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17th Saudi Arabia-Japan Joint Symposium

Dhahran, Saudi Arabia, November 11-12, 2007

Catalysts for ultra deep hydrodesulfurization and/or aromatics

saturation of middle distillates

Yuji YOSHIMURAa), Makoto TOBAa), Yasuo MIKIa), Yoshihiro MORITAb),

Takahisa HORIEb), Yuichi TAKAMORIb), Hisaya ISHIHARAb), Takashi KAMEOKAb).

a) National Institute of Advanced Industrial Science and Technology (AIST),

Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565, Japan
b) Catalysis Research Center, Catalyst & Chemicals Industries Co., Ltd., 13-2
Kitaminato-Machi, Wakamatsu-Ku, Kitakyushu, 808-0027, Japan

In developing the ultra deep hydrodesulfurization (HDS) catalysts, lots of efforts
have been focusing on how to prepare the so called Type II Co(Ni)MoS structures in the
highly dispersed and stabilized conditions. In general, an increase in MoS2 dispersion
will cause a loss of crystallinity of MoS2 phases and then result in an activity loss due to
its agglomeration, etc. We have developed a novel method to prepare the highly
dispersed and highly crystalline MoS2 phases, and finally developed the CoMo and
NiMo catalysts for ultra deep HDS, named as LX-NC1. On the other hand, developing
of the aromatics saturation catalysts are of interest for further upgrading of sulfur free
diesel, and producing the sulfur- and nitrogen-free blend stock from the non straight run
feedstocks, such as Light Cycle Oil (LCO). We have developed the highly active and
sulfur tolerant Pd-Pt catalysts for aromatics saturation, which catalysts will be used in
the 2nd stage process coupled with the 1st stage process using the Ni(Co)Mo catalysts.

1. Introduction
The need to reduce diesel exhaust emissions requires stringent specifications for
diesel fuel. Automotive manufacturers from around the world have proposed future
specifications for diesel fuel in Category 4 of the Worldwide Fuel Charter [1]. These
Novel transition metal
Aromatics (wt%)

sulfide catalysts
30 High
aromatics ULSD
Straight run
light gas oil
10 Novel noble metal catalysts
0.1 1 10 100 1000 10000
Sulfur (ppm)
Fig.1 Trends in low sulfur and/or low aromatics diesel production
17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

specifications include lowering levels of sulfur (<10ppm) (Fig.1) and aromatics and
lowering the T90 or T95 values.
Performances of HDS catalysts are crucial to the sustainable production of ultra
low sulfur diesel (ULSD) (S<10 ppm) in the existing units with minimal process
modifications. Recent advancement in HDS catalysts is marked, mostly due to the
development in the catalyst preparation technology to produce and control so-called
Type II sites [2] in order to maximize the HDS activity, in particular, by promoting the
hydrogenation pathway for the refractory sulfur compounds. Main concepts involved
are to increase the dispersions of MoS2 crystallites, and to maximize the MoS2 edge
decoration with Co (and Ni). Several approaches have been reported, i.e.,
controlling/skipping the calcinations step for minimizing the metals-support interaction
[3], using the proper chelating agents for controlling the MoS2 dispersion [3, 4], etc.
The support properties, such as pore structures, acid/base properties and sensitivity to
sulfur, etc., would also strongly contribute to the selective formation of Type II sites.
On the other hand, unsupported MoS2 catalysts, where all of the edge sites seemed to be
the potential Type II sites, are also active in HDS reactions even under the high p (H2S)
/p (H2) conditions [5]. Over the highly crystalline unsupported MoS2 particles, H2S
seemed to promote the hydrogenation route in HDS reaction, which is favorable for
HDS of the sulfur compounds with steric hindrances.
Therefore, we have introduced a new concept to increase the crystallinity of MoS2
crystallites in addition to increasing the dispersion of MoS2 crystallites as well as the
utilization of Co (and Ni). We have developed a novel HDS catalyst for ULSD
Lower levels of aromatics will help to maximize the regeneration cycle of the
exhaust gas treatment devices in addition to the reduction of PM emissions. The
two-stage hydrotreating has the flexibility to cope with the simultaneous reduction in
sulfur and in aromatics [6], i.e., CoMo or NiMo sulfide catalysts in the first stage and
sulfur-tolerant noble metal catalysts in the second stage. For reducing aromatics in the
straight-run light gas oils (SRLGO), catalytic function of aromatics saturation will be
mainly required for the noble metal catalysts. In contrast, for upgrading the low cetane
and highly aromatic light cycle oil (LCO) [7,8,9,10] to the low aromatic ULSD or low
sulfur gasoline blend stock, two different kinds of catalytic functions will be required
depending on the products, i.e., aromatics saturation for ULSD pool, and hydrocracking
(HYC)/selective ring opening (SRO) functions [10] for gasoline and ULSD pools. High
cost of hydrogen will be required for aromatics saturation of LCO, but some of the cost
up will be offset with the volume swell of products. Sulfur-tolerant noble metal
catalysts could be used under the mild reaction conditions to bypass the thermodynamic
limitations of aromatics saturation, but their increases in sulfur and nitrogen tolerance
are still required. Conversion of aromatics into alkyl-benzenes and paraffins by the

