into the naphtha, LGO and aromatics contents marginally, resulting in a shift in research
heavy gas oil, HGO fractions. Refiners are particularly interested interest to the development of new catalysts, catalysis and hydrot-
in the LGO fraction because of its use as a diesel or jet fuel
blending stock (Yui, 1994). However, the high concentrations of
aromatics makes its use as a diesel blending stock difficult, since * Author to whom correspondence may be addressed.
high concentrations of aromatics lower the cetane number of E-mail address: ajay.dalai@usask.ca

572 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 84, OCTOBER 2006
reating technology for aromatics hydrogenation (Cooper and et al. (1999) also studied the effects of hydrogen sulphide on the
Donnis, 1996). Some of the new process technologies developed hydrotreating of middle distillates over CoMo/Al2O3 catalyst.
include the two-stage process that has proven to be the most Using an isothermal fixed-bed reactor they discovered that the
efficient for maximum hydrogenation of aromatics when catalysts inhibiting effect of hydrogen sulphide in hydrogenation of
containing noble metals and nickel are used (Laherrere, 2003; aromatics decreased with increasing temperatures.
Stanislaus and Cooper, 1994; Mahay et al., 1992; Landau et al., In this study, the degree of hydrogenation of aromatics in LGO
1996). However, these hydrogenation catalysts are easily poisoned feed from Athabasca bitumen is investigated using a two-stage
by the high sulphur and nitrogen contents in the feedstock. process with NiMo/Al2O3 in stage one and NiW/Al2O3 in the
Hence, the feedstock will first have to be hydrotreated to reduce second stage. The effect of residence time on hydrogenation of
the sulphur and nitrogen contents prior to the hydrogenation aromatics in each stage of hydrotreating was also studied.
reactions to reduce the aromatics contents. Results from the two-stage process were compared to those from
The two-stage hydroprocessing technique was used by Mahay a single-stage where hydrotreating was performed over NiMo/
et al. (1992) to reduce the pronounced effects of nitrogen- Al2O3. Furthermore, the effect of H2S inhibition on aromatics
containing species inhibition during hydrocracking of synthetic hydrogenation was kinetically modelled using Langmuir-
crude gas oils on NiW/Al2O3 catalyst supported on silica- Hinshelwood approach.
alumina. Higher gas oil conversions were achieved and the
middle distillate product quality was remarkably improved as
the diesel fuel cetane number increased by 13%. Diesel tests also EXPERIMENTAL
indicated that the particulate emissions in exhaust gases were Hydrotreating was carried out in a fixed-bed reactor system
lowered by 20%. (10 mm internal diameter and 285 mm length). Commercial
Some workers (Nishijima et al., 1996) have also compared NiMo/Al2O3 and lab-prepared NiW/Al2O3 catalysts were used in
two-stage hydrogenation in co-processing oil and light cycle oil Stage I and Stage II, respectively.
(LCO) using both NiMo and NiW on alumina support. The latter NiW/Al2O3 catalyst was prepared by incipient wetness
catalyst was used for the second stage upgrading, because impregnation method with extruded -alumina. In this method,
sulphur was largely removed in the first stage hydrogenation 3.0 wt.% of Ni in nickel nitrate, 15 wt.% of tungsten in
over NiMo/Al2O3 catalyst. From their study, a large improve- ammonium metatungstate and 2.5 wt.% of phosphorus in
ment in the cetane index (from 36 in the feed to 53 at the end of phosphoric acid in water were impregnated onto the alumina
the second stage) was observed in the co-processing oil whereas support. Prior to impregnation, the support, -Al2O3 (obtained
the cetane improvement in the (LCO) remained modest (from 30 from Sud Chemical India Ltd., New Delhi) was dried at 120C
in the feed to 43 at the end of the second stage). The kinetics of overnight to remove any moisture. Following impregnation, the
