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Short communication

Hydrodesulfurization and hydrodearomatization activities of

catalyst containing ETS-10 and AlPO4-5 on Daqing FCC diesel
Ye Zhao a,b, Baojian Shen a,*, Wencheng Zhang b, Ran Tian b, Zhihua Zhang b, Jinsen Gao a
a

State Key Laboratory of Heavy Oil Processing; The Key Laboratory of Catalysis of CNPC; and Faculty of Chemical Science and
Engineering, China University of Petroleum, Beijing, Changping 102249, China
b
Research Center of Daqing Chemical Engineering, Petrochina Company Limited, Daqing 163714, China
Received 1 March 2007; received in revised form 20 October 2007; accepted 26 October 2007
Available online 20 November 2007

Abstract
A NiW loaded ETS-10/AlPO4-5/Al2O3 composite support catalyst was optimized and used in hydrodesulfurization (HDS) and hydrodearomatization (HDA) of Daqing FCC diesel feedstock. The result indicated that ETS-10 and AlPO4-5 showed positive synergism
eect. The eects of operating conditions on its catalytic performance were investigated by using a 100 mL hydrotreating test unit. The
catalyst showed a remarkable HDS conversion of 99.9% and a HDA conversion of 73.2%. A clean diesel product with ultra-low sulfur
content (<1.0 lg/g) and very low polycyclic aromatic content (<2.0 wt.%) was obtained.
2007 Elsevier Ltd. All rights reserved.
Keywords: ETS-10/AlPO4-5; HDS/HDA; Ultra-low sulfur diesel

1. Introduction
Hydrotreating catalysts are playing an important role in
the modern renery to produce clean fuel [13]. However,
it is a big challenge for conventional hydrotreating catalyst
to produce ultra-low sulfur and low aromatic diesel [4].
Therefore, it is imperative to develop more active and more
selective hydrotreating catalyst for hydrodesulfurization
(HDS) and hydrodearomatization (HDA) [59].
In the course of our eort to improve the performance
of HDS/HDA catalyst, a novel composite support, the
unique combination of titanosilicate ETS-10 with good
thermal stability [1013] and aluminophosphate AlPO4-5
of crystalline AlPO4 structure [14] with alumina, was rstly
developed, and the tailoring eects of ETS-10 and AlPO4-5
to alumina, as well as the promotions for HDS and HDA
with a NiW based model catalyst were reported [13,15
19]. In the present paper, we would like to report the investigations on the optimization of ETS-10 and AlPO4-5 con*

Corresponding author. Tel./fax: +86 10 89733369.

E-mail address: baojian@cup.edu.cn (B. Shen).

0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.10.022

Downloaded from http://www.elearnica.ir

taining hydrotreating catalyst by using real FCC diesel as

feedstock. The HDS/HDA performances of this catalyst
with alternated operating conditions by using a 100 mL
hydrotreating test unit are also presented.
2. Experimental
A typical procedure for catalyst preparation is as follows, the even mixture of ammonium-exchanged ETS-10
[13], AlPO4-5 [16] and pseudo-boehmite powder was
extruded, followed by drying at 393 K for 4 h and calcining
at 823 K for 4 h. The obtained composite support was designated as ATSP. For comparison, the composite supports
containing ETS-10 or AlPO4-5 merely, designated as AETS
or AAP, respectively, were also prepared under the similar
procedure. The catalysts NiW/ATSP, NiW/AETS, NiW/
AAP and NiW/Al2O3 with the same NiW loading
amounts of metal (28.9 wt.% of WO3 and 5.0 wt.% of
NiO) were prepared by pore volume impregnation method
and catalysts were designated as C-ATSP, C-AETS, CAAP and C-Al2O3, respectively. The HDS and HDA activity were evaluated in a continuous ow xed-bed reactor