17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

HYC/SRO reaction could be advantageous for the hydrogen consumption than the
aromatics saturation, but catalytic performances in HYC/ROS selectivity and life should
be further improved.
In this paper, we have focused on the sulfur-tolerant bimetallic Pd-Pt catalysts
for aromatics reduction of the industrial feedstocks such as hydrotreated SRLGO and
LCO via. aromatics saturation.

2 Experimental
2.1 Catalysis for ultra deep HDS
2.1.1. Catalysts
The NiMo/-Al2O3 and CoMo/-Al2O3 catalysts were prepared by pore filling
impregnation with aqueous solutions containing molybdenum and nickel (or cobalt)
precursors and chelating agents. The -Al2O3 was used as a support (Catalysts &
Chemical Industries, Co., Ltd.(CCIC), surface area of 209m2/g and pore volume of
0.81cm3/g). The conventional CoMo/-Al2O3 and NiMo/-Al2O3 catalysts (calcined)
were also used as references. Catalysts were sulfided at 360 oC for 2 hours in a flow of
H2S(5%)/H2(95%) before typical HDS reaction and characterization.
2.1.2 Characterization of catalyst
The numbers of stacking layers and slab lengths of MoS2 crystallites were measured
by TEM analyses (JEOL, JEM-2000EXII). The Mo K-edge EXAFS spectra were
measured at the Photon Factory (BL-10B) in the Institute of Materials Structure Science,
High Energy Accelerator Research Organization, KEK at Tsukuba in Japan. NO uptake
data were obtained by a NO pulse adsorption method (Ohkura Riken, R6015) for the
sulfided catalysts with/without post-reduction treatments at 340 oC. DRIFT analyses of
adsorbed NO on the sulfided catalysts were done using a FT-IR spectrometer (Thermo
Electron, NEXUS 670). All of the catalysts were sulfided at 360oC.
2.1.3 Evaluation of catalytic performances
HDS runs were done in a high-pressure fixed-bed continuous-flow reactor [11] and
in a pilot plant of CCIC. Two kinds of liquid feedstocks were used: (a) model
compounds consisting of tetralin (30wt%), n-dodecanne (69.7 wt%), 4,6-dimethyl
dibenzothiophene (4,6-DMDBT) (S=1000 ppm), and n-butylamine (N=20 ppm), and
(b) SRLGO containing 1.54wt% of sulfur and 130 ppm of nitrogen for long-term tests
in a pilot plant. The reaction conditions for the catalytic experiments were as follows:
total H2 pressure of 3.9 MPa, reaction temperature of 593 K, WHSV of 16 h-1, H2/feed
flow ratio of 500 l (NTP)/l for feedstock (a); total H2 pressure of 4.9 MPa, reaction
temperature of 613 K, LHSV of 1.5 h-1, H2/feed flow ratio of 250 l(NTP)/l for feedstock
(b). The feedstocks and products were analyzed by using a gas chromatograph (Agilent
6890) for model compounds, a SFC (Dionex 600SFC) for aromatics, a sulfur analyzer
(Mitsubshi TS-100V), a GC-SCD (Sievers 355) for the sulfur compounds.
2.2 Catalysis for aromatics saturation