two-stage aromatics hydrogenation, employing a simple-first catalyst was dried again at a temperature of 120C for 12 h and
order reversible reaction model have also been studied by Yui then calcined at 500C for another 4 h.
(1994). However, with the extensive research on HDA in gas oils In each case, 5 g of the catalyst in extrudate form was used.
(Mahay et al., 1992; Stanislaus and Cooper, 1994; Landau et al., Figure 1 shows the schematic representation of the catalyst
1996; Guan et al., 2004), reports on the two-stage HDA kinetics loading in the reactor. From bottom to top in the micro-reactor
in bitumen-derived light gas oils, taking into account hydrogen are layers of 22 mm glass beads followed by a 25, 10 and 10 mm
sulphide inhibition are scarce. of 16, 46 and 60 mesh silicon carbide (SiC), respectively. The
Hydrogen sulphide, which is produced as a by-product of catalyst bed was maintained at 9.5 cm in height with 90-mesh
sulphur removal has been reported to significantly inhibit size SiC (diluent) to provide complete catalyst wetting and
hydrogenation of aromatics compounds (Van Gestel et al., 1992; reduce radial dispersion. The large pellet sizes of the catalyst as
Girgis and Gates, 1991; Massoth et al., 1982). Ishihara et al. well as the compact nature of catalyst bed packing provided by
(2003) investigated phenanthene (PHE) hydrogenation reaction the diluent reduced the bed porosity; thus minimizing any
inhibition over NiMo/Al2O3 induced by the presence of dibenzo- diffusion effects and providing plug flow conditions for isother-
thiophene (DBT) molecule in a conventional fixed-bed reactor. mal reactions (Bej et al., 2000). The plug flow conditions were
Results from their study showed that PHE hydrogenation slightly also ensured by the different layers of SiC and inert glass beads.
increased in the presence of low concentration of DBT. On the top part of the catalyst were 8 mm of the 60, 46 and 16
Furthermore, the progressive reintroduction of DBT in the feed mesh SiC and 20 mm of glass beads. Finally, an empty space of
after the reaction without DBT led to a significant decrease in the about 20 mm reactor was left. In the two-stage process, the
PHE hydrogenation activity as well as DBT conversion. Their catalyst was packed in the same way as that described for one-
results show that although the presence of sulphur in a feed is stage process.
essential to preserve good catalytic performance, some hydrogen- The reactor was heated by an electrically controlled furnace
ation catalytic sites can be permanent poisoned, thus reducing and the temperature was measured by a single thermocouple
the hydrogenation activity. inserted in the middle part of the outside reactor skin.
Mild inhibition of biphenyl hydrogenation over CoMo/Al2O3 Temperature gradient was within 2C, thus ensuring isothermal
catalyst due to hydrogen sulphide has been reported by Satterfield temperature along the length of the reactor.
and Gultekin, 1981. Kasztelan et al. (1994) studied the influence LGO blend from Athabasca bitumen was used as feedstock.
of H2S partial pressure on the activity of model MoS2/Al2O3 over Properties of the feedstock are summarized in Table 1.
a wide range of H2S partial pressure from 00.3 MPa, under a Experiments were performed by varying the reactor temperature
total pressure of 6 MPa, at 320410C and 0.5-0.7 h1. Moderate from 350390C at three LHSV ratios (ratio of Stage I to Stage II)
inhibiting effects of H2S with H2S partial pressure up to 0.06 MPa of 1.5:1, 1:1 and 1:1.5 h1. Pressure and hydrogen-to-oil ratio
on aromatic hydrogenation were observed. For H2S partial were maintained constant at 11.0 MPa, and 550 ml/ml,
pressures higher than 0.06 MPa, no apparent inhibiting effect of respectively. The total reaction time for both stages was 1.67 h.
H2S on the hydrogenation activity was detected. Ancheyta-Juarez

