Applied Catalysis A: General 303 (2006) 116–120

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Sulfur reduction in FCC gasoline using catalyst additives

M.A. Bari Siddiqui a,*, Shakeel Ahmed a, A.M. Aitani a, C.F. Dean b
a
Center for Refining & Petrochemicals, King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia
b
Process & Control Systems Department, DPED, Dhahran, Saudi Aramco, Saudi Arabia
Received 12 December 2005; received in revised form 5 February 2006; accepted 6 February 2006
Available online 13 March 2006

Abstract
Among the various options available for the reduction of gasoline sulfur in fluid catalytic cracking (FCC), a viable option would be the use of
FCC catalyst additives. Alumina supported zinc, titanium and gallium additives were prepared, mixed with Y-zeolite based FCC catalyst and the
catalyst-additive mixture was evaluated for their sulfur reduction ability in micro-activity test unit (MAT). A 30% reduction in gasoline sulfur was
achieved with Ga/alumina additive. The sulfur reduction ability of the Ga/alumina additive was higher than zinc/alumina and titanium/alumina
additives. The additives slightly reduced catalyst’s cracking activity with no change in coke yield.
# 2006 Elsevier B.V. All rights reserved.

Keywords: FCC additive; Gasoline sulfur; MAT testing

1. Introduction A number of options for FCC gasoline sulfur reduction are

Many countries worldwide are introducing regulations to
reduce sulfur levels in gasoline to less than 30 ppm within the
coming few years. In some countries, regulation of gasoline
sulfur will drop to 10 ppm by 2008. To meet this regulation,
refiners are addressing various options to reduce sulfur in
gasoline. Sulfur in gasoline increases SOx emissions in
combustion gases, reduces the activity of vehicle catalytic
converters, and promotes corrosion of engine parts. It has been
claimed that reducing sulfur content in gasoline to 30 ppm will
improve the effectiveness of catalytic converters in reducing
NOx, CO, and un-burned hydrocarbons. Some refiners have
already met the 50 ppm sulfur specification and some others are
about to meet the 30 ppm specification.
In order to meet the strict sulfur regulations, it is necessary to
adopt new technologies to reduce gasoline sulfur, mainly the
fluid catalytic cracking (FCC) gasoline which contains high
level of sulfur compounds derived from vacuum gas oil (VGO)
and atmospheric residue. Of the total gasoline production
volume approximately a third comes from the FCC process,
which contributes to more than 90% of the total sulfur content
in the gasoline pool. To effectively reduce gasoline pool sulfur,
refiners must focus on FCC gasoline [1].
* Corresponding author. Fax: +966 3 860 4509.
E-mail address: mabari@kfupm.edu.sa (M.A. Bari Siddiqui).
0926-860X/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2006.02.012
available, but none of them is ideal. Some options imply high
capital and operation costs, and others lower the octane number
due to the saturation of the olefins. Sulfur reduction by additives
or catalysts inside the FCC unit offers some refiners economic
advantages over the standard solution-selective gasoline
hydrotreating or HDS methods. This alternative is attractive
because it does not require an additional process and the capital
costs would be low compared to the other alternatives.
Numerous publications in the open and patented literature
discussed the use of additives to reduce gasoline sulfur
compounds such as thiophene, tetrahydrothiophene, alkyl-
thiophenes, and benzothiophene. Taking into account the Lewis
basic character of these thiophenic compounds, sulfur
reduction additives must have acidic nature. Various additive
compositions were tested including Ni, Cu, Zn, and Ag
aluminates [2], Zn/alumina [3–5], V/alumina [6,7], and Zn–Mg
spinels [8]. Effects of operating conditions, feed composition
and catalyst type on sulfur in naphtha were studied [9–11].
Myrstad et al. [4] disclosed a composition comprising a
hydrotalcite material impregnated with a metal additive, i.e., a
Lewis acid, preferably Zn, the impregnated hydrotalcite
material can be incorporated into the matrix of an FCC
catalyst, or can be used as a separate compound next to an FCC
catalyst. Additives containing Zn and Ti were more effective
than additives containing only Zn or Ti [6]. Andersson et al.
[12] studied Zn additives supported on alumina, titania and
 M.A.B. Siddiqui et al. / Applied Catalysis A: General 303 (2006) 116–120
hydrotalcite. Studies reported by Lappas et al. [13], Shan et al.
[14], and Corma et al. [15,16] focused on sulfur reduction
mechanism. A recent study [8] reported that Lewis acid sites are
located on aluminum and that they are rendered active by the
presence of Zn.
In this study, Zn/alumina, Ti/alumina, and Ga/alumina
additives were prepared and evaluated in MAT to assess their
effectiveness in reducing sulfur species in gasoline.
2. Experimental
2.1. Materials
A commercial equilibrium USY-FCC catalyst and VGO
were obtained from a local refinery. This catalyst was used as a
base catalyst in all MAT tests. The catalyst and additives were
steam deactivated, at 810 8C for 8 h. The properties of VGO
which contains 2.5 wt.% of sulfur, are presented in Table 1.
Alumina support used in preparing additives was a spray-dried
g-alumina CP-100 acquired from Alcoa, USA. The surface area
of this alumina sample was 150 m2/g. Metal salts were obtained
from Aldrich and high-purity gases were used in MAT and GC
analyses.
2.2. Additives preparation procedure
The additives were prepared using a spray-dried g-alumina
and the incipient wetness method was adopted to impregnate
metals. The incipient volume of solution required to impregnate