17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

2.2.1 Catalysts
Pd-Pt catalysts were prepared using different supports: USY zeolite and Yb-USY
zeolites. USY zeolite (SiO2/Al2O3=13.9) was obtained from Tosoh Co.. Yb-USY
zeolites were prepared by impregnation of USY zeolite with Yb acetate solution. The
bimetallic Pd-Pt catalysts supported on zeolites were prepared by incipient wetness
impregnation using [Pd(NH3)4]Cl2 and [Pt(NH3)4]Cl2(mole ratio Pd:Pt=4:1). The total
amount of metal loading was 1.2wt%. These impregnated catalysts were dried at 333 K
and then calcined in an oxygen stream at 573 K for 3 h, and then reduced in situ in H2
before the catalytic tests. For LCO upgrading, the higher silica content of USY zeolite
(SiO2/Al2O3 =80) was used as a support.
2.2.2 Characterization of catalyst
Metal dispersion (DR) of the Pd-Pt catalysts was determined by using a CO pulse
adsorption method. Acid strength and the amounts of each catalyst sample were
determined by using microcalorimetric measurements of the differential heat of
adsorption of ammonia at 303K after the catalysts were evacuated at 673 K for 4 h. The
EXAFS of Pt LIII-edge and Pd K-edge were measured for samples of each catalyst using
a double-crystal monochromator at the Photon Factory (BL-12C, 10B) of the Institute of
Material Structure Science (KEK-PF).
2.2.3 Evaluation of catalytic performances
Hydrogenation runs were done in a high-pressure fixed-bed continuous-flow
reactor under an up-flow mode for model compounds hydrogenation. Three kinds of
feedstocks were used: (a) model compounds consisting of tetralin(30wt%),
n-hexadecane(69.7 wt%), 4,6-dimethyldibenzothiophene (4,6-DMDBT) (S=300 ppm),
and n-butylamine(N=20 ppm), (b) hydrotreated SRLGO containing 263 ppm of sulfur,
26.3% of aromatics(19.4% of mono-ring aromatics, and 6.9% of di- and tri-rings
aromatics), and 8 ppm of nitrogen, and (c) LCO obtained from FCC unit where a
mixture of DSVGO (60%) and DSVR (40%) was used as a feed oil: density (@15 C) =
0.9124 g/cm3, sulfur = 6090 ppm, nitrogen = 225 ppm, and cetane index = 25.8.. The
conditions for the catalytic experiments were a total H2 pressure of 3.9 MPa, reaction
temperature of 553 K, WHSV of 16 h-1(for model compounds), WHSV of 4 h-1(for
hydrotreated SRLGO), H2/feed flow ratio of 500 l(NTP)/l. Reaction conditions for
LCO upgrading are shown later.

3. Results and Discussion

3.1 Catalysis for ultra deep HDS
3.1.1 Structure of the developed catalysts
Fig.2 shows the TEM picture of the developed NiMo/-Al2O3 catalyst. Average
slab length of 4.4 nm and average number of stacking layer of 1.7 indicated that MoS2
crystallites were highly dispersed with minimal stacking [12]. These values were
smaller than those of the conventional NiMo/-Al2O3 and CoMo-Al2O3 catalysts.

