Applied Catalysis A: General 243 (2003) 207214

Inhibition effects of nitrogen compounds on the

hydrodesulfurization of dibenzothiophene: Part 2
Georgina C. Laredo a, , Efran Altamirano b , J. Antonio De los Reyes b
a

Instituto Mexicano del Petrleo, Programa de Tratamiento de Crudo Maya. Eje, Central Lzaro Crdenas 152,
07730 San Bartolo Atepehuacan, Mexico
b Depto. de Ingeniera de Procesos e Hidrulica, Divisin de Ciencias Bsicas e Ingeniera,
Universidad Autnoma Metropolitana-Iztapalapa, Av. Michoacn y La Pursima, 09340 Vicentina, Mexico
Received 23 January 2002; received in revised form 23 May 2002; accepted 24 May 2002

Abstract
The inhibiting effect of certain basic and non-basic nitrogen compounds on the hydrodesulfurization of dibenzothiophene,
at conditions commonly used in the hydrotreatment of diesel feedstocks, has been experimentally determined. Nitrogen
compounds studied herein are indole, indoline and o-ethylaniline. The inhibition behavior of these compounds is highly
non-linear, showing strong inhibition at concentrations as low as 28 ppm (as nitrogen). The inhibiting effect of the non-basic
compound, indole, was found to be comparable to that of the basic compounds, indoline and o-ethylaniline, although indoline
and o-ethylaniline show a slightly higher inhibiting strength than their parent compound, indole. This behavior suggests
that the coverage of active sites by nitrogen compounds is established on the early stages of the reaction and remains nearly
constant throughout the experiment, and shows that their inhibiting behavior is due to a strong initial adsorption of the nitrogen
compound and a slow kinetics of desorption, rather than to the hydrogenation of the non-basic species to basic ones.
The experimental data for dibenzothiophene hydrodesulfurization in the presence of indole, indoline and o-ethylaniline
was quantitatively represented by a modified LangmuirHinshelwood type rate equation.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Hydrodesulfurization (HDS); Hydrodenitrogenation (HDN); Hydrotreatment (HDT); Hydrogenation; Inhibition; Reaction kinetics;
Dibenzothiophene; Nitrogen compounds; Indole; Indoline; o-Ethylaniline

1. Introduction
Nitrogen compounds naturally occurring in atmospheric gas oil (AGO) and light cycle oil (LCO),
used as feedstocks for diesel fuel production, are traditionally considered as being responsible for color
and gum formation. Moreover, they have been identified as strong inhibitors of the HDS reactions during
the hydrotreatment process, [1,2] even when they
Corresponding author. Tel.: +52-55-3003-6615.
E-mail addresses: jarh@xanum.uam.mx, glaredo@imp.mx
(G.C. Laredo).

are present in very low concentrations [3]. Usually,

the basic nitrogen compounds have been considered
stronger inhibitors for the HDS reactions than the
non-basic moieties [1,2]. However, strong inhibition
of these reactions by non-basic nitrogen compounds
has been observed, either due to hydrogenation reactions occurring during this process, that lead to
the formation of basic species [4,5], or to a strong
adsorption of the non-basic compounds over the support surface [68]. For carbazole, Nagai and Kabe
[4] and LaVopa and Satterfield [9] reported a strong
inhibiting effect on the thiophene and dibenzothiophene hydrodesulfurization reactions, comparable to

0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 3 2 1 - 6

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G.C. Laredo et al. / Applied Catalysis A: General 243 (2003) 207214

those of the basic compounds pyridine, piperidine and

acridine. The high value of the adsorption characterizing carbazole was attributed to products of a rapid
hydrogenation converting it to basic compounds. As
for indole, Furimsky and Massoth [2] have reported a
long-time adsorption of this compound, with a slow
recovery of the catalyst activity for hydrodesulfurization of dibenzothiophene and hydrogenation of
naphthalene after its removal from the feed.
In a recent work, Laredo et al. [10] reported an
inhibiting strength order of indole > quinoline >
carbazole. In order to find out if this unusual behavior is due to the strong adsorption of the non-basic
parent compound or to the basic nature of the hydrogenation products resulted during the hydrotreatment process, the main objective of this work was to
determine the inhibiting effect of indole and its hydrogenation products indoline and o-ethylaniline on
the dibenzothiophene hydrodesulfurization reaction at
pressures and temperatures commonly used in the hydrotreatment of diesel and at sulfur and nitrogen concentrations relevant to deep hydrodesulfurization. A
LangmuirHinshelwood type equation that quantitatively describes the observed behavior is also provided.