VOLUME 84, OCTOBER 2006 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 573
Table 1. Properties of LGO blend feedstock

Property Value
Density (15C), g/cc 0.9007
Carbon, wt.% 85.5
Hydrogen, wt.% 12.06
Total sulphur, wppm (ASTM D-4629) 17420
Total nitrogen, wppm (ASTM D-4629) 461
Basic nitrogen, wppm 247
Aromatics, wt.% (13 C -NMR) 17.1
Cetane index, CI (ASTM D-976) 36
Simulated distillation, C (ASTM D2887 HT)
IBP 169.6
10 wt.% 183.0
30 wt.% 230.2
50 wt.% 279.6
80 wt.% 349.1
90 wt.% 375.5
FBP 439.2

RESULTS AND DISCUSSION


It is known that NiMo/Al2O3 catalyst is active for hydrodenitro-
genation and hydrodesulphurization reactions and NiW/Al2O3
catalyst is active for aromatic hydrogenation reaction. However,
this catalyst deactivates quickly in the presence of nitrogen and
sulphur (Sun et al., 2004). Therefore, NiMo/Al2O3 catalyst was
used in Stage I and NiMo/Al2O3 and NiW/Al2O3 catalysts were
used in two-stage processes in Stage II. However, the amount of
catalyst was not optimized in this work.
In single-stage process, NiMo/Al2O3 catalyst was used to
remove nitrogen and sulphur from different gas oil such as
Figure 1. Reactor catalyst loading profile
vacuum light gas oil (VLGO), atmospheric light gas oil (ALGO)
and hydrotreated light gas oil (HLGO). In this stage, process was
The light gas oil fraction was first hydrotreated over sulphided optimized to maximize aromatic hydrogenation and the optimum
NiMo/Al2O3 in the stage one reactor to reduce sulphur and operating conditions were 379C, 11.0 MPa and 0.6 h1. It was
nitrogen contents. Hydrogen sulphide was them removed from observed that temperature has the significant effect on aromatic,
the Stage I effluents before hydrotreating over the sulphided nitrogen and sulphur conversion (Owusu-Boakye, 2005).
NiW/Al2O3 catalyst in the Stage II reactor. In two-stage process, temperature was varied from 340 to
The feed and products were tested for total sulphur, nitrogen 390C when pressure and LHSV were maintained constant at the
and aromatics contents. The sulphur and nitrogen concentra- optimum values of 11.0 MPa and 0.6 h1, respectively. LHSV
tions were measured with an Antek 9000 NS analyzer that uses ratios were varied from 1:1.5 to 1.5:1. In this process, maximum
combustion/fluorescence or chemiluminescence techniques. nitrogen and sulphur conversions were obtained at the tempera-
Concentrations of the individual aromatics groups (mono, di and ture, pressure and LHSV of 390C, 11.0 MPa and 0.6 h1, respec-
polyaromatics) as well as the total aromatics content were tively (see Table 2).
determined by supercritical fluid chromatography. Scheme 1
describes the general flow pattern of the two-stage process. Two-Stage Hydrotreating and H2S Inhibition Studies
Several classes of reactions occur simultaneously in hydrotreat-
ingHDA, HDS and HDNand the presence of some of the
reactants and products are known to markedly affect reactivity
(Girgis and Gates, 1991). In particular, H2S produced from HDS
reactions has been reported to be responsible for the hindrance
of aromatics hydrogenation as well as HDS and HDN reactions
(Ishihara et al., 2003; Kabe et al., 1999; Nagai et al., 1988).
In this research, the effects of hydrogen sulphide inhibition on
aromatics hydrogenation (HDA), cetane index (CI) improve-
Scheme 1. Two-stage hydrotreating process of light gas oil ment, hydrodesulphurization (HDS) and hydrodenitrogenation

574 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 84, OCTOBER 2006
Table 2. Overall aromatics, sulphur and nitrogen concentration in the LGO blend after two-stage hydrotreating process
Temperature, Pressure, LHSV, Saturates Aromatic contents, % Sulphur, Nitrogen,
C MPa h1 wppm wppm
Mono- Di- Poly- Total
Feed 63.3 20.7 12.2 3.6 36.5 17420 461
350 11.0 1.5 83.2 14.6 2.2 0.03 16.8 262 <10
365 11.0 1.5 87.4 10.9 1.7 0.03 12.6 690 <10
380 11.0 1.5 92.7 6.3 1.0 0.02 7.3 233 <10
390 11.0 1.5 92.2 6.7 1.1 0.05 7.8 167 <10
350 11.0 1.2 86.7 11.9 1.4 0.02 13.3 78 <10
365 11.0 1.2 91.2 8.0 0.9 0.00 8.9 97 <10
380 11.0 1.2 92.9 6.4 0.7 0.00 7.1 88 <10
390 11.0 1.2 92.3 7.0 0.7 0.00 7.7 79 <10
350 11.0 1.0 87.2 11.5 1.3 0.00 12.8 109 <10
365 11.0 1.0 91.4 7.7 0.9 0.00 8.6 95 <10
380 11.0 1.0 93.0 6.2 0.8 0.00 7.0 80 <10
390 11.0 1.0 93.9 5.8 0.3 0.00 6.4 68 <10