17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

The Mo3d and Ni2p XPS spectra for

the developed NiMo/-Al2O3 and the
conventional NiMo/-Al2O3 catalysts
(calcined) showed that sulfidation of
Mo and Ni
phases were more advanced for the
developed NiMo catalyst, i.e., Mo4+
Mo K-edge EXAFS data showed that
average coordination numbers of S and
Mo around Mo atom were 5.9 and 3.7,
respectively for the developed NiMo
catalyst, comparing 5.3 and 3.4,
respectively for the conventional NiMo
catalyst (calcined). This indicated that Fig.2 TEM picture of sulfided
highly crystalline MoS2 crystallites were NiMo/-Al2O3 catalyst
dispersed on the developed NiMo catalyst.
Fig.3 shows the NO uptake for
the sulfided catalysts after
post-reduction treatments. NO is
adsorbed on the sulfur coordi-
natively unsaturated sites (CUS).
New CUS sites were formed for
each of catalysts with increasing
the reduction temperature, but
highly crystalline MoS2 structure
over the developed NiMo catalyst
retarded the CUS formation, i.e.,
stronger Me-S affinity. However,
this indicated the lowest amounts
of CUS compared with the
conventional NiMo catalyst
Fig.3 NO uptake for the sulfided catalysts
(calcined) and CoMo catalyst.
NO absorbance spectra were also obtained for the developed and conventional
NiMo/-Al2O3 and CoMo/-Al2O3 catalysts. NO molecules adsorbed on CUS on Co
sulfide phases (absorption band at about 1865 cm-1) and MoS2 edge sites (1700 cm-1)
[13]. Interestingly, frequency shifted downward, i.e., weaker N-O bond, for the
developed catalyst. This is indicative of the increase in the electron density of CUS sites.
This might be due to an increase in basic properties of the neighboring S2- to donate the
electron to CUS sites after the crystallinity improvement of MoS2. This increase in

17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

basicity of S2- and CUS sites might be linked with the abstracting ability of H+ from
S-compounds in the E2 elimination reaction [14,15].
3.1.2 HDS performances of the developed catalysts
Table 1 shows the HDS activity and selectivity for 4,6-DMDBT for the
conventional NiMo catalyst (calcined) and developed NiMo and CoMo catalysts. Table
2 shows the HYD activity and selectivity for tetralin.

Table 1 HDS performances of the sulfided NiMo and CoMo catalysts

Conversion (mol%) Product distribution (mol%) Selectivity (-)
Catalysts TH- HH- PH- DM- DM- DM-BCH/ DM-BCH+DM-
(%) Total DDS HYD DM-BP
NiMo/Al2O3 (conv.) 82.0 83.5 22.5 61.0 22.5 1.2 0.3 0.2 50.0 9.3 0.19 2.63
NiMo/Al2O3 90.3 91.3 19.7 71.6 19.7 0.7 0.5 0.4 50.5 19.5 0.39 3.55
CoMo/Al2O3 83.4 84.1 35.5 48.6 35.5 0.2 0.2 0.3 38.5 9.4 0.25 1.35

Reaction schemes of tetralin hydrogen- Table 2 HYD performances of the catalysts

ation and HDS of 4,6-DMDBT are
shown in Fig.4. The developed Conversion Selectivity
NiMo/-Al2O3 catalyst showed the (mol%) (-)
highest HDS activity (90.3%) with the HYD
most dominant hydrogenation pathway NiMo/Al2O3 (conv.) 7.0 1.7
(HYD=71.6%). In contrast, the NiMo/Al2O3 8.6 1.9
developed CoMo/-Al2O3 catalyst CoMo/Al2O3 4.5 0.9
showed the higher HDS activity (83.4%)
with the most dominant direct desulfurization pathway (DDS=35.5%), though about
50% of HDS are still via. HYD pathway. As shown in Table 3, the developed

