JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY

Volume 36, Issue 6, December 2008

Online English edition of the Chinese language journal
Cite this article as: J Fuel Chem Technol, 2008, 36(6), 684690

RESEARCH PAPER

Mutual influences of hydrodesulfurization of

dibenzothiophene and hydrodenitrogenation
of indole over NiMoS/-Al2O3 catalyst
XIANG Chun-e, CHAI Yong-ming, LIU Yun-qi, LIU Chen-guang
State Key Laboratory of Heavy Oil Processing, Key Laboratory of Catalysis, China National Petroleum Corporation, College of Chemistry &
Chemical Engineering, China University of Petroleum (East China), Qingdao 266555, China

Abstract: The influence of indole on the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and the influence of DBT on the
hydrodenitrogenation (HDN) of indole were investigated over a presulfided NiMoS/J-Al2O3 catalyst in a fixed-bed high-pressure
microreactor. A significant negative effect of indole on the HDS of DBT was observed. The inhibitory effect of indole on the
hydrogenation route (HYD) was stronger than on the direct desulfurization route (DDS). Indole and its HDN intermediate products
suppressed HDS of DBT through the competitive adsorption on active sites of the catalyst. DBT and H2S produced in situ promoted
the conversion of coordinatively unsaturated sites (CUS) to Brnsted acid sites on the catalyst surface, which in turn facilitated the
cleavage of C(sp3)N bond in indoline; the conversion of indole and the relative concentration of o-ethylanline (OEA) then increased.
Although the presence of sulfur atoms is essential for the formation of active sites on the catalyst for HDN, a small amount of sulfur
species is sufficient to maintain the HDN active sites; higher content of sulfides may bring on a negative influence on the HDN of
indole.
Keywords: NiMoS/J-Al2O3; hydrodesulfurization; hydrodenitrogenation; dibenzothiophene; indole; in situ produced H2S; mutual
influence

Stringent diesel and gasoline specifications are being

introduced in many countries to minimize the environmental
pollution. However, the activity of a catalyst for
hydrodesulfurization (HDS) in the hydrotreating process of
diesel is depressed by organic heterocompounds and
polyaromatic hydrocarbons, especially by nitrogen
containing compounds[1,2].
The poisoning effects of basic N-compounds such as
quinoline and pyridine on HDS reaction have been widely
reported. However, the effects of nonbasic N-compounds
such as indole and carbazole on HDS are not well understood,
though 70% of the total N-compounds in the feed are
nonbasic. In addition, the nonbasic N-compounds can be
converted into basic ones after hydrogenation, which have
higher inhibiting effects on the HDS reaction[2,3]. To improve
the performance of catalysts for HDS, it is necessary to
investigate the influence of nonbasic N-compounds and its
intermediates on HDS reaction. Meanwhile, it is also
essential to study the effects of S-compounds on
hydrodenitrogenation (HDN) reaction in order to improve the

HDN activity. Therefore, in this study, the mutual influences

between the HDS of dibenzothiophene (DBT) and the HDN
of indole were investigated over NiMoS/Al2O3 catalyst.

1
1.1

Experimental
Chemicals and catalyst preparation

Indole, CS2, and cyclohexane of analytic pure grade were

used. DBT (purity >99.7%) was synthesized by the
procedure
advocated
by
Xu[4].
Ammonium
tetrathiomolybdate (ATTM) was prepared according to a
patent[5].
NiMoS/J-Al2O3 catalyst was prepared by successive
incipient wetness impregnation of J-Al2O3 with an aqueous
solution of ATTM, followed by an aqueous solution of
nickel nitrate. After each impregnation step, the catalyst was
dried in an oven at 60C for 12 h, and then calcined at 250C
for the first step and 500C for the second step under
nitrogen stream for 3 h. The loading calculated in the form of

Received: 09-May-2008; Revised: 13-Sep-2008

Corresponding author. Tel: 0532-86981716, E-mail: cgliu@hdpu.edu.cn
Foundation item: Supported by the Major State Basic Development Program of China (973 Program, 2004CB217807).
Copyright 2008, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.

Downloaded from http://www.elearnica.ir

XIANG Chun-e et al. / Journal of Fuel Chemistry and Technology, 2008, 36(6): 684690

oxide precursor (MoO3+NiO) was 24% and the atomic ratio

of Ni/(Ni+Mo) was 0.3.