2344

Y. Zhao et al. / Fuel 87 (2008) 23432346

with the catalyst loading of 100 mL. The catalysts were presulded in situ with 2 vol.% CS2 in kerosene. The feedstock, Daqing FCC diesel, have density of 0.8702 g/mL,
sulfur content of 1052.0 lg/g and total aromatic content
51.2 vol.%.
The total sulfur content was measured by a coulometric
sulfur analyzer. The total aromatic content analyses were
determined by the standard method of uorescence indicator adsorption by using Dalian TSY-1132 instrument. The
composition was analyzed by BOMEM MB-160 near infrared (NIR) spectra.
3. Results and discussion
3.1. Eect of support composition on catalyst activity
The catalyst activities of C-Al2O3, C-AETS, C-AAP and
C-ATSP at 8.0 MPa, 633 K, 1.0 h 1 and 500:1 (H2/oil, v/v)
are listed in Table 1. It was obvious that the catalytic activity of the catalysts containing ETS-10 or AlPO4-5 was
enhanced in comparison with that of C-Al2O3. In detail,
compared with catalyst C-Al2O3, HDS and HDA conversions increased by 1.4% and 2.8% for catalyst C-AETS,
and increased by 0.5% and 5.7% for catalyst C-AAP. This
indicated that catalyst containing AlPO4-5 (catalyst CAAP) showed better HDA activity than the catalyst containing ETS-10 (catalyst C-AETS), whereas, the HDS
activity of catalyst C-AETS was better than that of CAAP. The dierence of activity and selectivity for C-AETS
and C-AAP may be resulted from the dierent characteristic of molecular sieves ETS-10 and AlPO4-5 [17,18]. Thus,
when various amount of ETS-10 or AlPO4-5 were introduced to alumina to prepare the corresponding composite
support, the dierent degree of inuences on the dispersion
of metal active component could be caused. The data in
Table 1 indicates that the catalyst C-ATSP (containing
both AlPO4-5 and ETS-10) owns the highest HDS (conversion 99.7%) and HDA (conversion 72.9%) activities. It
reduced the sulfur content from 1052.0 lg/g to 2.7 lg/g,
and aromatics from 51.2 vol.% to 13.9 vol.%. It was clear
that simultaneous introduction of ETS-10 and AlPO4-5
at a proper ratio could not only take advantage of their
Table 1
The HDS and HDA activities of C-Al2O3, C-AETS, C-AAP and C-ATSP
under conditions of 8.0 MPa, 633 K, 1.0 h 1, 500:1 (H2/oil, v/v)
Catalyst

HDS conversion (%)

(Sulfur content, lg/g)

HDA conversion (%)

(Aromatic content, vol.%)

C-Al2O3
C-AETS
C-AAP
C-ATSP

97.6
99.0
98.1
99.7

56.4
59.2
62.1
72.9

(25.6)
(10.2)
(19.5)
(2.7)

(22.3)
(20.9)
(19.4)
(13.9)

Note: HDS conversion (%) = [(Sfeed Sproduct)]/Sfeed  100; HDA conversion (%) = [(Afeed Aproduct)]/Afeed  100. Where Sfeed and Sproduct are
the total sulfur contents (m%) in the feedstock and liquid product,
respectively, and Afeed and Aproduct are the total aromatic contents (vol.%)
in the feedstock and liquid product, respectively.

individual advantages (HDS or HDA), but also cause positive synergism eects amidst them, which results in a
remarkable enhancement in the catalytic activity of the catalyst C-ATSP.
The evaluation data showed that decreasing ETS-10/
AlPO4-5 ratio would result in the increase of HDS and
HDA conversions and the highest HDS and HDA conversions achieved were 99.7% and 72.9% for catalyst C-ATSP,
in which the ratio of ETS-10 to AlPO4-5 was 1:2 (wt/wt). It
was found that the introduction of ETS-10 and AlPO4-5
can also bring a certain amount of moderate Bronsted acid
sites [19], which favor eliminating the refractory 4,6DMDBT and its steric-hindered derivatives through the
isomerization-hydrogenation pathway.
Table 2 compares the NIR compositional analysis data
of Daqing FCC diesel before and after hydrotreating over
C-ATSP catalyst. The content of alkanes in hydrotreated
diesel increased by 12%, which may mainly result from saturation of olens, saturation and ring opening of monoaromatics with short side chain, and ring opening of single ring
cycloparan. It is known that reaction rate constant of
diaromatics and triaromatics was far greater than that of
monoaromatics. In the present work, the content of polycyclic aromatics (diaromatics and triaromatics) decreased
from 33.1 wt.% to 4.6 wt.%, and accordingly, the calculated Cetane Number increased from 26.7 to 47.7.
3.2. Eect of reaction conditions on HDS and HDA activities
HDS and HDA activities of C-ATSP catalyst were
investigated at various reaction temperatures (573 K,
593 K, 603 K, 613 K, 623 K, 633 K and 643 K) at
8.0 MPa, 1.0 h 1, 500:1 (H2/oil, v/v). HDA conversion
increased with temperature elevating from 19.8% (573 K)
until 68.8% (633 K), after 633 K it turned to decrease.
HDS conversion also increased with temperature elevating
from 99.2% (573 K) until 99.9% (603 K). No further HDS
conversion increasing was observed when higher temperature was used. The NIR compositional analysis data of
the hydrotreated diesel products over catalyst C-ATSP at
temperature range from 573 K to 613 K also suggest that
Table 2
Comparison of the compositional NIR analysis of FCC diesel feed and the
hydrotreated diesel over catalyst C-ATSP under the conditions of
8.0 MPa, 633 K, 1.0 h 1, 500:1 (H2/oil, v/v)
Item