Fig.4 Reaction networks

17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

Table 3 Properties of SRLGO and ULSD

CoMo/-Al2O3 catalyst showed the
lowest tetralin HYD activity (4.5%) Feed Product
compared with the developed NiMo Density @15C g/cm3 0.8506 0.8240
catalyst (8.6%). This selective Cetane Index - 58 66
Sulfur ppm 1.11 7
hydrogenation of 4,6-DMDBT
Nitrogen ppm 105 1>
compared with aromatic compound of Total aromatics wt% 33.0 22.3
tetralin would be an advantage of the Mono-aromatics wt% 19.2 19.4
developed CoMo catalyst in mini- Di-aromatics wt% 11.3 2.4
mizing the hydrogen consumption. Tri+-aromatics wt% 2.5 0.5
Table 3 shows the properties of Distillation properties
IBP C 218 181
product obtained after hydrotreating
T10 C 269 248
SRLGO over the developed T30 C 291 278
NiMo/-Al2O3 catalyst. Deeper T50 C 302 293
hydrodenitrogenation and some T70 C 321 312
hydrogenation of aromatic T90 C 349 343
FBP C 379 376
compounds simultaneously occurred.
* Reaction conditions: T=340 C, P=4.9MPa, LHSV=1.5h-1
Boiling range shifted to lighter were
H2/oil=250 Nl/l; product after the time on stream of 50 h.
mainly due to the aromatics

3.1.3 HDS performances of the developed catalysts in the pilot plant runs
The above-mentioned developed catalysts were finally manufactured industrially
after several optimizations. As the new concepts introduced in our catalyst technology
were related with the Highly Dispersed Nano Crystalline Type II Active Phases, so the
newly HDS catalyst was named as LX-NC1, and was commercialized by Catalyst &
Chemical Industries Co., Ltd (CCIC).

Fig.5 HDS activity of LX-NC1

17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

Fig. 5 shows the performances of LX-NC1 and the conventional CoMo/-Al2O3

catalyst of CDS-LX6 (CCIC) in hydrotreating of SRLGO (S=1.542 wt%, N=130 ppm)
in a pilot plant. Improvement in HDS activity was significant, and an improvement was
about 20C at the product sulfur of 7 ppm. HDS activity of LX-NC1 was quite stable,
and the temperature compensation rate was about 0.5 C/month during the stable runs.
3.2 Catalysis for aromatics saturation
3.2.1 Structure of the developed catalysts
Table 4 shows the dispersion data for Pd-Pt/Yb (5wt%)-USY zeolite and Pd-Pt/USY
zeolite catalysts: Pd+Pt=1.2 wt%, Pd/Pt atomic ratio=4, SiO2/Al2O3 ratio of
zeolite=13.9 for both of the catalysts. Yb modification (atomic ratio of Yb to Pd+Pt was
3.1) caused an increase of the dispersion of reduced catalysts (DR), despite the loss of
the strong acidic sites of zeolite [16]. Yb modification of USY zeolite decreased the
dispersion of the reduced-sulfided catalysts (DRS). The basic Yb species might donate
electrons to the Pd-Pt phases to promote the surface sulfidation (DR-DRS), but retard the
agglomeration of Pd-Pt particles under the sulfiding and hydrotreating conditions as
confirmed with the TEM pictures.

Table 4 Effect of Yb modification on catalytic performances

Catalysts Pd-Pt/USY(13.9) Pd-Pt/Yb-USY(13.9)

Dispersion (DR) (%) 57.1 67.7
Dispersion (DRS) (%) 17.4 11.8
=(DR-DRS)/DR (%) 69.5 82.6
HYD of tetraline(%)* 33.1 47.0
trans -decalin/cis -decalin (-) 2.8 3.8
HDS of 4,6-DMDBT (%)* 50.3 75.0
3,3'-DMBCH/3,3'-DMCHB** 1.1 4.3
TOFHYD (102h-1)*** 7.1 15.0
TOFHDS (h-1)**** 2.0 2.1