Results and discussion

2.1
1.2

HDS and HDN reactions were carried out in a fixed-bed

high pressure microreactor (a stainless steel pipe of 7 mm i.d.,
420 mm long). 2 mL of NiMoS/J-Al2O3 catalyst (2040
mesh) was diluted with 3 mL of quartz sand to achieve
plug-flow conditions in the reactor.
Prior to the reaction, the catalyst was treated in H2 (2.0
MPa) to reduce the active metal sulfides at a heating rate of
40C/h from room temperature to 120C. This was held for 1
h, followed by heating to 300C. Finally, this temperature
was maintained for 2 h. After the treatment, the temperature
was decreased to 200C and the liquid reactant was fed to the
reactor by a pump.
The inhibitory effects of indole on HDS of DBT were
studied at the following conditions: 300340C, 2.0 MPa H2,
H2/feed volume ratio of 300, and liquid hour space velocity
(LHSV) of 10.0 h1. 2.3% of DBT dissolved in cyclohexane
was used as the reaction feed, equivalent to the sulfur content
in the feed of weight (wS) 4000 g/g, in which indole was
added at a concentration of wN = 5002000 g/g (the
nitrogen content in the feed by weight).
The effects of DBT and CS2 on the HDN of indole were
studied at the following conditions: 300C, 3.0 MPa H2,
H2/feed volume ratio of 300, and LHSV of 10.0 h1. DBT
and CS2 with a sulfur content of 10004000 g/g were added
to the indole-cyclohexane (nitrogen content of 500 g/g)
feed.
1.3

Effects of indole on the HDS of DBT

Catalytic tests

Analytical procedures

The reaction products were cooled down and separated

into gaseous and liquid fractions in a high-pressure separator.
Identification of liquid products was carried out with a
Varian 3800 gas chromatograph and a Finnigan SSQ710
mass spectrometry. The quantitative analysis of products was
performed with an Agilent HP 6820 GC equipped with a
flame ionization detector and CP-5 capillary column.
The activities of total, direct desulfurization route (DDS)
and hydrogenation route (HYD) were calculated by the
following equations:
ATotal = F0x/m
(1)
ADDS = ATotal sBP
(2)
AHYD = ATotal sCHB
(3)
Where ATotal, ADDS, and AHYD are the total, DDS, and HYD
activity, respectively; F0 is the flow rate of DBT (mol/s); x is
the conversion of DBT; m is the mass of catalyst (kg); sBP
and sCHB are the selectivity of biphenyl (BP) and
cyclohexylbenzene (CHB), respectively.

The reaction products of the HDS of DBT indicate that the

HDS of DBT goes via two parallel pathways[68]. The first
one is called hydrogenation (HYD), which consists of a
preliminary hydrogenation of one aromatic ring, giving
tetrahydro- and hexahydro-dibenzothiophenes that can be
desulfurized to form CHB. The second pathway is called
direct desulfurization (DDS), which yields BP. Under
moderate conditions, the transformation of BP to CHB can
be negligible[8], thus the selectivity of BP and CHB is
supposed to be a good representation of the reaction activity
of DDS and HYD route.
The HDS of DBT was studied in the presence of indole
with different concentrations at 300qC and 340qC, 2.0 MPa,
LHSV of 10.0 h1, H2/Oil (V/V) of 300. The conversion of
DBT, HDS activity, and selectivity of BP and CHB are listed
in Table 1. In the absence of indole, the HDS of DBT mainly
follows the DDS route, whereas the contribution of HYD
route is about 21.0%. However, in the presence of indole, the
HYD pathway for the HDS of DBT is strongly suppressed,
as AHYD decreases from 70 mol/(Kgs) to 14 mol/(Kgs)
and sCHB is lower than 5.0%. ADDS increases from 258
mol/(Kgs) to 309 mol/(Kgs) at first; after reaching a
maximum, it decreases with the increase of nitrogen content,
indicating that indole not only suppresses the HYD route, but
inhibits the DDS pathway as well.
The effects of indole on the HDS of DBT at 340oC are
similar to those at 300oC. HYD route is also intensely
suppressed by indole at 340oC, whereas the inhibition of the
DDS route becomes obvious with high nitrogen content. As a
consequence, the conversion of DBT decreases gradually
with the increase of nitrogen content; the sCHB declines even
as the sBP increases simultaneously.
Table 1 Effects of indole content on the reaction activity of the
HDS of DBT
Activity /