were studied at different space velocities ratios and temperatures where M = mid boiling point temperature (C) and = specific
using a two-stage hydrotreating unit. Overall aromatics sulphur gravity.
and nitrogen concentration in the LGO blend after two-stage Significant differences in the cetane indices of the single- and
hydrotreating process is given in Table 2. Results from the two- two-stage processes were observed at higher reaction temperatures
stage process were compared to that of a single-stage process (i.e., 380 390C) where about 7 10% increments were observed
where hydrotreating was carried out over NiMo catalyst. The for the latter process. At the lower temperatures (340 350C),
hydrotreating data from both process technologies were compared only 2 3% increase in the CI occurred in the two-stage unit. The
in terms of relative gain, defined as: highest cetane index in the single-stage process was 44 at 365C
whereas for the two-stage process, a higher temperature of 380C
ktwo stage ksingle stage was required to obtain the best cetane value of 46. It is also
Relative gain, ki = * 100%
ksingle observed from Table 2 that further increase in reactor temperature
stage
above 380C (in the two-stage) and 365C (in the single-stage)
where, ki is the reaction rate constant for HDA, HDS or HDN. had limitations for additional increase in CI and this is because
these temperatures are close to the equilibrium temperature for
Impact of H2S removal and LHSV ratio on HDA hydrogenation of aromatics.
Figure 2 illustrates the relative gain in HDA rate constants at Figure 3 shows the impact of the H2S removal on the overall
different LHSV ratios (Stage I:Stage II) in the two-stage process cetane index improvement in the two-stage process at different
compared to the single-stage process. A general decrease in gain reaction temperatures and LHSV ratios. Just like hydrogenation
in rate constants, kA was observed with increasing temperature of aromatics the best CI occurred at 380C at LHSV ratio of
and this was because of the enhancement in the HDA activity 1.5:1.0. These observations are in agreement with literature
with increasing temperature and due to relatively less impact of (Yui, 1994). There may be mild hydrocracking of gas oil at
inter-stage removal of hydrogen sulphide at relatively high 390C producing lower molecules and thus reducing CI of the
temperature. The negative gain in the reaction rate constants liquid product.
between 365 390C and 390C for the LHSV ratios of 1.0:1.5
and 1.0:1.0, respectively, indicated higher conversions in the
single-stage process compared to the two-stage process. The best
activity for HDA in the two-stage was observed for the LHSV
ratio of 1.5:1.0 at all reaction temperatures, which showed that
the longer reaction time and the higher hydrogenation activity of
the NiW catalyst in Stage II had a significant impact on the
hydrogenation reaction. Therefore, relatively higher reaction
time may be maintained in Stage II by loading more NiW
catalysts to maximize HDA activity.

Impact of H2S removal and LHSV ratio on cetane index


Results of the cetane index (CI) improvements in the single-
and the two-stage hydrogenation processes are shown in Table 3.
The CI was calculated using the ASTM D976 cetane index
correlation:

CI = 454.74 1641.416 + 774.742 0.554 M + 97.803(log M )2 Figure 2. Effect of H2S removal on the reaction rate constants of AHYD
in the two-stage process (pressure: 11.0 MPa, H2/oil ratio: 550 ml/ml)

