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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).
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
208
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.
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.
209
(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.
210
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 ( ).
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].
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).
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
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-
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 ( ).
212
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 ( ).
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
KN (l/mmol)
0.86
1.14
1.37
0.74
1.30
1.88
R2
0.9707
0.9887
0.9914
Fig. 6. Comparison between experimental and calculated pseudo-first-order rate constants for dibenzothiophene hydrodesulfurization inhibited
by indole ( ), indoline (), o-ethylaniline ( ).
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
214