Selectivity

mol (kgs)1

smol/ %

wN

DBT conversion

/o C

g/g

xmol/%

ATotal

ADDS

AHYD

BP

CHB

300

92.0

331

258

70

77.8

21.0

340

500

90.2

325

309

14

95.3

4.4

1000

80.3

289

281

6.6

97.1

2.3

1500

68.7

247

242

3.8

97.7

1.5

2000

64.2

231

227

2.7

98.2

1.2

99.9

360

266

88

73.8

24.5

500

99.7

359

317

41

88.2

11.4

1000

87.9

351

330

21

93.9

6.0

1500

76.6

317

303

13

95.6

4.0

2000

70.8

300

290

96.5

3.1

XIANG Chun-e et al. / Journal of Fuel Chemistry and Technology, 2008, 36(6): 684690

In general, the HYD route is inhibited even under low

nitrogen content, whereas the inhibition for the DDS route
can only be observed at quite high nitrogen content. The
inhibitory effects of indole on both HYD and DDS route
become weaker at higher temperature.
2.2

Inhibition mechanism of indole on the HDS of DBT

To get a better understanding of the inhibition mechanism,

the product distribution of the indole HDN was analyzed. A
rapid hydrogenation of indole (IND) to indoline (HIN) is
followed by two different paths. The first is direct
hydrogenation of the aromatic ring of indoline to form
octahydroindoline (OHI), which is rapidly transformed to
ethylcyclohexylamine (OECHA). Another is C(sp3)N bond
rupture to form orthoethylaniline (OEA)[9]. The reaction
network is represented in Fig. 1.
The indole conversion, HDN ratio, and relative products
concentration with varied nitrogen contents in the feed are
listed in Table 2. It is evident that with increasing nitrogen
content, the conversion, HDN ratio, the relative
concentration of ECH, ECHE, and OEA decrease, whereas
the relative concentration of HIN increases.
It is commonly assumed that Mo atom at the edges and
corners of MoS2 crystallites in Mo/J-Al2O3 catalyst are
catalytically active sites. At least one sulfur vacancy at a site
is needed to allow the reacting molecule to bind chemically
with Mo atom[10,11]. The promoter atom (Ni or Co) substitutes
the Mo atom, forming so-called Ni-Mo-S or Co-Mo-S
structure. The sulfur atom between Ni and Mo atom is less
strongly bonded than the sulfur atom between two Mo atoms
and can be more easily removed. Under current situation,
indole strongly inhibits the HYD route for the HDS of DBT,
whereas the DDS pathway is only slightly suppressed. This
indicates that the hydrogenolysis and hydrogenation of DBT
may proceed on different active sites.
As shown in Table 1, the HYD route in HDS of DBT is
inhibited even under low nitrogen concentration, which can
be explained by the competitive adsorption between DBT

and indole. When DBT hydrogenation occurs, at least two

neighboring vacancies are needed for adsorbing DBT
molecule through benzene ring in the side-on mode[1215]. For
the HDN of indole, the reaction begins with the
hydrogenation of pyrrole ring and most likely is adsorbed in
a flat conformation through pyrrole ring at the same DBT
active sites. The electron cloud density of N-ring in indole
(56) is greater than that of benzene ring in DBT (66); thus,
the indole molecule can adsorb on the catalytic sites for
hydrogenation prior to the DBT molecule.
One vacancy at a metal atom is needed to perform the
DDS reaction of DBT, in which case the molecule is
adsorbed via end-on mode perpendicular to the catalyst
surface[16]. HIN may be adsorbed in the same mode as DBT
molecule on the vacancy through lone-pair electron of
nitrogen atom because the conjunctive effect of nitrogen
atom disappears. Indole has a negative effect on the DDS
route, but it is observed only at high nitrogen content; the
apparent activity of DDS route was even enhanced at low
nitrogen content (Table 1). This can be explained by the
competitive adsorption of DBT and N-compounds. With low
nitrogen content, the amount of N-containing intermediates
is too small to cause significant inhibitory effect on DDS
route. As the HYD route is largely blocked, more DBT
molecules can react through DDS route. The inhibition on
DDS route becomes obvious with increasing nitrogen
content.

