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Abstract
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
40
Novel transition metal
Aromatics (wt%)
sulfide catalysts
30 High
aromatics ULSD
Straight run
20
light gas oil
Low
aromatics
10 Novel noble metal catalysts
GTL/BTL/BDF
0
0.1 1 10 100 1000 10000
Sulfur (ppm)
Fig.1 Trends in low sulfur and/or low aromatics diesel production
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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
production.
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
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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
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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.
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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.
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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).
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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
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3.2.3 HYD performances of the developed catalysts in the pilot plant runs (HYD of
ULSD)
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.
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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.
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Acknowledgement
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.
References
[1] http://www.worldfuels.com/
[2] R. Candia, O. Srensen, J. Villadsen, N-Y. Topse, B.S. Clausen, H. Topse, Bull.
Soc. Chim. Belg. 1984, 93(8-9), 763-773.
[3] J.A.R. van Veen, E. Gerkema, A.M. van der Kraan, A. Knoester, J.Chem. Soc.,
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