SiO2/Al2O3 molar ratio of USY zeolite was 13.9

* HDS: hydrodesulfurization of 4,6-DMDBT; HYD: conversion of tetralin.
Feedstock: 4,6-DMDBT(S=300ppm)/n-butylamine (N=20ppm)/tetralin(29.7wt%)/n-C16
Reaction conditions: T=553K, P=3.9MPa, WHSV=16h-1, H2/Feed=500Nl/l.
Each activities are after the time on stream of 50h.
** ratio of 3,3'-dimethyldicyclohexyl to 3,3'-dimethylcyclohehyylbenzenne
*** TOF calculated based on DRS
**** TOF calculated based on DR-DRS

3.2.2 HYD performances of the developed catalysts (test reactions with tetralin)
Table 4 also shows the tetralin HYD activity and 4,6-DMDBT HDS activity for
Pd-Pt/USY and Pd-Pt/Yb-USY zeolite catalysts. Yb modification showed a doubling in
the TOF in HYD with the little changes in the TOF in HDS [17]. The highest value of
trans-decalin/cis-decalin ratio after Yb modification suggests that adsorption of the
hydrogenated tetralin intermediate on the HYD active sites was attenuating, thus

17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

facilitating its desorption and readsorption. The high selectivity of

3,3-dimethylbicyclohexyl (3,3-DMBCH) to 3,3-dimethylcyclohexylbenzene
(3,3-DMCHB) after Yb modification was due to the promotion of the hydrogenation
route, which accompanied their high HYD activity.
Table 5 shows the comparison in HDS of 4,6-DMDBT and tetralin HYD activities
between Pd-Pt/Yb-USY zeolite and the developed NiMo/-Al2O3 catalyst.
Pd-Pt/Yb-USY zeolite catalyst. The former catalyst showed quite a high HDS and an
equivalent HYD activity comparing with the latter catalyst, even under the 40 C lower
reaction temperature.

Table 5 Catalytic performances of noble metal catalyst and NiMo catalyst.

Reaction Hydrogenation Hydrodesulfurization

Catalysts temperature of tetralin of 4,6-DMDBT
(C) HDA (%) * HDS (%)*

Pd-Pt/Yb-USY(13.9)** 280 46.2 75.0

NiMo/Al2O3 *** 320 7.5 82.0

* Each of activities was obtained after the time on stream of 50h.

** Reaction conditions: T=280 C, P=3.9MPa, WHSV=16h-1, H2/Feed=500Nl/l.
*** Reaction conditions: T=320 C, P=3.9MPa, WHSV=16h-1, H2/Feed=500Nl/l.
Feedstock: 4,6-DMDBT(S=300ppm)/n-butylamine (N=20ppm)/

3.2.3 HYD performances of the developed catalysts in the pilot plant runs (HYD of
Table 6 shows the HDS and hydrodearomatization (HDA) performances of
Pd-Pt/Yb-USY zeolite catalyst in hydrotreating a ULSD (S=6ppm, total
aromatics=21.0wt%). Most of the aromatics were converted into the naphthenic
compounds after hydrotreating, but the aromatics contents would be easily conditioned
by changing the reaction conditions.

Table 6 Properties of low aromatic ULSD

This work Sweden GTL
Properties Units
Feed Product Class 1 Diesel
Cetane Intex - 59.5 65.3 52.1 92.3
Density15 C g/cm 0.8277 0.7953 0.8132 0.7843
Sulfur content mass ppm 6 0.1 1 <1
Total aromtics content mass 21.0 0.5 3.4 0
Polyaromatics content (di+tri+) mass 1.7 <0.1 0.1 0
Distillation properties
10 C 212 206 195 241
50 C 287 247 233 299
T90 C 342 311 272 330
Elemental analysis
H/C - 1.87 2.12 2.04 2.18

