Ind. Eng. Chem. Res.

1997, 36, 1519-1523 1519

Hydrodesulfurization of Catalytic Cracked Gasoline. 1. Inhibiting

Effects of Olefins on HDS of Alkyl(benzo)thiophenes Contained in
Catalytic Cracked Gasoline
S. Hatanaka*,† and M. Yamada
Department of Applied Chemistry, Faculty of Engineering, Tohoku University, Aoba, Aramaki,
Aoba-ku, Sendai 980-77, Japan

O. Sadakane
Petroleum Research Laboratory, Mitsubishi Oil Company Ltd., 4-1 Ohgimachi, Kawasaki-ku,
Kawasaki, 210 Japan

The HDS reaction feature of CCG on Co-Mo/γ-Al2O3 was investigated in detail to make clear
the important factors for the deep HDS of CCG. Two kinds of CCG, which are produced from
different origins and contain 229 and 61 ppm sulfur, respectively, were examined. GC-AED
analyses showed that both CCG contain 11 alkylthiophenes, 2 alkylbenzothiophenes, 3
alkylthiacyclopentanes, and 2 disulfides. In the reaction at 210 °C, 1.6 MPa using a conventional
flow reactor of pilot scale, the total sulfur content decreased from 229 to 127 ppm, whereas 22
ppm of thiols was produced. The HDS reactivities of alkylbenzothiophenes were higher than
those of alkylthiophenes, and HDS reactivity decreased with increasing the number of alkyl
groups. The reactivities of these sulfur compounds in CCG were much lower than those of the
corresponding pure compounds obtained by the individual reaction of pure sulfur compounds.
The low reactivity of sulfur compounds in CCG was found to be ascribed to the inhibiting effect
of olefins in CCG by comparing the HDS reactivity of thiophene in different solvents including
olefins. The inhibiting effect of olefin seems to be caused by two types of adsorption of olefin,
that is, weak adsorption and strong adsorption.

Introduction in the petroleum fraction. While inhibiting effects of

Recently, the process development to meet the severe
limitation of sulfur content in fuel oils is a very
important theme. Every effort has been extensively
made for understanding the reactivities of individual
sulfur components in feedstocks to be treated and the
HDS catalysis. For example, with respect to the HDS
mechanism, various mechanisms have been proposed
using pure sulfur compounds (e.g., thiophene, ben-
zothiophene, and dibenzothiophene) (Kwart et al., 1980;
Prins et al., 1989), since a one-point mechanism was
proposed (Lipsch and Schuit, 1969). With respect to the
fine structure of the catalyst active sites, a Co-Mo-S
model has been proposed (Topsøe and Clausen, 1984)
using some sophisticated techniques (Mossbauer and
EXAFS) and widely accepted.
However, in contrast to the detailed discussions about
the HDS mechanisms of pure sulfur compounds, the
details of a hydrotreating mechanism of petroleum
feedstocks remain unknown. For example, the studies
about HDS of catalytic cracked gasoline (CCG) (Desai
et al., 1994), hydrotreating of olefin-containing naphtha
(Satchell and Crynes, 1975; Ali and Anabtawi, 1995) and
LCO (Baron et al., 1992), and HDS of pyrolytic gasoline
(Casagrande et al., 1955; Meerbott and Hinds, 1955)
suggest that the HDS features of sulfur compounds in
the hydrotreatment of a petroleum fraction are different
from those of individual sulfur compounds.
One of the reasons for these differences seems to be
caused by the effects of various compounds contained
* Corresponding author. Telephone: +81-44-344-3128.
Fax: +81-44-344-3645.
† Present address: Petroleum Research Laboratory, Mit-
subishi Oil Co. Ltd., 4-1 Ohgimachi, Kawasaki-ku, Kawasaki,
210 Japan.
S0888-5885(96)00377-6 CCC: $14.00
hydrogen sulfide have been extensively studied (Sat-
terfield and Roberts, 1968; Metcalfe, 1969; Kasahara et
al., 1995), a few studies have been reported on the
effects of hydrocarbons on the HDS reaction. An
inhibiting effect of heptane on HDS of five kinds of
sulfur compound mixtures (dimethyl disulfide, diethyl
disulfide, benzenethiol, thiacyclopentane, and thiophene)
at 370 °C and 20-30 MPa has been reported (Phillipson,
1971). It has been reported that the presence of cis-2-
butene does not have any particular influence on
thiophene HDS on a single crystal of Mo at 340 °C and
atmospheric pressure (Bussell and Somorjai, 1987). An
inhibiting effect of naphthalene or tetralin on HDS of
4,6-dimethyldibenzothiophene at 2.5 MPa has been
observed (Isoda et al., 1994).
The present work tries to make clear the important
factors which affect the hydrotreatment of CCG and also
to make clear the difference between the HDS feature
of CCG and that of an individual sulfur compound. For
this, we have characterized the sulfur compounds
contained in CCG and compared the HDS reactivities
of the sulfur compounds in CCG with those of individual
sulfur compounds dissolved in some model compounds.
Experimental Section
Feedstock. (a) CCG. CCG-A produced from low
sulfur atmospheric residue and CCG-B produced from
desulfurized vacuum gas oil were used here.
(b) Pure Sulfur Compounds. Commercial-grade
thiophene, 2-methyl- or 3-methylthiophene, 2,5-dimeth-
ylthiophene, 2-ethylthiophene, and benzothiophene with-
out further purification were dissolved in toluene at 2.83
× 10-4 mol/mol of toluene and supplied for activity tests.
This concentration of sulfur compounds corresponds to
© 1997 American Chemical Society
1520 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997