FCC diesel feed

Product

Saturates (wt.%)
Alkanes (wt.%)
Cycloalkanes (wt.%)
Monocycloalkanes (wt.%)
Dicycloalkanes (wt.%)
Tricycloalkanes (wt.%)
Aromatics (wt.%)
Monoaromatics (wt.%)
Diaromatics (wt.%)
Triaromatics (wt.%)
Calculated cetane number

40.7
27.9
13.0
11.0
1.8
0.4
58.6
24.2
27.6
5.5
26.7

68.9
39.7
26.5
10.4
10.3
7.1
31.2
26.7
3.9
0.7
47.7

Y. Zhao et al. / Fuel 87 (2008) 23432346

the aromatic content decreased from 45.8 wt.% to

39.3 wt.% when the reaction temperature increased from
573 K to 613 K, and most of diaromatics (decreased from
27.6 wt.% in feed to 4.8 wt.% in product at 613 K) and triaromatics (decreased from 5.52 wt.% in feed to 0.32 wt.%
in product at 613 K) were saturated to monoaromatics or
cycloparan. The aromatics accumulated in the product
were mainly monoaromatics, which is critical to deep
hydrogenation saturation for aromatics [3,20,21].
The eect of LHSV on hydrogenation reaction under the
reaction condition of 6.0 MPa, 633 K, 500:1 (H2/oil, v/v) of
C-ATSP catalyst was evaluated. With the increase of LHSV
from 1.0 h 1 to 2.6 h 1, the HDS conversions decreased
from 99.9% to 99.6% (HDS conversions decreased to
94.8% at 593 K, 6.0 MPa, 2.6 h 1, 450:1(H2/oil, v/v)), and
the HDA conversions decreased from 66.8% to 21.9%. It
was interestingly found that most of triaromatics and diaromatics disappeared even at a higher LHSV condition.
The eect of reaction pressure on hydrogenation reaction under the reaction condition of 633 K, 1.0 h 1, 500:1
(H2/oil, v/v) of C-ATSP catalyst was also evaluated. As
reaction pressure increased from 6.0 MPa to 9.0 MPa the
HDA conversions linearly increased from 42.4% to 75.0%
obviously, however, the HDS conversion just decreased
slightly from 99.9% to 99.6%.
The HDS and HDA performance of catalyst C-ATSP
under the reaction condition of 8.0 MPa, 633 K, 1.0 h 1
at various H2/oil volume ratios from 300 to 1400 were also
Table 3
Comparison of the HDS and HDA evaluation results of C-ATSP and
reference catalyst A to Daqing FCC diesel feeda
Item

FCC diesel
feed

Reference catalyst
A

C-ATSP

Density (g/mL)
Sulfur content (lg/g)
HDS conversion (%)

0.8722
1052.0

0.8370
15.0 (89.9)
98.6 (91.5)

Aromatic content
(vol.%)
HDA conversion (%)

51.2

29.8 (46.8)

41.8 (8.6)

Cetane Number
Product yield (vol.%)

31.3

37.4
100.8

0.8320
2.0 (45.5)
99.8
(95.7)
18.4
(39.7)
64.1
(22.5)
40.3
101.6

Reaction conditions: 8.0 MPa, 633 K, 1.0 h 1, 500:1 (H2/oil, v/v); the
data in the parentheses were obtained under the reaction conditions:
8.0 MPa, 593 K, 2.6 h 1, 450:1 (H2/oil, v/v).