VOLUME 84, OCTOBER 2006 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 575
Figure 4. Impact of H2S inhibition on HDS in the two-stage process
(pressure: 11.0M Pa, H2/oil ratio: 550 ml/ml)
Figure 3. Effect of H2S removal and LHSV ratio on the overall cetane
index in the two-stage process (pressure: 11.0 MPa, H2/oil ratio: Kinetic Studies
550 ml/ml)
The feed material used in this work is a complex mixture of
nitrogen and sulphur compounds. During hydrotreating, HDN
Impact of H2S on HDS and HDN reaction of nitrogen species produces NH3 and HDS reaction of
The impact of removal of hydrogen sulphide on HDS in the two- sulphur species produces H2S. The feed material used in our
stage compared to the single-stage is shown in Figure 4. Similar work contains significantly large amount of sulphur compounds
to the results for the HDA activity, the relative gain in the rate (~40 times of nitrogen amount). So, it can be assumed that the
constants decreased with increasing reaction temperature. This effect of NH3 on the HDN and HDS reactions would be negligible
was because majority of hydrogen sulphide was produced in the compared to that of H2S because of the competitive adsorption
Stage I of the two-stage unit and adsorption of hydrogen sulphide of these two compounds on the catalyst surface. Also, it was
on the active sites of the catalysts decreased with increasing assumed that the sulphur compounds do not have any inhibition
temperature. Consequently, the rate of sulphur removal (conver- on HDS and vice-versa.
sion) increased with further increase in temperature in both Sulphur compounds vary from simple thiols (R-SH) to the
stages leading to a net decrease in the overall gain. This observa- simple sulphides (R-S-R) and to the polycyclic sulphides, such as
tion is consistent with other studies in literature (Kabe et al., compounds with two aromatic rings. On the other hand, nitrogen
1999; Nagai et al., 1988; Botchwey et al., 2003). The positive compounds are present in the form of basic and non-basic. During
gain in the rate constants implied higher HDS activity in the two- hydrotreating reaction the non-basic nitrogen compounds form
stage than the single-stage. HDS activity at LHSV ratios of 1:1 more basic nitrogen compounds. Therefore, data related to basic
and 1.5:1 were similar with the former exhibiting a higher and non-basic nitrogen compounds in the product is not possible
activity only at the lower temperatures (350 365C). From this to correlate with the amount of basic and non-basic nitrogen
analysis, it can be inferred that equal catalyst loadings or a compounds present in the feed. Therefore, it was not possible to
higher amount of NiMo catalyst loading in Stage I will maximize include individual reactive and refractory sulphur and nitrogen
HDS activity in the two-stage process so long as there is an inter- species in HDS and HDN kinetics and hence, a kinetic study was
stage removal of H2S. performed on the basis of total nitrogen and sulphur
Unlike the HDA and HDS processes, very high HDN activities compounds.
(95 100% conversion) were observed for both the single- and Hydrogen sulphide is usually taken as an inhibitor in competi-
two-stage processes within the temperature range studied tion with aromatics and sulphur for the same adsorption sites.
(350 390C) (Owusu-Boakye, 2005). This implies that HDN The purpose of this section of the research was to obtain
was not retarded by the presence of hydrogen sulphide during mathematical kinetic models describing the rate of HDA and
hydro-treating and this is consistent with other studies (Landau HDS during upgrading of light gas oil as a function of the active
et al., 1996; US EPA, 1999) that have reported negligible inhibi- components of the system such as the concentration and temper-
tion of HDN by hydrogen sulphide. ature. Furthermore, the inhibition effect of hydrogen sulphide on
the single- and two-stage HDA and HDS was studied. The basis
for comparison of the overall kinetics of the two-stage and the
Table 3. Cetane index improvement in single- and two-stage single-stage processes was the equal reaction time of 1.67 h
processes at a pressure of 11.0 MPa when LHSV was maintained between the two processes.
constant at 1.5 and 1 h1 for the single- and two-stage processes, The two-stage and the single-stage hydrotreating kinetics
respectively were modelled using the Langmuir-Hinshelwood (L-H) approach.
Cetane index, CI This model was selected over that of the power law in order to
Temperature (C) Single-stage Two-stage account for hydrogen sulphide inhibition. The experiments for
350 42 0.8 43 0.8
the kinetic studies were performed by varying temperature from
350 390C at a pressure of 11.0 MPa.
365 44 0.9 44 0.9
380 43 0.9 46 0.9
Kinetics of HDA
It has been well established that hydrogenation of aromatics is
390 41 0.8 45 0.9
an equilibrium reaction that is shifted in favour of aromatics
with increasing temperature:

576 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 84, OCTOBER 2006

Aromatics+nH2
Saturates
(1)

Using the single-site mechanism form of the Langmuir-


Hinshelwood rate of reaction, HDA can be kinetically
modelled by:
dC A k F K A K H 2 PH 2C A k RC AH
rA = = (2)
dt 1 + K AC A + K H 2S PH 2S