17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

An ultra-low aromatics diesel was also produced by hydrotreating a low sulfur

diesel (440 ppm sulfur, 22.1% mono-ring aromatics, 5.4% of di- and tri-ring aromatics),
and 8 ppm nitrogen) over the Pd-Pt/Yb-USY zeolite catalysts under more severe
reaction conditions using a bench-scale reactor, where the reaction conditions were T =
280-317 C, P = 4.9 MPa, H2/Feed = 500 NL/L, LHSV = 2 h1. Stable production of low
aromatics diesel (< 5wt%) was confirmed over this catalyst. Figure 6 shows Z-contrast
images of the ultra-microtome cut sample of the spent Pd-Pt/Yb-USY zeolite catalyst
used for 2700 h. The bimetallic Pd-Pt particles, which appeared as white spots, were
still highly dispersed, even after the time on stream of 2700 h.

Fig.6 TEM picture (Z-contrast image) of spent Pd-Pt/Yb-USY zeolite catalysts

3.2.3 LCO upgrading over the Pd-Pt catalysts in the pilot plant runs
Table 7 shows the catalytic performances of Pd-Pt/USY zeolite ((SiO2/Al2O3 =80)
based catalyst in hydrotreating the hydrodesulfurized and hydrodenitrogenated LCO [9].
With the 2-stage hydrotreating of LCO, LCO could be successfully converted into the
low aromatics (<10wt%), ultra low sulfur (<10ppm) and high cetane index (<42) diesel
blend stock. Further modification of catalytic functions, i.e., addition of selective ring
opening/hydrocraking functions, are in progress.

4. Conclusions
1. We have introduced a new concept to increase the crystallinity of MoS2 in addition to
increasing the dispersion of MoS2 crystallites as well as the utilization of Co (and Ni)
for the deeper HDS. According to this concept, we have finally developed a novel HDS
catalyst of LX-NC1 for sulfur-free diesel fuel production in the existing units operating
with almost the same conditions as in the production of <50 ppm sulfur diesel fuel.

17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

Table 7 Properties of feed LCO and hyodrtreated LCO

Feed 1st reactor 2nd reactor

LCO product product
Transition Noble metal
metals sulfide catalyst
H2/Oil NL/L - 500 400
ppH2 MPa - 5.0 5.0
LHSV h - 2.0 1.0
Temperatute C - 345 280 300
Density @15C g/cm 0.9124 0.8905 0.8433 0.8332
Cetane index - 25.8 28.7 39.2 41.4
Sulfur ppm 6090 117 6.4 2.7
Nitrogen ppm 225 20 0.4 0.1
Total aromatics wt% 76.1 73.5 9.9 3.1
Monoaromatics wt% 32.4 57.9 8.7 2.7
Diaromatics wt% 41.3 15.3 1.2 0.4
Tri+ aromatics wt% 2.4 0.3 0 0
Distillation properties
IBP C 170 174 164 156
T10 C 205 206 195 187
T30 C 227 223 212 208
T50 C 247 239 227 222
T70 C 267 259 244 239
T90 C 302 291 277 278

2. The bimetallic Pd-Pt catalyst supported on Yb-modified USY zeolite, i.e.,

Pd-Pt/Yb-USY zeolite catalyst, showed excellent HDS and HDA activity, and showed
high sulfur and nitrogen tolerance. ULSD containing less than 5% aromatics (di+
aromatics <1%) could be produced over these catalysts at moderate reaction conditions,
and their activities were confirmed during a time-on-stream of 2700 h in a bench-scale
high-pressure plant.
3. LCO could be successfully converted into the low aromatics (<10wt%), ultra low
sulfur (<10ppm) and high cetane index (<42) diesel blend stock by the two-stage
hydrotreating of LCO, using the Pd-Pt based catalysts in the 2nd stage. Its sustainable
activities were confirmed over more than 7000h in a bench-scale high-pressure plant.

LCO upgrading work has been carried out as a research project of the Japan
Petroleum Energy Center (JPEC) with the subsidy of the Ministry of Economy, Trade
and Industry, Japan.

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17th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 11-12, 2007

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