Petroleum Science and Technology

ISSN: 1091-6466 (Print) 1532-2459 (Online) Journal homepage: https://www.tandfonline.com/loi/lpet20

Selectively Hydrodesulfurization of FCC Naphtha

over Monolayer Dispersion Catalysts

Changlong Yin , Ruiyu Zhao & Chenguang Liu

To cite this article: Changlong Yin , Ruiyu Zhao & Chenguang Liu (2003) Selectively
Hydrodesulfurization of FCC Naphtha over Monolayer Dispersion Catalysts, Petroleum Science and
Technology, 21:9-10, 1617-1624, DOI: 10.1081/LFT-120023242

To link to this article: https://doi.org/10.1081/LFT-120023242

Published online: 20 Aug 2006.

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PETROLEUM SCIENCE AND TECHNOLOGY

Vol. 21, Nos. 9 & 10, pp. 1617–1624, 2003

Selectively Hydrodesulfurization of FCC

Naphtha over Monolayer Dispersion Catalysts

Changlong Yin,* Ruiyu Zhao, and Chenguang Liu

Key Laboratory of Catalysis, CNPC,

State Key Laboratory of Heavy Oil Processing, College
of Chemistry and Chemical Engineering,
University of Petroleum (East China), Dongying,
Shandong, China

ABSTRACT

Metal oxides and salts can disperse spontaneously to the surface and
pores of zeolite or alumina as atomically monolayer dispersion. In
this paper a series of supported solid base catalysts were prepared by
the method of monolayer dispersion, and the dispersion thresholds
were determined by means of X-ray diffraction quantitative phase
analysis. The fundamental functions of cobalt-molybdenum sulfide
catalysts on monolayer dispersion catalysts were evaluated by hydro-
desulfurization of FCC naphtha in a 100 mL high-pressure reactor

*Correspondence: Changlong Yin, Key Laboratory of Catalysis, CNPC, State

Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical
Engineering, University of Petroleum (East China), Dongying, Shandong 257061,
China; Fax: þ86-546-839-2284; E-mail: catgroup@hdpu.edu.cn.

1617

DOI: 10.1081/LFT-120023242 1091-6466 (Print); 1532-2459 (Online)

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1618 Yin, Zhao, and Liu

unit. Experimental results indicated that the catalyst prepared by

monolayer dispersion method in this article gives higher selectivity
than the traditional hydrogenation catalyst and the oxide catalyst
from hydrotalcite-like compounds. And the catalyst may show
greater hydrodesulfurization activity and less olefin saturation
under the moderate reaction conditions.

Key Words: Hydrodesulfurization; Monolayer dispersion; FCC

naphtha.

INTRODUCTION

Fluid catalytic cracked (FCC) naphtha currently forms a major part

of the gasoline product pool, and it provides a large proportion (85–95%)
of the sulfur in the gasoline. In order to meet with product specifications
or to ensure compliance with new environmental regulations, the sulfur
compounds may require removal, which are expected to become more
stringent in the future.
Cracked naphtha, as it comes from the catalytic cracker and without
any further treatments, has a relatively high octane number as a result of
the presence of olefinic components. Hydrodesulfurzition of the sulfur
compounds in the cracked naphtha will cause a reduction in the olefin
content, and consequently a reduction in the octane number, and the
octane number of the naphtha product decreases as the degree of
desulfurization increases.
Many studies have been carried out on selective catalysts, which can
remove sulfur while minimizing hydrogenation of olefins and octane
reduction by various techniques (Hillerova et al., 1994). Hydrotalcite
compounds have been used in recent years as catalysts and as precursors
of oxide catalysts and catalyst supports (Davis, 1991; Schaper et al.
1989). It would be desirable to have an efficient process for selectively
removing sulflur from olefin containing fuel feedstocks, like cracked
naphtha. This would minimize loss of octane value using an inexpensive
procedure under a wide range of conditions. It has now been found that
the selectivity for hydrodesulfurization was improved significantly by
using a catalyst support comprising essentially a hydrotalcite-like
composition (Clause et al., 1992).
It has been shown that metal oxides and salts can disperse
spontaneously to the surface and pores of zeolite or alumina as atomic
monolayer dispersion (Giordano et al., 1975). The reason of the
spontaneous dispersion is the decrease of free enthalpy of the whole
system, owing to that the dispersion results in significant increase in
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Hydrodesulfurization of FCC Naphtha 1619

entropy and formation of surface bonds comparable to the original

bonds of the compounds (Xie et al., 1984).
In this article, a series of supported solid base catalysts were prepared
by the method of monolayer dispersion, and the dispersion thresholds
were determined by means of X-ray diffraction quantitative phase anal-
ysis. The fundamental functions of cobalt-molybdenum sulfide catalysts
on monolayer dispersion catalysts were evaluated by hydrodesulfurization
of FCC naphtha in a 100 mL high pressure reactor.