Fig. 1

Reaction network for HDN of indole on NiMoS/J-Al2O3

catalyst

IND: indole; HIN: indoline; OHI: octahydroindole; OEA: o-ethylanline; EB:

ethylbenzene; OECHA: o-ethylcyclohexylamine; ECHE: ethylcyclohexene;
ECH: ethylcyclohexane

Table 2 Relative products concentration of indole HDN reaction

t

wN

/o C

g/g

ECH

ECHE

300

500

11.56

1000

2.44

1500
2000
340

Relative products concentration wmol/%

Conversion

HDN

EB

OECHA

OEA

HIN

IND

xmol/%

xmol/%

10.57

0.90

0.30

28.70

4.29

43.68

56.31

23.02

5.29

0.23

0.20

15.09

6.80

69.95

30.05

7.96

1.10

3.59

0.13

0.17

9.90

7.84

77.27

22.73

4.82

0.58

2.50

0.09

0.14

7.43

8.47

80.78

19.22

3.18

500

58.03

25.91

0.00

0.00

14.15

0.00

1.92

98.08

83.94

1000

20.46

9.40

5.23

0.00

32.98

0.84

31.09

68.91

35.10

1500

6.65

7.00

1.69

0.00

22.16

1.87

60.62

39.38

15.34

2000

3.16

4.67

0.84

0.00

13.26

2.24

75.82

24.18

8.67

XIANG Chun-e et al. / Journal of Fuel Chemistry and Technology, 2008, 36(6): 684690

Fig. 3

Fig. 2 Effects of the DBT content on the conversion and HDN

concentration of indole HDN

ratio of indole

: ECH; : ECHE; : EB; 1: OEA; : HIN; : IND

: indole conversion; : HDN ratio

Some metal atoms available for DDS may be blocked

simultaneously, because the amount of N-containing
intermediates increases and high content of indole in the
reactor may also cover the hydrogenation sites through
side-on mode.
2.3

Effects of DBT on the HDN of indole

To investigate how sulfides influence HDN reaction, the

HDN of indole was studied in the presence of DBT at 300qC,
3.0 MPa, LHSV of 10.0 h1, H2/Oil (V/V) of 300. The
conversion and HDN ratio of indole in the presence and
absence of DBT are presented in Fig. 2. DBT has a great
influence on the conversion of indole; the conversion
increases from 45% in the absence of indole to 68% by
adding 1000 g/g sulfur. However, the HDN ratio is only
enhanced by 4% in the presence of 1000 g/g sulfur, and it
decreases slightly with further increase of sulfur content.
The relative products concentration of indole HDN under
different sulfur contents is depicted in Fig. 3. The main
products are ECH, ECHE, and HIN in the absence of DBT.
Hydrogenation of OEA to OECHA was very slow in the
presence of large amounts of indole[17], therefore, one can
deduce that indole reacted mainly through the path of
HINoOHIoOECHAoECHE(ECH). With the increase of
sulfur content in the feed, the relative concentration of OEA
increases considerably, whereas that of HIN decreases
slightly, suggesting that the cleavage of the C(sp3)N bond
is promoted by DBT. However, the cleavage of the
C(sp2)N bond is not promoted by DBT as the relative
amount of EB, the hydrogenolysis product of OEA,
maintains at the same level. In the presence of DBT, the
selectivity of OEA is the highest among all products, and
OEA may cover active sites and produce a self-inhibitory
effect[18]. The relative concentrations of ECH and ECHE
declines slightly with the increase of sulfur content
indicating that DBT has a negative effect on the

Effects of DBT content on the relative product

HINoOHIoOECHAoECHE(ECH) path.
2.4

Effects of H2S on the HDN of indole

To decipher whether the effects of DBT on HDN of indole

results from DBT itself or from H2S released in the HDS
reaction, the HDN of indole with CS2 in the feed was
conducted, where H2S was generated in situ from CS2 under
H2 stream. The conversion and HDN ratio of indole (wN =
500 g/g) under different CS2 contents are shown in Fig. 4.
CS2 has a positive influence on indole conversion. Low
content of CS2 may also enhance the HDN ratio slightly;
however, with CS2 content of wN > 1000 g/g, the HDN ratio
decreases slightly. These suggest that the effects of CS2 on
HDN of indole are coherent with those of DBT.
Figure 5 shows the relative concentration of products in
HDN of indole under different CS2 contents. Comparing with
Fig. 3, the tendency of main products suggests again that the
effect of CS2 on the HDN of indole is consistent with that of
DBT. In conclusion, H2S generated in situ has the same
influence as DBT on the HDN of indole; both of them may
enhance the rupture of C(sp3)N bond and improve the
conversion of indole, bringing only limited effects on HDN
ratio.
2.5

Roles of sulfides in the HDN of indole

The conversion and HDS products of DBT were also

analyzed in the mutual HDS and HDN process. Even the
highest sulfur content of DBT can be converted completely
and the main product is BP, meaning that the pressure of H2S
released in the HDS of DBT was equal to that released from
CS2. In situ generated H2S has the same influence as DBT on
indole HDN, indicating that the influence of DBT on HDN
of indole may be caused by the H2S released in the HDS
reaction, rather than the presence of DBT.