Table 1. Physical and Chemical Properties of the HDS Table 2. Properties of CCG
Catalyst
CCG-A CCG-B
shape 1/ in. trilobe surface area, m2 g-1 200
22
support r-Al2O3 total pore volume, 0.61 composition,a vol %
metal content, cm3 g-1 saturates 41.9 44.6
wt % bulk density, 0.63 (0.68)a aromatics 27.7 33.6
MoO3 15.0 g cm-3 olefins (olefin structure breakdownb) 30.4 21.8
CoO 4.6 1-olefins
H2CdCR2 2.3 2.2
a 0.6-1.0 mm crushed catalyst for microreactor. H2CdCHR 5.0 3.0
internal olefins
100 wt ppm of sulfur content. Thiophene dissolved in HRCdCR2 9.8 8.6
HRCdCHR 13.3 8.0
n-heptane, n-octane, or a mixture of toluene (80 wt %) total sulfur,c ppm 229 61
and olefins (20 wt %) was also supplied for activity tests. density, g/cm3 @ 15 °C 0.778 0.780
Olefins used here were commercial-grade 1-octene and distillation temperature,d °C
diisobutylene without further purification. IBP 48 68
Analyses. (a) CCG and CCG-HDS Products. 10% 88 90
30% 110 111
Feedstock and HDS products were analyzed by the 50% 136 134
following methods. The contents of total sulfur and 70% 165 146
thiol-type sulfur were measured by oxidative microcou- 90% 201 174
lometry (ASTM-D3120) and a potentiometric method EP 231 205
(ASTM-D3227), respectively. Sulfur compounds were research octane number 87.0 86.7
quantitatively analyzed by a GC-AED (Hewlett Packard a By ASTM D-1319. b Type ratio was calculated by 1H-NMR
5921A) equipped with a 50 m PONA column. Identifi- data on the assumption that R2CdCR2 type olefin was not
cation of sulfur compounds was performed by GC-MS. included. NMR peak assignment for the olefin types, ppm by TMS
Olefin types were measured by 1H-NMR. standard: H2CdCR2, 4.50-4.80; H2CdCHR, 4.80-5.10 and 5.60-
6.00; HRCdCR2, 5.10-5.25; HRCdCHR, 5.25-5.60. c By ASTM
(b) Pure Sulfur Compounds and Their HDS D-3120. d By ASTM D-2887.
Products. In addition to the methods used in a, GC
and PIONA-GC (Analytical Controls Inc.) were used for microreactor. Metal composition and physical proper-
the measurement of hydrogenation reactivity of the ties of the catalyst are shown in Table 1.
olefins in the reaction of thiophene/toluene/olefin sys- HDS Reaction Procedure. Two conventional fixed-
tems. bed flow reactors (a bench pilot reactor of 1 in. i.d. and
Catalyst. CoO-MoO3/γ-Al2O3 catalyst was prepared a microreactor of 1/2 in. i.d.) were used for the catalyst
by a conventional pore-filling method using a prescribed presulfiding and HDS activity tests. CoO-MoO3/γ-
amount of Mo and Co aqueous solutions. CoO and MoO3 Al2O3 catalyst was presulfided at 250 °C for 2 h and
contents are 4.6 and 15.0 wt %, respectively. After then 300 °C for 2 h in the stream of a dibutyl disulfide/
drying at 110 °C for 12 h, the catalyst was calcined at straight run naphtha (bp 80-160 °C, total sulfur 250
550 °C for 1 h. A total of 60 mL of the catalyst was wt ppm)/hydrogen mixture. Following the presulfiding,
packed in a bench pilot reactor, and 4 mL of the catalyst in order to stabilize the activity, the catalyst was aged
crushed to 0.6-1.0 mm particles was packed in a at 300 °C for 48 h in the stream of a straight run