Where -rA, kF and kR are the rate of reaction, forward and


reverse rate constants, respectively, KH2, KA and KH2S are the
equilibrium adsorption constants of hydrogen, aromatics and
hydrogen sulphide, respectively. CA and CAH are the product
concentration of aromatics and the saturated species, respec-
tively. PH2S and PH are partial pressures of hydrogen sulphide
and hydrogen gas, respectively, and t is the residence time.
However, negligible equilibrium effects were observed from Figure 5. Arrhenius and Vant hoff plot for two-stage AHYD
the hydrogenation data leading to the following assumptions for
The values of ki, Ki, KH, and KH2S in two-stage process were
developing the final kinetic model: (1) the surface reaction was
obtained using trial and error method and then by matching the
rate limiting; (2) reaction is pseudo first order in the forward
model predicted data with those obtained from experiments for Ci
reaction; (3) the reaction occurred in a plug flow regime with
(concentration of aromatics or sulphur in the product). A non-
negligible diffusion and mass transfer effects; (4) reaction
linear least squares approach was used to solve Equations (5) to
occurred in excess amounts of hydrogen at constant partial
(7), in order to obtain values of ki and Ki. The values of ki and Ki
pressure; (5) hydrogenation is inhibited by hydrogen sulphide
are tabulated in Table 4, based on the agreement of Ci obtained
that is produced from the HDS process and H2S is an ideal gas.
from the model and experiments. Apparent activation energy and
The partial pressure of hydrogen sulphide was calculated
heats of adsorption were also determined from the slopes of the
from the ideal gas law equation:
curve fitting by plotting the inverse of temperature against the
n H 2S logarithm of apparent kinetic and adsorption equilibrium constants
PH 2S = RT = C H 2S RT = b(C so C sp ) (3)
V (ln (k, K) vs. 1/T) (Figure 5). The high correlation coefficients
(0.9899 0.9979) obtained from the regression analysis indicated
Where PH2S is the partial pressure of H2S, nH2S is the number of
a good fit of the model to the experimental data.
moles of H2S, R is the universal gas constant, T is temperature,
Results of the apparent kinetic parameters of the single- and
Cso is the feed sulphur concentration and Csp is the product
two-stage processes are presented in Table 4. The following
sulphur concentration in either Stage I or Stage II; b is a
observations were made from the kinetic parameters when
constant.
hydrogen sulphide was removed from the two-stage process: (1)
The final equation, which is the combination of Equations (2)
the rate constants, kA derived from the single-stage hydrogena-
and (3), is given by:
tion activity were lower (1.86.2105s1) than those from the
dC AI k Ai K Ai K Hi PH 2C Ai two-stage hydrogenation process. Thus, a faster rate of reaction
rAi = = (4)
dt 1 + K Ai C Ai + K H 2Si PH 2Si favoured the two-stage process; (2) the equilibrium adsorption
constants of aromatics were lower than those for hydrogen
Where kA is the apparent rate constant and all other terms are sulphide in the single-stage process, whereas, for the two-stage
as defined. The subscript i, refers to either single- or two-stage process, the opposite was observed. Hence, the aromatic species
kinetics. The integral form of rate equation solved by MAPLE 6.0 in the single-stage were weakly adsorbed (low conversion) due
software, a trademark of Waterloo Maple Inc. is:

C K + ln C Ao + ln C AO K H 2S PH 2S
kK A K H PH (t AO A )
K exp( kK K P
A H H ))
A 1 + K H 2S PH 2S
(1 + K H 2S PH 2S )LambertW (5)
1 + K H 2S PH 2S



CA =
KA

3 3 8 4 125 5 54 6
Where LambertW( x) = x x2 + x x + x x + ( o)7 (6)
2 3 4 5

C K + ln C Ao + ln C AO K H 2S PH 2S
kK A K H PH (t AO A )
K exp( kK A K H PH
))
A 1 + K H 2S PH 2S
and X = (7)
1 + K H 2S PH 2S



VOLUME 84, OCTOBER 2006 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 577
Table 4. Summary of the apparent kinetic parameters of the overall kinetics studies in the single- and two-stage processes
(temperature: 340390C; pressure: 11.0 MPa; total residence time: 1.67 h)