XIANG Chun-e et al. / Journal of Fuel Chemistry and Technology, 2008, 36(6): 684690

Fig. 4

Effects of CS2 content on the conversion and HDN ratio of

Fig. 5

Effect of CS2 content on relative product concentration of

indole

indole HDN

: conversion; : HDN ratio

: ECH; : ECHE; : EB; 1: OEA; : HIN; : IND

The result is in good agreement with that of Satterfield:

HDN reaction was promoted by the HDS product H2S rather
than thiophene itself[19].
In the absence of sulfides, the HDN of indole is mainly
through HINoOHIoOECHAoECHE(ECH) path and the
conversion of indole is low. DBT and in situ generated H2S
promotes the rupture of C(sp3)N bond of HIN, and hence
the chemical equilibrium between indole and HIN shifts
toward the right direction. In the presence of sulfides, the
main product of indole is OEA. However, the HDN activity
of OEA is very low, because the bond energy of C(sp2)N is
high and the hydrogenolysis of C(sp2)N bond needs highly
unsaturated molybdenum atoms to adsorb OEA in side-on
mode[20]. These may be the reasons that sulfides cannot
promote the HDN ratio of indole.
Two kinds of catalytic sites were postulated on NiMoS
catalyst[21]: site I is a vacancy (CUS) in Ni-Mo-S structure
responsible for hydrogenation, whereas site II is a Brnsted
acid site responsible for hydrogenolysis. As shown in Fig. 6,
a sulfur vacancy can be converted to a Brnsted acid site and

an -SH group in a reversible process, which includes the

adsorption and dissociation of an H2S molecule. C(sp3)N
bond breaks via elimination or nucleophilic substitution
followed by CS hydrogenolysis on Brnsted acid site and
an -SH group[22,23]. Therefore, the increase of Brnsted acid
sites has a positive effect on the cleavage of C(sp3)N bond,
which is verified in this study. The increase of relative
concentration of OEA with increasing sulfur content
indicates that the amount of active sites for hydrogenolysis of
C(sp3)N bond depends on the H2S/H2 ratio.

Fig. 7

Conversion and HDN ratio of indole after CS2 being

Fig. 6 Interconversion between coordinatively unsaturated site

(CUS) and Brnsted acid site in the presence of H2S

Fig. 8

Products relative concentration of indole HDN after CS2

removed from reaction system

being removed from reaction system

: conversion; : HDN ratio

0: ECH; : ECHE; : OEA

XIANG Chun-e et al. / Journal of Fuel Chemistry and Technology, 2008, 36(6): 684690

High content of DBT has an negative effect on the

HINoOHIoOECHAoECHE(ECH) path under current
situation. In order to verify this phenomenon, the HDN of
indole was studied particularly after 4000 g/g of CS2 was
withdrawn from the feed. 17 samples were collected at an
interval of 1 h or 2 h and the results are depicted in Figs. 7
and 8.
Comparing the results in Figs. 7 and 4 (sulfur content 4000
g/g), it can be seen that the conversion and HDN ratio
increase immediately after the withdrawal of CS2, but
declines with extending the reaction time. After the reaction
lasted for 13 h, the conversion and HDN ratio of indole
leveled off. Comparing the relative product concentration of
the first sample and that of the sample with the sulfur content
of 4000 g/g, it can be seen that the relative concentrations
of ECH and ECHE increased by 22.2% and 3.8%,
respectively, whereas the relative concentration of OEA
decreased by 36.9%. However, the relative concentration of
ECH decreased evidently with the reaction time.
On the surface of catalyst, the active sites for
hydrogenation and those for hydrogenolysis in the HDN
process can convert each other reversibly (Fig. 6). In the
initial stage after the withdrawal of CS2, the CUS occupied
by H2S decreases; this favors the hydrogenation reaction.
The inhibition of hydrogenation by H2S has also been
reported[24,25]. The decrease of conversion and HDN ratio
subsequently results from the sulfur atom loss on the catalyst
surface. Therefore, it can be concluded that although the
formation of active sites for HDN must be in the presence of
sulfur atoms, the maintenance of active sites does not require
too much sulfur atoms. The relative concentration of ECH
increases at first and then declines with the increase of sulfur
loss, whereas the relative concentration of ECHE does not
change notably. Therefore, it may be concluded that ECHE
and ECH are different from OECHA in the formation
mechanism, which need to be further verified by more
studies.

Conclusions

DBT or CS2 brings on a negative influence on the HDN of

indole.

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