Figure 1. Sulfur compounds contained in CCG-A by GC-AED.

 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997 1521
Table 3. Sulfur Compounds in CCG-A before and after HDSa
reaction temperature, °C
feedstock 210 220
sulfur compound sulfur, ppm sulfur, ppm conversion, % sulfur, ppm conversion, %
thiophene 7 4 43 3 57
thiacyclopentane 5 2 60 1 80
2-methylthiophene 11 7 36 6 46
3-methylthiophene 10 5 50 3 70
2-methylthiacyclopentane 3 3 0 2 33
3-methylthiacyclopentane + 2-ethylthiophene 5 5 0 4 20
2,3-dimethylthiophene 5 3 40 2 60
2,4-dimethylthiophene 7 5 29 4 43
2,5-dimethylthiophene + 3-ethylthiophene 4 2 50 2 50
3,4-dimethylthiophene 3 1 67 1 67
C3-thiophenes 15 15 0 12 20
C4-thiophenes 7 6 14 5 29
benzothiophene 63 2 97 0 100
methylbenzothiophenes 63 28 56 12 81
dimethyl disulfide 4 1 75 0 100
diethyl disulfide 1 1 0 0 100
unknown 16 15 6 7 56
thiols 0 22 17
total sulfur 229 127 45b (54)c 81 65b (72)c
a Reaction conditions: pressure, 1.6 MPa, LHSV, 3.5 h-1, H2/feed ratio, 338 N L/L. b HDS %. c Conversion of sulfur compounds.

naphtha/hydrogen mixture. After these catalyst pre-

treatments, the feedstocks were flown into the reactors
with hydrogen. The reaction conditions were as fol-
lows: 150-225 °C, 1.3-1.6 MPa, LHSV 3.5 h-1, H2/feed
ratio 338 N L/L.