Kinetic Parameters lnkAI lnkAII lnKAI lnKAII lnKH2SI lnKH2SII lnKHI lnKHII
Aromatics hydrogenation (HDA)
EA and H(kJ/mol) 85 4.2 67 3.3 33 1.7 59 3.0 39 2.0 24 1.2 7.6 0.38 7 0.36
ln (kAo),ln(Ko )* 14 0.70 10.6 0.53 4.8 0.24 8.2 0.41 3.5 0.20 5.4 0.27 2.3 0.14 4.8 0.24
R2 0.9967 0.9854 0.9995 0.9963 0.9729 0.9999 0.9833 0.9988
Hydrodesulphurization (HDS)
lnksI lnksII lnKSI lnKSII lnKH2SI lnKH2SII lnKHI lnKHII
ES and H(kJ/mol) 55 2.8 22 1.1 44 2.2 67 3.4 50 2.5 24 1.2 114 5.7 -33 1.6
ln (kso),ln(Ko)* 5.2 0.26 0.78 0.04 5.5 0.28 9.0 0.45 8.0 0.40 2.4 0.12 19 0.98 4.4 0.22
R2 0.9963 0.9972 0.9868 0.9973 0.9941 0.9943 0.9863 0.9984

* kAo, kso: y intercept of the Arrhenius equation (activation energy)


* KO: y intercept of the Vant Hoff equation (heat of adsorption)

to H2S inhibition while in the two-stage process, the aromatic


species were strongly adsorbed, leading to a higher HDA activity
and consequently, higher conversions; (3) the activation energy
of hydrogenation in the single-stage was 85 kJ/mol (more
temperature sensitive) but upon removal of hydrogen sulphide
for the two-stage process, the activation energy dropped to
67 kJ/mol (less temperature sensitivity). This implies when
HDA in the bitumen-derived light gas oil is being retarded by
H2S, more energy will have to be provided to the system in order
to overcome the energy barrier and reduce the aromatic contents
to appreciably low levels (<10 vol.%) in compliance with the
current diesel fuel specifications (U.S. EPA, 1999).
Figure 6. Arrhenius and Vant Hoff plots for two-stage HDS
Kinetics of HDS
HDS kinetics was modelled according to the following reaction The apparent kinetic parameters for HDS were also determined
mechanism: using non-linear least squares method. The activation energy
and heats of adsorption were calculated directly from the slopes
Heteroatom sulphur species + Hydrogen Hydrocarbon of the Arrhenius and Vant Hoff plots (Figure 6). High correla-
Hydrocarbon + H2S (8) tion coefficients (greater than 0.985) were obtained from the
regression analysis, indicating a good fit of the model to the
The final rate equation is: experimental data.
Results of the effect of inter-stage removal of hydrogen
dC Si ksi K Si K Hi PH 2C Si sulphide on the kinetic parameters of HDS in both the single-
rsi = = (9)
dt 1 + K C
Si Si + K P
Hi H 2 + K P
H 2 Si H 2 Si
and the two-stage processes are also shown in Table 4. For the
analysis of the single-stage overall kinetics, the activation energy
Where rSi and kSi are the rate equation and apparent rate of HDS was 55 kJ/mol. The heats of adsorption for sulphur and
constant of HDS, respectively, KS, KH2, KH2S are the adsorption hydrogen sulphide were 44 and 50 kJ/mol, respectively.
equilibrium constants of sulphur, hydrogen and hydrogen Therefore, H2S was strongly adsorbed on to the active sites of the
sulphide, respectively, and PH2S is the partial pressure of catalyst as compared to adsorption of the sulphur species.
hydrogen sulphide. The integral form of the rate expression is: Furthermore, the adsorption equilibrium constants for H2S were
higher than those for total sulphur. The results suggest that in
(1 + K HI PH 2 + K H 2SI PH 2SI ) LambertW ( x ) the HDS of light gas oil, the reaction was retarded by the H2S
C SI =
(10)
produced in the reaction. This result is consistent with literature
K sI
(Nagai et al., 1988) where higher equilibrium adsorption
where
C K + ln(C SO ) + ln(C SO )K HI PH 2 + ln(C SO )K H 2SI PH 2SI
ksI K HI K SI PH 2 t SO SI
kSI K HI K SI PH 2
K sI exp
1 + K HI PH 2 + K H 2SI PH 2SI (11)


( ) =
(1 + K HI PH 2 + K H 2SI PH 2SI )
Lambert W() is as defined in Equations (6) and (7).