EXPERIMENTAL

Preparation of Catalysts

The supported solid base catalysts were prepared by directly mixing

and calcining Mg(NO3)2
6H2O, active components and alumina. A series
of such catalysts samples with different MgO contents were prepared
in order to test the dispersion threshold of MgO on alumina. The
catalysts containing same active components supported on oxide from
hydrotalcite-like compounds (Zhao et al., 2001) and alumina were also
prepared for comparison. The active components were MoO3-CoO,
which deduced from ammonium heptamolybdate and cobalt nitrate,
respectively. The catalysts were dried at 383K overnight, then calcined
at 773K for 4 h. The contents of MoO3 and CoO in these catalysts were
10.0 and 3.0 wt%, respectively.

Characterization of the Catalysts

X-ray powder diffraction analysis was carried out with a Rigaku

D/max-IIA diffractometer using a graphite-filter CuK radiation at a
scan rate of 2 degrees per min. The dispersion thresholds were determined
by means of X-ray diffraction quantitative phase analysis with the
alumina as an inner standard.

HDS Reaction Procedure

Catalytic activity measurements were carried out in a high pressure

reactor. The catalyst is made into 3–4 mm strip, dried in air at 500 C for
5 h, and a 100 mL of catalyst is loaded into the reactor. Presulfiding is
carried out at 220 C for 3 h, and 240 C for 3 h and 260 C for 3 h with a
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1620 Yin, Zhao, and Liu

liquid stream containing 3 w% CS2 in straight-run naphtha. FCC

naphtha feed is then pumped into the reactor at the test temperature.
The reaction conditions are temperature, 260, 280, and 300 C,
pressure, 1.0–2.0 MPa, H2/feed ratio, 150–300, LHSV, 2–3 h 1.
The average hydrodesulfurization activity is calculated as the
percent conversion of total sulfur in feed and in units of HDS%. Olefin
saturation is measured by the PIONA analyses using gas chromatography
techniques and in units of percent olefin hydrogenation.

RESULTS AND DISCUSSION

Spontaneous Dispersion and Threshold Determination

A series of catalysts with different MgO contents were determined by

XRD, the XRD patterns of which were shown in Fig. 1. The weight ratio
of MgO on the catalyst is 15.0, 13.7, 12.0, and 0.0 wt%, respectively. The
contents of MoO3 and CoO in these catalysts were 10.0 and 3.0 wt%,
respectively. It is found from Fig. 1 that the XRD patterns of the cata-
lysts occur remarkable variations with the weight ratio of MgO on the
catalyst. There is no XRD peak of MoO3 when the weight ratio of MgO
on the catalyst is less than 12.0 wt%, however, there appear notable XRD

Figure 1. The XRD patterns of catalysts with different MgO contents after heat
treatment at 500 C for 4 h. The weight ratios of MgO on the catalyst are (a)
15.0 wt%, (b) 13.7 wt%, (c) 12.0 wt%, and (d) 0.0 wt%, respectively.
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Hydrodesulfurization of FCC Naphtha 1621

peaks of MoO3 when the weight ratio of MgO on the catalyst is larger
than 13.7 wt%. It is well known that the monolayer dispersion threshold
of MoO3 on alumina is about 12 wt%. This implies that the loading of
MgO causes the decrease in monolayer dispersion threshold value of
MoO3 on supports. Therefore, the weight ratio of MgO on the catalyst
must be less than a critical value to keep the monolayer dispersion of
MoO3 on the support.
It is also found from Fig. 1 that the XRD intensity of MoO3 is
proportional to the weight ratio of MgO. The regressed curve is obtained
by plotting the relative XRD intensity of MoO3 against the MgO
contents on catalysts, as illustrated in Fig. 2.
From the Fig. 2, it is found that there is a point above which the
residual crystalline of MoO3 appears, and the MgO content in this point
is called the critical value of MgO for the monolayer dispersion of
10 wt% MoO3 on the catalyst. It can be calculated from the regression
line that the critical value of MgO for the monolayer dispersion of 10wt%
MoO3 on the catalyst is 12.4 wt%. Therefore, the MgO content of the
monolayer dispersed catalyst used for evaluation of hydrodesulfurization
of FCC naphtha is determined as 12 wt% to keep the monolayer dispersion
of MoO3 on the catalyst.

Hydrodesulfurization of FCC Naphtha

The reaction conditions for HDS reaction of FCC naphtha in 100 mL

reactor were summarized in Table 1. The properties of FCC naphtha feed-

1.4

1.2

1.0
Residual crystalline

0.8

0.6

0.4

0.2

0.0
5 10 15 20
Content of MgO, wt%

Figure 2. The relative XRD intensity of MoO3 vs. MgO contents on catalysts.
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1622 Yin, Zhao, and Liu

Table 1. Reaction conditions for HDS reaction on monolayer dispersed catalyst.

Test no. 1 2 3 4 5 6 7

Temperature ( C) 260 260 280 280 280 280 300

Pressure (MPa) 1.0 2.0 2.0 2.0 1.0 1.0 2.0
H2/feed ratio 150 150 150 150 150 300 150
LHSV (h 1) 2.0 2.0 2.0 3.0 2.0 2.0 3.0
Feed time (h) 30 20 20 20 20 20 20

Table 2. The properties of feedstock and the hydrodesulfurization products.