Result and Discussion

Characterization of Sulfur Compounds in Feed-

stocks. The properties of two kinds of CCG examined
here are analyzed and are shown in Table 2. It is
important to acquire the detailed information about the
sulfur compounds contained in the feedstocks. As
shown in Table 2, CCG-A contains 229 ppm sulfur and
CCG-B contains 61 ppm sulfur. The GC-AED analysis
of CCG-A is shown in Figure 1. Eleven alkylthiophenes,
2 alkylbenzothiophenes, 3 alkylthiacyclopentanes, and
2 disulfides are observed. These identification results
basically agree with a report analyzing CCG containing
1000 wt ppm sulfur (Albro et al., 1994). The composi-
tions of these sulfur compounds in CCG-A are shown
in Table 3. The total amount of alkylthiophenes is about
half that of alkylbenzothiophenes. CCG-B also contains
the same sulfur compounds.
As shown in Table 3, CCG contains olefins (20-30
vol %), saturates (paraffins, naphthenes) (40-45 vol %),
and aromatics (about 30 vol %). 1H-NMR analyses show
that olefin types in CCG-A and CCG-B are similar to Figure 2. HDS conversion of individual sulfur compounds and
CCG-A. Reaction conditions: pressure, 1.3 MPa (CCG-A, 1.6 MPa);
each other. That is, about 80% of the olefins contained LHSV, 3.5 h-1; H2/feed ratio, 338 N L/L. (a) Alkylthiophene
in both CCG are internal type. concentration 2.83 × 10-4 mol/mol of toluene (100 ppm sulfur in
Hydrodesulfurization of CCG. The compositions toluene). (b) Thiol yield was calculated into conversion. (c) Bench
of sulfur compounds in the HDS products of CCG-A pilot plant data.
reacted in a bench pilot plant are also shown in Table
3. As shown in this table, after HDS the total sulfur The calculated results are plotted in Figure 2. It is
content clearly decreases, whereas thiols are produced. noted that the difference of the reactor scale (bench pilot
In order to compare the overall HDS reactivity of CCG-A reactor or microreactor) does not affect the results,
with that of CCG-B, HDS (%) and conversion (%) are suggesting the high reliability of the present results.
defined in the following equations respectively consider- As shown in this figure, removing the effect of thiol
ing and removing the formation of thiols. formation, the HDS reactivity of CCG-A is not so
different from that of CCG-B.
HDS (%): (1 - product sulfur/feed sulfur) × 100 The following points are suggested from Table 3.
Alkylbenzothiophenes are more reactive than alkyl-
conversion (%): {1 - (product sulfur - thiophenes. It is noted that the reaction rate constant
thiol sulfur)/feed sulfur} × 100 of benzothiophene is 6 times larger than that of
1522 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997
Table 4. Effects of the Hydrocarbons on Thiophene HDSa
reaction HDS,
hydrocarbon condition % conversion, %
toluene A 68.8
n-heptane A 68.9
toluene B 52.8
n-octane B 54.8
toluene (80 wt %) + 1-octene (20 wt %) B 0.5
toluene (80 wt %) + diisobutyleneb (20 wt %) B 9.4
a Reaction conditions: (A) thiophene concentration, 1.56 × 10-3 mol/mol; temperature, 180 °C; pressure, 1.3 MPa; H /feed ratio, 2.33
mol/mol; catalyst/feed, 0.48 g of cat‚min/mol. (B) thiophene concentration, 2.83 × 10-4 mol/mol; temperature, 150 °C; pressure, 1.3 MPa;
H2/feed ratio, 1.60 mol/mol; catalyst/feed, 0.34 g of cat‚min/mol. b Composition: 2,4,4-trimethyl-1-pentene, 74.9 mol %; 2,4,4-trimethyl-
2-pentene, 20.6 mol %; others, 4.5 mol %.
thiophene. With increasing the number of alkyl sub-
stitution groups, the HDS reactivity decreases. It is also
noted that 2-methylthiophene is less reactive than
3-methylthiophene, being due to the steric hindrance
of a methyl group substituted at the 2-position of
thiophene. Thiacyclopentane and disulfides are ex-
tremely reactive.
These reactivities observed here may be different from
their intrinsic HDS reactivity. In order to understand
the important factors which affect the HDS reactivity
of CCG, the intrinsic HDS reactivity of pure sulfur
compounds was investigated and compared with the
above feature in the following section.
Hydrodesulfurization of Pure Sulfur Com-
pounds. In order to observe the intrinsic reactivity of
sulfur compounds contained in CCG, HDS reaction of
individual sulfur compounds dissolved in toluene was