578 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 84, OCTOBER 2006
temperatures (340 350C), only 2 3% increase in the CI
occurred in the two-stage unit. The highest cetane index in the
single-stage process was 44 at 365C whereas for the two-stage
process, a higher temperature of 380C was required to obtain
the best cetane value of 46. It is also observed from Table 3 that
further increase in reactor temperature above 380C (in the two-
stage) and 365C (in the single-stage) had limitations for
additional increase in CI since these temperatures are close to
the equilibrium temperature for hydrogenation of aromatics.

Experimental versus model predictions


The best kinetic parameters for predicting the experimental
results for HDA, HDS and MHC were selected based on the sum
of square errors (SSE) approach. The criterion for this method
was to minimize the differences between the experimental and
the predicted results.
Figure 7. Correlated versus experimental concentrations of total
aromatics, CA at the different LHSV ratios
SSE = ( yi p yi exp )2 (12)

where SSE is the divergence, yip is the model prediction and yexp
is the experimental results. Figures 7 and 8 compare the experi-
mental and calculated product concentrations of aromatics and
sulphur, respectively. As can be seen, the kinetic models
predicted with reasonable accuracy the experimental results over
the entire temperature range.

CONCLUSIONS
1. HDA and HDS are both inhibited by hydrogen sulphide
produced from the HDS activity.
2. The inhibition can be reduced by two-stage hydrotreating with
inter-stage removal of hydrogen sulphide. The activity for HDA
could be achieved by maintaining LHSV ratio of 1.5:1.0 in
Figure 8. Correlated versus experimental concentrations of product Stage I:Stage II in the temperature range of 350 390C. The
sulphur, Cs at the different LHSV ratios cetane index of the product was optimum at 380C and LHSV
ratio of 1.5:1.0. No inhibition of the H2S was observed in the
constants of hydrogen sulphide have been reported during HDN activity.
inhibition reaction of dibenzothiophene compounds. 3. HDA and HDS in LGO feedstock from Athabasca bitumen
In the case of the two-stage kinetic analysis, the activation can be described by the Langmuir-Hinshelwood kinetic
energy was 22 kJ/mol while the heats of adsorption were 67 and models. For the analysis of the single-stage overall kinetics,
24 kJ/mol for the total sulphur and hydrogen sulphide, respec- the activation energy of HDS was 55 kJ/mol whereas in case
tively. Unlike the single-stage, the adsorption equilibrium of the two-stage kinetic analysis, the activation energy of
constants of total sulphur were significantly higher than H2S HDS was 22 kJ/mol. These models predicted well the
indicating weak adsorption of hydrogen sulphide. The inter-stage experimental data.
removal of H2S from the two-stage process greatly enhanced the
HDS activity as activation energy decreased from 55 kJ/mol in
the single-stage to 22 kJ/mol in the two-stage process. NOMENCLATURE
b constant parameter
Relationship between the kinetic data and the
CA product concentration of aromatics
improvement of cetane index and activity of CAH concentration of saturated products
HDS and HDA CAO concentration of aromatics in feed
From Table 4, significant decrease in activation energy was CI cetane index
observed in case of both hydrodearomatization (HDA) and Cs product concentration of sulphur species
hydodesulphurization (HDS) when the experiments were Cso concentration of sulphur species in feed
performed in the temperature range of 350 - 390C. For example, Csp concentration of sulphur in hydrotreated product
the activation energy decreased from 85 to 67 and from 55 to E activation energy (kJ/mol)
22 kJ/mol in case of HDA and HDS, respectively, which indicates exp experimental
significant improvement in HDA and HDS reactions. However, it H2S hydrogen sulphide
was difficult to correlate the kinetic data with the cetane index HDA aromatics hydrogenation
(CI). Cetane index is the function of mid boiling point tempera- HDN hydrodenitrogenation
ture and specific gravity. Figure 3 shows that, the CI increased HDS hydrodesulphurization
with the increase in temperature from 350 to 380C and further HT hydrotreating
increase in temperature decreased the cetane index. At the lower kA rate constant for HDA

VOLUME 84, OCTOBER 2006 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 579
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580 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 84, OCTOBER 2006