Reactor 4842). The typical procedure was as follows: dibenzothiophene (0.3 g, 0.00163 mol) was
dissolved in 100 ml of hexadecane to a concentration
of 0.39 wt.% (0.0163 mol/l), equivalent to 675 ppm
of sulfur. The nitrogen compound (indole, indoline
and o-ethylaniline) was added at concentrations of
1.617.9 mmol/l, equivalent to 28323 ppm as nitrogen. The mixture was poured into the autoclave and
the catalyst (1 g) was transferred to the reactor avoiding exposure to air. The amount of nitrogen compound
needed to form a monolayer over the catalyst surface
was calculated to be 30 ppm as nitrogen [11].
After purging with nitrogen, the temperature was
increased to 280320 C and hydrogen was introduced
until the required pressure (5.1 MPa) was reached. Reaction pressure was maintained by adding hydrogen
during the experiment. Reaction time measurement
started when the agitation (1500 rpm) began.
2.3. Analytical

2. Experimental

For accomplishing product identification in the samples, a Perkin-Elmer gas chromatograph model Autosystems XL with a flame ionization detector (FID)
was used. A 30 m 0.53 m capillary column coated
with a non-polar methyl silicone phase (DB-1, J & W)
was employed.

2.1. Catalyst and reagents

2.4. Kinetic calculations

The catalyst used was a CoMo/-Al2 O3 commercial catalyst (IMP-DSD-14, 2.3 wt.% Co, 10 wt.%
Mo) with the following characteristics: bulk density
0.70.77 g/cm3 ; pore volume 0.45 cm3 /g; and surface
area 150 m2 /g. The extrudates were crushed, sieved to
a 149177 mm size range and sulfided in a fixed bed
reactor using a gas mixture of 10% H2 S and 90% H2
by volume at 280 C for 4 h.
Dibenzothiophene was obtained from Fluka
(98%+) and the nitrogen compounds from Merck
(98%+). Hexadecane (99%) from Aldrich was used
as solvent. Dry hydrogen (99.9%) and hydrogen sulfide (99%+) were obtained from Infra.

The dibenzothiophene hydrodesulfurization rate

constants for all the experiments were calculated using
the integral method in order to get comparative results.
The dibenzothiophene conversion showed a first-order
behavior when graphing ln[(CDBT )/(CDBT )0 ] versus
time. The slope and the correlation coefficient were
calculated via least-squares fitting. Correlation coefficients higher than 0.95 were obtained in all cases.

2.2. Apparatus and procedure

HDS, and HDSHDN experiments were carried
out in a 400 ml stirred autoclave (Parr Pressure

2.5. Control of the kinetic regime

A set of experiments was performed to check the absence of intraparticle and interphase mass transfer limitations. Different sizes of catalyst particles (150, 500
and 840 m) were tested and the results indicated that
a kinetic regime was established in all cases. Further,
a 27 kcal/mol value was obtained for the apparent activation energy of the dibenzothiophene hydrodesulfur-

G.C. Laredo et al. / Applied Catalysis A: General 243 (2003) 207214

ization reaction in the 280320 C temperature range,

showing that we were working in the absence of diffusional limitations.
3. Results and discussion
3.1. Dibenzothiophene hydrodesulfurization
reaction
Initial experiments were undertaken to verify the
dibenzothiophene hydrodesulfurization behavior at

209

320 C and 5.1 MPa, using hexadecane as solvent.

The results show the typical product distribution already reported elsewhere [12,13] with DBT being
converted to biphenyl (BP) and cyclohexylbenzene
(CHB) (Fig. 1a). Dibenzothiophene hydrodesulfurization follows a first-order behavior, and the
kinetic equation used was the result of a simplification described previously in Laredo et al. [10]
from a LangmuirHinshelwood equation [1416],
giving:
rHDS = kDBT CDBT

(1)

Fig. 1. Dibenzothiophene hydrodesulfurization over a CoMo/Al2 O3 catalyst at 320 C and 5.1 MPa, without nitrogen compounds. (a)
Products distribution as a function of time. Biphenyl (), cyclohexylbenzene (). (b) First-order behavior for DBT conversion.

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G.C. Laredo et al. / Applied Catalysis A: General 243 (2003) 207214

Fig. 2. Hydrodenitrogenation of indole: product distribution as a function of time at 320 C and 5.1 MPa over CoMo/Al2 O3 . Indole (),
indoline (), o-ethylaniline (), ethylbenzene (), ethylcyclohexane ( ).