carried out at several temperatures. The obtained
conversions are shown in Figure 2. From this figure, it
is clear that the reactivity decreases as benzothiophene
> thiophene > 3-methylthiophene > 2-methylthiophene
> 2-ethylthiophene > 2,5-dimethylthiophene within the
temperature range examined. It is noted that this order
of reactivity is the same as that of sulfur compounds in
CCG HDS. The reaction rate constant of benzothiophene
is 2 times larger than that of thiophene, and this result
is different from the results of CCG HDS, in which the
reaction rate constant of benzothiophene is 6 times
larger than that of thiophene. This difference may be
caused by the effects of competitive adsorption of various
sulfur compounds and hydrocarbons contained in CCG.
It is also noted that no formation of thiol was
observed. Therefore, thiol produced in CCG HDS is not
the intermediate of the HDS of sulfur compounds.
Comparing the HDS conversion shown in Figure 2
with that of the corresponding sulfur compounds in CCG
HDS, it is noticeable that the conversion in the indi-
vidual reaction is much higher than that in the CCG
HDS. In other words, the intrinsic reactivity of indi-
vidual sulfur compounds is depressed in CCG HDS. In
the following section, the reason for the low reactivity
of sulfur compound in CCG HDS was studied in more
detail.
Effects of CCG Hydrocarbons on HDS. In order
to investigate the factors which depress the intrinsic
reactivity of sulfur compounds contained in CCG as
mentioned above, the effects of the CCG hydrocarbons
on HDS were studied. As is already observed in the
first section, the major components of CCG are paraf-
fins, olefins, and aromatics. The effects of these com-
pounds on HDS reactivity of thiophene were examined
by using thiophene dissolved in toluene, n-heptane,
n-octane, 1-octene/toluene, or diisobutylene/toluene as
reaction feeds. The obtained results are shown in Table
4. As shown in Table 4, it is noted that the total sulfur
thiophene sulfur conversion hydrogenation
to thiol + sulfide, % of olefin, %
68.8 0
68.9 0
52.8 0
54.8 0
20.0 19.5 18.8
19.2 9.8 3.5
2
Figure 3. Response of HDS % in the presence of olefin. Reaction
conditions: temperature, 150 °C; pressure, 1.3 MPa; H2/feed ratio,
1.60 mol/mol; catalyst/feed, 0.34 g of cat‚min/mol. Feed: thiophene
concentration, 2.83 × 10-4 mol/mol in toluene or in 80 wt % toluene
+ 20 wt % diisobutylene.
content does not decrease only when olefins are present.
In other words, HDS of thiophene does not proceed in
the presence of olefin. It is also noted that the decreases
of thiophene conversion are accompanied by the forma-
tion of thiols and sulfides. The presence of each olefin
clearly depresses the HDS reactivity of thiophene in two
ways, that is, thiol production and inhibiting effects of
olefins on HDS active sites.
Inhibiting Effect of Olefin on HDS. In order to
study the reason for the inhibiting effect of olefins in
more detail, HDS activity tests of thiophene in the
presence of olefins were studied further. After the HDS
reaction of thiophene reached to its steady state, the
feed was switched from thiophene/toluene to thiophene/
diisobutylene/toluene. The change of thiophene HDS
accompanied by the change of the feed is shown in
Figure 3. As shown in this figure, olefin strongly
inhibits the thiophene conversion only when the feed
contains olefin. The depressed conversion is almost
recovered when the feed is switched back to the feed
without olefin. As shown in Figure 3, when the olefin-
containing feed is flown into the reactor again, the
thiophene conversion responded in the same way as the
first time. That is, the inhibiting effect of olefins is
almost reversible.
However, a small portion of conversion loss remained
after the feed was switched back to the feed without
olefin. Then, the reaction temperature was swung to
200 °C for a moment. As is also shown in Figure 3, by
the temperature swing, the small conversion loss re-
mained after the change of feed was recovered.
The above results suggest that olefin has two kinds
of inhibiting effects. One is reversible and may be due
to equilibrium adsorption. The other is irreversible and
may be due to oligomeric compounds which are easily
desorbed at higher temperature.