Test no. Feed 1 2 3 4 5 6 7

Sulfur (mg/g) 1290.0 661.4 578.8 377.0 321.0 488.6 298.6 212.1
Research Octane 92.0 90.6 89.7 89.4 89.1 90.5 90.0 88.7
Motor Octane 85.5 84.3 83.5 83.2 82.9 84.2 83.7 82.6
Composition (wt%)
n-Paraffins 3.6 4.5 5.1 6.4 5.6 4.8 4.9 6.7
Branched paraffins 21.5 23.1 24.0 26.7 25.3 23.9 23.7 27.2
Olefins 41.8 38.8 36.0 31.2 33.5 35.3 35.5 28.9
Naphthenes 10.6 11.4 11.9 12.7 12.7 11.9 12.1 13.7
Aromatics 19.2 19.0 19.0 19.1 19.4 20.2 20.2 20.2
Others 3.4 3.2 3.9 3.8 3.6 3.9 3.4 3.3

stock and the hydrodesulfurization products with the catalyst prepared by

monolayer dispersion method were shown in Table 2. The contents of
MgO, MoO3, and CoO in the catalyst were 12.0, 10.0, and 3.0 wt%, respec-
tively.
It can be seen from Tables 1 and 2 that reaction conditions influence
the activity and selectivity of the catalyst. In general, temperature not
only facilitates the hydrodesulfurization activity, but also increases the
hydrogenation activity, as indicated by the fall of the octane number in
products with higher reaction temperature. High hydrogen pressure and
H2/feed ratio accelerate relatively both the desulfurization and hydroge-
nation activities of the catalyst. All these three conditions have a better
matching value, at which the catalyst shows better activity and selectivity.
It can be concluded from the results that the catalyst shows better activity
at 280 C, 1.0 MPa and H2/feed ratio 300, the octane value of the product
is 90.0 and the HDS is 76.8.
Figure 3 shows the activities of HDS and olefin hydrogenation
for different catalysts at the same reaction conditions. It can be concluded
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Hydrodesulfurization of FCC Naphtha 1623

90

HDS, % & Olefin hydrogenation, %

80
70
60
50
40
30
20
10
0
catalyst 1 catalyst 2 catalyst 3
HDS% Olefin hydrogenation %

Figure 3. The activities of HDS and olefin hydrogenation for different catalysts.
Catalyst 1, traditional Co-Mo/Al2O3; Catalyst 2, Co-Mo on oxide from
hydrotalcite-like compounds; Catalyst 3, Co-Mo catalyst prepared by monolayer
dispersion.

100 HDS %
Olefin hydrogenation, % & HDS, %

olefin hydrogenation %
80

60

40

20

0
1 2 3 4 5 6 7
Test no.

Figure 4. The distribution of olefin hydrogenation and HDS percent yield of the
desulfurized products.

from Fig. 3 that under the near yield of HDS, catalyst 3 gave the
lowest olefin hydrogenation yield. That is to say that the catalyst
prepared by monolayer dispersion method has higher selectivity for
hydrodesulfurization of FCC naphtha.
Figure 4 shows the distribution of olefin hydrogenation and HDS
percent yield of the desulfurized products for FCC naphtha on the
catalyst prepared by monolayer dispersion method. When the HDS%
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1624 Yin, Zhao, and Liu

amounts to 60–80%, the olefin hydrogenation only reaches 15–25%, the

loss of research octane number is mere about 2. It can be concluded that
the catalyst prepared by monolayer dispersion method in this article gives
higher selectivity than the traditional hydrogenation catalyst and the
oxide catalyst from hydrotalcite-like compounds. Moreover, the catalyst
may show greater hydrodesulfurization and less olefin saturation activ-
ities under the moderate reaction conditions, such as 260–280 C,
1–2 MPa.

CONCLUSIONS

The metal oxides and salts can disperse spontaneously to the surface
and pores of zeolites or alumina as atomically monolayer dispersion, the
monolayer dispersion threshold of oxide can be determined by means of
X-ray diffraction quantitative phase analysis. The monolayer dispersed
catalyst shows higher selectivity than the traditional hydrotreating
catalyst. It gives greater hydrodesulfurization activity and less olefin
saturation under the moderate reaction conditions, such as 260–280 C,
1–2 MPa.

REFERENCES

Hillerova, E., Vit, Z., Zdrazil, M. (1994). Appl. Catal. 118:111.

Davis, R. J., Derounane, E. G. (1991). Nature 349:313.
Schaper, H., Berg-Slot, J., Stork, W. H. (1989). J. Appl. Catal. 54:79.
Clause, O., Rebours, B., Merlen, E. (1992). J. Catal. 133: 231.
Giordano, N., Bart, J. C. J., Vaghi, A. et al. (1975). J. Catal. 36:81.
Xie, Y. C., Gui, L. L., Liu, Y. et al. (1984). Proc. Int. Congr. Catal. 8th
5:147.
Zhao, R., Yin, C., Liu, C. (2001). Prepr. Pap.-Am. Chem. Soc. 46:30.

Received September 10, 2002

Accepted October 7, 2002