2345

investigated. It showed that HDA conversions increased

from 43.2% to 74.6% markedly as H2/oil ratio increased,
and the trend of the increment was not drastic as H2/oil
ratio large than 500:1. HDS activities achieved the highest
conversion of 99.9% when H2/oil was 500:1.
3.3. Performance of catalyst C-ATSP
To evaluate the activity of catalyst C-ATSP, a commercial catalyst, which consisting of same active metals of
molybdenum and nickel as well as alumina support, was
selected as the reference catalyst. Table 3 shows the evaluation results of catalyst C-ATSP and reference catalyst A
at the conditions of 8.0 MPa, 633 K, 1.0 h 1, 500:1 (H2/
oil, v/v). It indicated that HDS conversion of catalyst CATSP (99.8%) was higher than that of reference catalyst
A (98.6%). Also HDA conversion of catalyst C-ATSP
(64.7%) signicantly higher than that of reference catalyst
A (42.8%). Compared with feedstock, cetane number increment of catalyst C-ATSP was 9 unit, higher than that of
reference catalyst A (6 unit). At the same time, catalyst
C-ATSP also the shows the higher liquid yield of
101.6 vol.%. The evaluation data at a relatively low conversion are also listed in Table 3, the new catalyst (C-ATSP)
still showed a higher HDS and HDA conversions than that
of the reference catalyst under reaction conditions of
8.0 MPa, 593 K, 2.6 h 1, 450:1(H2/oil, v/v).
The evaluation results of the optimized catalyst C-ATSP
are listed in Table 4. It shows that HDS and HDA conversions of diesel achieved 99.9% and 28.5%, respectively at
the reaction conditions of 6.0 MPa, 593 K, 1.0 h 1, 500:1
(H2/oil, v/v), with sulfur content 1.3 lg/g and polyaromatics content less than 5.0 wt.% (NIR method) which satisfy
the Europe IV diesel specications. Furthermore, Under
the reaction condition of 8.0 MPa, 613 K, 1.0 h 1, 500:1
(H2/oil, v/v), HDS and HDA conversions achieved 99.9%
and 73.2%, respectively, with sulfur content <1.0 lg/g
and polyaromatics content less than 2.0 wt.%, and the
liquid yield of the product is over 100 vol.% under these
conditions. When a higher LHSV (2.6 h 1), lower reaction
temperature (593 K) and H2/oil ratio (450:1, v/v) conditions was used at 6.0 MPa, a fairly good HDS conversion
(94.8%) was also observed. Unfortunately, the HDA conversion (16.8%) was very low under the same reaction
condition.

Table 4
The HDS and HDA evaluation results of the optimized catalyst C-ATSP to Daqing FCC diesel under dierent operation conditions
Operation conditions
Feedstock
593 K, 6.0 MPa, 1.0 h
613 K, 8.0 MPa, 2.0 h
633 K, 8.0 MPa, 1.0 h
593 K, 6.0 MPa, 2.6 h
613 K, 8.0 MPa, 2.6 h
Selected specications

,
1
,
1
,
1
,
1
,
of

500:1 (H2/oil, v/v)

500:1 (H2/oil, v/v)
500:1 (H2/oil, v/v)
450:1 (H2/oil, v/v)
450:1 (H2/oil, v/v)
Europe IV diesel

Sulfur content
(lg/g)

HDS
conversion (%)

Aromatic
content (vol.%)

HDA
conversion (%)

Polycyclic aromatic
content (m%)

1052.0
1.3
10.1
<1.0
54.7
13.4
<50

99.9
99.0
99.9
94.8
98.7

51.2
36.6
37.6
13.7
42.6
32.1

28.5
26.6
73.2
16.8
37.3

29.8
<5.0
<7.0
<2.0

<8

2346

Y. Zhao et al. / Fuel 87 (2008) 23432346

4. Conclusion
A novel NiW loaded hydrotreating catalyst with ETS10 and AlPO4-5 composite support was developed to
improve HDS and HDA of FCC diesel. ETS-10 and
AlPO4-5 showed positive synergism eect and the good
combination of ETS-10 to AlPO4-5 was 1:2 (wt/wt). The
HDS and HDA conversions were 99.9% and 73.2%, respectively, cetane number increased by 9 unit when Daqing
FCC diesel was used as feedstock under conditions of
8.0 MPa, 633 K, 1.0 h 1, 500:1 (H2/oil, v/v).
Acknowledgement
The authors gratefully acknowledge the funding of
this project by MOST 973 Project of China
(2004CB217806) and by PetroChina Co.
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