In HDS of CCG, lower conversion of olefin hydrogena-
tion as well as higher conversion of HDS is very
important to keep the octane value high. Concerning
this problem, it has been reported that olefin is easily
hydrogenated and the octane value fatally drops at
higher pressure and temperature reaction conditions
(Desai et al., 1994). Their report suggests that it is not
easy to keep the octane value high in HDS of CCG at
higher severity conditions. Therefore, the present
experiment was undertaken to investigate the possibil-
ity of deep HDS under lower severity conditions. As a
result, it was first found that olefin strongly inhibits
HDS of CCG. The present results suggests that new
catalyst with high HDS selectivity is necessary for deep
HDS of CCG under lower severity conditions, keeping
the octane value high.
Literature Cited
Albro, T. G.; Dreifuss, P. A.; Wormsbecher, R. F. Quantitative
Determination of Sulfur Compounds in FCC Gasolines by AED.
J. High Resolut. Chromatogr. 1993, 16, Jan, 13.
Ali, S. A.; Anabtawi, J. A. Olefins can limit desulfurization of
reformer feedstock. Oil Gas J. 1995, July 3, 48.
Baron, K.; Miller, R. E.; Tang, A.; Palmer, L. Hydrotreating of
Light Cycle Oil. NPRA Annual Meeting, New Orleans, LA, 1992;
Paper AM-92-20.
Bussell, M. E.; Somorjai, G. A. A Radiotracer (14C) and Catalytic
Study of Thiophene Hydrodesulfurization on the Clean and
Carbided Mo(100) Single-Crystal Surface. J. Catal. 1987, 106,
93.
Casagrande, R. M.; Meerbott, W. K.; Sartor, A. F.; Trainer, R. P.
Selective Hydrotreating over Tungsten Nickel Sulfide Catalyst.
Treatment of Cracked Gasolines. Treatment of Cracked Gaso-
lines. Ind. Eng. Chem. 1955, 47, April, 744.
Desai, P. H.; Lee, S. I.; Jonker, R. J.; De Boer, M.; Vrieling, J.;
Sarli, M. S. Reduce Sulfur in FCC Gasoline. Fuel Reformulation
1994, Nov/Dec, 43.
Isoda, T.; Ma, X.; Mochida, I. Reactivity of Refractory Sulfur
Compounds in Diesel Fuel (part 2). Inhibition of Hydrodesulfu-
Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997 1523
rization Reaction of 4,6-Dimethyldibenzothiophene by Aromatic
Compound. Sekiyu Gakkaishi 1994, 37, 506.
Kasahara, S.; Koizumi, N.; Iwahashi, J. K.; Yamada, M. Effect of
Fe, Co, Ni on Hydrodesulfurization Activity of Sulfided Mo/Al2O3
(Part 1). Sekiyu Gakkaishi 1995, 38, 345.
Kwart, H.; Schuit, G. C. A.; Gates, B. C. Hydrodesulfurization of
Thiophenic Compounds: The Reaction Mechanism. J. Catal.
1980, 61, 128.
Lipsch, J. M. J. G.; Schuit, G. C. A. The CoO-MoO3-Al2O3
Catalyst. Part 3. Catalytic Properties. J. Catal. 1968, 15, 179.
Meerbott, W. K.; Hinds, G. P., Jr. Reaction studies with Mixtures
of Pure Compounds. Selective Hydrotreating over Tungsten
Nickel Sulfide Catalyst. Ind. Eng. Chem. 1955, 47, April, 749.
Metcalfe, T. B. Inhibition par le sulfure d’hydrogène de la réaction
d’hydrodésulfuration des produits pétroliers. Chim. Ind. Gen.
Chim. 1969, 102, Nov, 1300.
Phillipson, J. J. Kinetics of Hydrodesulfurization of Light and
Middle Distillates. AIChE National Meeting, Houston, Feb
1971; Paper 31b.
Prins, R.; De Beer, H. J.; Somorjai, G. A. Structure and Function
of the Catalysis and the Promoter in Co-Mo Hydrodesulfur-
ization Catalysts. Catal. Rev.-Sci. Eng. 1989, 31 (1 & 2), 1.
Satchell, D. P.; Crynes, B. L. High olefins content may limit
cracked naphtha desulfurization. Oil Gas J. 1975, Dec 1, 123.
Satterfield, C. H.; Roberts, G. W. Kinetics of Thiophene Hydro-
genolysis on a Cobalt Molybdate Catalyst. AIChE J. 1968, 14,
Jan, 159.
Topsøe, N. Y.; Topsøe, H. Characterization of the Structures and
Active Sites in Sulfided Co-Mo/Al2O3 and Ni-Mo/Al2O3 Cata-
lysts by NO Chemisorption. J. Catal. 1983, 84, 386.
Topsøe, H.; Clausen, B. S. Importance of Co-Mo-S Type Struc-
tures in Hydrodesulfurization. Catal. Rev.-Sci. Eng. 1984, 26
(3 & 4), 395.
Received for review July 2, 1996
Revised manuscript received January 7, 1997
Accepted January 13, 1997X
IE9603777
X Abstract published in Advance ACS Abstracts, February
15, 1997.