The value obtained for kDBT at 320 C (Fig. 1b) using

the integral method, previously described in the experimental section, was 1.27 102 min1 . This value
will be used as a reference for the results obtained in
the experiments where this reaction was inhibited by
nitrogen compounds.

hexadecane as solvent is shown in Fig. 2 (indole concentration, 17.7 mmol/l). The products identified by
GC/MS were indoline (HIN), o-ethylaniline (OEA),
ethylbenzene (EB) and ethylcyclohexane (ECH). This
product distribution agrees with previous mechanistic
indole hydrodenitrogenation studies (Fig. 3) [17,18].

3.2. Indole hydrodenitrogenation

3.3. Inhibition by nitrogen compounds

The product distribution from the indole hydrodenitrogenation at 320 C and 5.1 MPa, versus time using

The dibenzothiophene hydrodesulfurization reaction was carried out at 320 C and 5.1 MPa in the

Fig. 3. Reaction pathways for the HDN of indole suggested by Zhang and Ozkan [18]. Indole (IND), indoline (HIN), o-ethylaniline (OEA),
ethylbenzene (EB), octahydroindole (OHIN), o-ethylcyclohexylamine (OECHA), ethylcyclohexene (ECHE), ethylcyclohexane (ECH).

G.C. Laredo et al. / Applied Catalysis A: General 243 (2003) 207214

211

Table 1
Inhibiting effect of nitrogen compounds on DBT HDS at 5.1 MPa and 320 Ca
Indole

Indoline

Initial concentration


kDBT

102

(mmol/l)

(ppm)b

(min1 )

1.57
3.16
6.20
12.41
17.81

28
57
112
224
323

0.55
0.45
0.38
0.33
0.28

a
b

R2

0.96
0.95
0.98
0.98
0.98

o-Ethylaniline

Initial concentration


kDBT

102

(mmol/l)

(ppm)b

(min1 )

1.57
3.05
6.10
12.20
17.57

28
56
110
221
318

0.50
0.41
0.31
0.27
0.22

R2

0.98
0.98
0.95
0.95
0.99

Initial concentration


kDBT
102

(mmol/l)

(ppm)b

(min1 )

1.57
3.11
5.99
12.43
17.87

28
55
109
217
313

0.45
0.35
0.28
0.23
0.19

R2

0.98
0.99
0.97
0.98
0.95

DBT initial concentration 0.0163 mol/l, 675 ppm as sulfur.

As nitrogen.

presence of different concentrations of indole, indoline and o-ethylaniline. The results of these experiments were fitted to a pseudo-first-order rate equation,
with correlation coefficients (R2 ) better than 0.95 in all
cases (Table 1). Therefore, the dibenzothiophene hydrodesulfurization behavior for this set of experiments
could be appropriately represented by the following
equation:

rHDS = kDBT
CDBT

(2)


where kDBT
is the pseudo-first-order rate constant for
the dibenzothiophene hydrodesulfurization reaction
inhibited by nitrogen compounds. An inhibition fac-

tor () was calculated in order to show the degree of

inhibition in each experiment (Fig. 4):
=


kDBT kDBT
kDBT

(3)

The inhibiting effect increases as the nitrogen concentration increases, tailing off at higher concentrations.
In this work, the inhibiting strength increased in the
following order:
indole < indoline < o-ethylaniline
Although the differences between them are small,
the slightly higher inhibiting effect of indoline and

Fig. 4. Dibenzothiophene hydrodesulfurization inhibition factors for pure nitrogen compounds evaluated at 5.1 MPa and 320 C. Indole
( ), indoline (), o-ethylaniline ( ).

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G.C. Laredo et al. / Applied Catalysis A: General 243 (2003) 207214

o-ethylaniline, suggests that the indole inhibiting effect could not be attributed only to hydrogenation reactions converting it into basic compounds [19,20], as
it has been suggested by Ho [21] and Odebunmi and
Ollis [5], because if that was the case, all these compounds should have the same strength at the same nitrogen concentration, i.e. the o-ethylaniline inhibition
strength. Then, the inhibition behavior seems related
to the strong adsorption of the specific nitrogen compound directly on the catalyst surface [2224].
3.4. Kinetic model for inhibition by indole, indoline
and o-ethylaniline
The excellent representation of the experimental results by a pseudo-first-order rate equation (Table 1)
implies that the inhibition effect is approximately constant during each test. The inhibiting strength does not
seem to be affected by the conversion of the parent nitrogen compound, the formation or disappearance of
basic compounds or the degree of organic nitrogen removal. This behavior suggests that the coverage of the
available active sites by nitrogen compounds is established in the early stages of the reaction and remains
nearly constant throughout the experiment, probably

due to the slow kinetics of desorption of these compounds [2]. Therefore, the variation in the nitrogen
compound concentration along time was not considered in the development of the model.
In order to perform kinetic calculations the following model was proposed by Laredo et al. [10] in a
previous paper:
rHDS =

kDBT CDBT
1 + K N n CN n

(4)

where KN is the apparent nitrogen compound adsorption equilibrium constant (l/mol) and represents the
behavior of all the nitrogen compounds that contribute
to the inhibition, CN the initial nitrogen compound
concentration (mol/l) and n is the fitting exponent.

The pseudo-first-order rate constant kDBT
(Table 1)
for dibenzothiophene hydrodesulfurization in the presence of each nitrogen compound is expressed by the
following equation:

kDBT
=

kDBT
1 + K N n CN n

(5)


Plots of kDBT /kDBT
versus initial concentration of
indole, indoline and o-ethylaniline using a fitting exponent of 0.5 are shown in Fig. 5. It is noteworthy that

Fig. 5. Obtention of the adsorption term concentration exponent n on the representation of the dibenzothiophene hydrodesulfurization
inhibition by indole ( ), indoline (), o-ethylaniline ( ).

G.C. Laredo et al. / Applied Catalysis A: General 243 (2003) 207214

213

Table 2
Apparent adsorption constants for the nitrogen compounds
Nitrogen compound

Indole
Indoline
o-Ethylaniline
a

pKa
3.6
5.0
4.3

Gas-phase basicity
(kcal/mol) [26]

215.6
221.4
205.8a

0.5
0.5
0.5

Apparent adsorption constant

KN n (l/mmol)n

KN (l/mmol)

0.86
1.14
1.37

0.74
1.30
1.88

R2

0.9707
0.9887
0.9914

Estimated from available data [26].

Fig. 6. Comparison between experimental and calculated pseudo-first-order rate constants for dibenzothiophene hydrodesulfurization inhibited
by indole ( ), indoline (), o-ethylaniline ( ).

the fitting exponent obtained for indole in this set of

experiments agrees with the value obtained in a previous work [10].
The corresponding adsorption constants KN for indole, indoline and o-ethylaniline are shown in Table 2.
The highest adsorption constant KN was obtained for
o-ethylaniline (1.88 l/mmol), which was a stronger inhibitor than indole and indoline. Moreover, according
with the results found in this work, the inhibiting effect
does not seem to be attributable to the basic strength
of the nitrogen compounds because neither the pKa
nor the gas-phase basicity values [25,26] follow the
same trend as the adsorption constants.
Finally, in order to verify the agreement of the

model with our experimental results, kDBT
values

were calculated using Eq. (4) and were compared

with the experimental data (Fig. 6). The predicted
values are in very good agreement with the experimental data in the whole range of nitrogen compounds
concentrations tested, supporting the validity of the
model.

4. Conclusions
The inhibiting effect of the non-basic nitrogen compound indole on the dibenzothiophene hydrodesulfurization reaction is comparable to that of basic nitrogen
compounds, such as indoline and o-ethylaniline. The
inhibiting effect of the nitrogen compounds included

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G.C. Laredo et al. / Applied Catalysis A: General 243 (2003) 207214

in this study increases in the order:

indole < indoline < o-ethylaniline
The inhibiting effect of these compounds is very
strong, even at concentrations as low as 28 ppm as
nitrogen. A modified LangmuirHinshelwood rate
equation can be used to represent the non-linear inhibiting effect of indole, indoline and o-ethylaniline
on the dibenzothiophene hydrodesulfurization over all
the range of concentrations studied, using a 0.5 exponent for the initial nitrogen compound concentration
in the adsorption term.
Basic hydrogenation products, o-ethylaniline and
indoline have a slightly stronger inhibiting effect than
the non-basic parent compound indole at equivalent
concentrations. This experiment probes that the inhibiting behavior is due to a strong initial adsorption of
the nitrogen compound and a slow kinetics of desorption, rather than to the hydrogenation of the non-basic
specie to basic ones.
Acknowledgements
This work has been carried out as part of a research project in the frame of the Fondos para las
Instituciones de Educacin Superior (FIES) Program, financed by Instituto Mexicano del Petrleo
(IMP). Efrain Altamirano is grateful with CONACYT
(Mxico) for a scholarship.
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