metals (zinc, titanium, gallium) on alumina was determined by
measuring the amount of deionized water required to barely wet
1 g of calcined alumina. The solution of metal nitrate was added
slowly to the pre-weighed alumina and mixed thoroughly with
the help of a Teflon coated spatula. The mixture was left for 1 h
at room temperature to ensure complete wetting of alumina.
After that the sample was dried at 50 8C in an air-flow oven for
3 h. Then the temperature was increased to 110 8C and the
sample was left overnight for complete drying. Finally the
additive sample was calcined at 500 8C for 3 h.
2.3. Activity measurements
Additives were blended with base-catalyst in a 1:10 ratio.
The base-catalyst-additive blends were tested in a fixed bed
Table 1
Properties of vacuum gas oil (VGO)
Property Value
3 Initial temperature
Density (g/cm ) 0.882
API (8) 29.1
Carbon (wt.%) 85.08
Hydrogen (wt.%) 12.08
Sulfur (wt.%) 2.46
Nitrogen (ppm) 960
Initial boiling point (IBP) (8C) 214
Boiling point at 50% (8C) 428
Final boiling point (FBP) (8C) 588
117
MAT unit as per the ASTM method D3907. Detailed
experimental procedure has been given before [17]. The
catalyst-to-oil ratio was varied from 3 to 6 by changing the
amount of catalyst. One gram of feed was used and feed
injection time was 30 s. The reaction temperature in the MAT
experiments was 518 8C.
Gaseous product from MAT was analyzed using two
Shimadzu gas chromatographs (GC 17 A) equipped with
FID and TCD for quantitative determination of light hydro-
carbons up to C4 and fixed gases, respectively. Three different
liquid cuts were considered: gasoline (C5, 221 8C), LCO (light
cycle oil, 221–343 8C), and HCO (heavy cycle oil, +343 8C).
The weight percentage of these liquid products were
determined by a simulated distillation GC according to ASTM
D-2887 in order to calculate conversion and yield. The
conversion was defined as 100% less the weight percent of LCO
and HCO.
The total sulfur and the type of sulfur compounds present in
the gasoline fraction (C5-221 8C) of cracked VGO product were
determined in a GC, Chrompack 9001, attached to a sulfur
chemiluminescence detector (SCD) (Sievers model 355). The
sulfur detector provides high sensitivity with linear and
equimolar response over five orders of magnitude per sulfur
atom, while maintaining high selectivity for sulfur over
hydrocarbons. The GC is equipped with a back flushing valve
system at the inlet of the column. This system prevents very
high boiling point components form entering the column and
the detection system. The back flush valve timing was
optimized to only inject analytes boiling up to 221 8C.
Identification of a few sulfur compounds was done by matching
retention times of pure compounds and identification of
remaining compounds was done by matching the boiling
points. The internal standard method was used for quantifica-
tion. The GC conditions are presented in Table 2. The
conditions were optimized to obtain a fairly good resolution of
peaks.
3. Results and discussion
3.1. Activity
MAT conversion versus catalyst-to-oil ratio for base catalyst
and base-catalyst-additive blends is shown in Fig. 1. Higher
catalyst-to-oil ratios were needed for blends to achieve same
Table 2
SCD-Gas chromatograph conditions for sulfur analysis
Column
60 8C
Initial time 1 min
Heating rate 8 8C/min
Final temperature 220 8C
Injector temperature 300 8C
Detector temperature 800 8C
Carrier gas flow Helium, 5 cm3/min
Split ratio 1:10
Column type CP Sil-5CB SUL FS, 30 m long, 0.32 mm i.d.
118 M.A.B. Siddiqui et al. / Applied Catalysis A: General 303 (2006) 116–120
Fig. 1. Percent conversion vs. catalyst/oil ratio for Catalyst A, Catalyst A,
commercial-blend, Zn-blend, and Zn–Ga-blend.
conversion compared with base catalyst. At a catalyst/oil ratio
of 4.0, 71% conversion was achieved with base catalyst, 68%
with base-catalyst/Zn additive and base-catalyst/Ti additive and
64% with base-catalyst/Ga additive. Lower activity of base-
catalyst/additives compared with base-catalyst alone could be
due to dilution effect of additives.
Fig. 2 shows coke yield as a function of conversion for base
catalyst without additive and with additives. Coke yield was
lower, between conversion levels of 65–75%, with additives
compared with base catalyst, except with Ga additive. Higher
coke yields were observed for Ga because of higher reduction in
Fig. 2. Coke (wt.%) vs. percent conversion.
benzothiophene, which is the precursor of coke as per the
mechanism given by Corma et al. [16]. Lower coke yields were
expected as cracking activity was decreased with additive
blends. Coke yield would have been higher if the cracking
activity was not affected, as blending of additives would reduce
the zeolite content and increase matrix content of catalyst-
additive blend mixture. Matrix dominated catalyst are known to
yield more coke in MAT experiments [4].
3.2. Total gasoline sulfur
The sulfur content of FCC-gasoline obtained by MAT VGO
cracking with base catalyst was between 510 and 661 ppm.
With Ga additive, sulfur content was reduced to 432–562 ppm.
An increase in gasoline sulfur concentration with increasing
conversion was observed both for base catalyst and additive
blends, as shown in Fig. 3. As VGO conversion increases, more
sulfur compounds come into the gasoline fraction of cracked
VGO. These compounds cannot not be removed by additives in
quantities proportional to their increase.
Extent of gasoline sulfur reduction by a catalyst-additive
blend was determined by the difference in gasoline sulfur content
obtained by base catalyst without additive and that obtained by
base catalyst-additive blends. This sulfur reduction ability was
compared at a constant conversion of 70% to assess the
effectiveness of the prepared additives (Zn/alumina, Ti/alumina,
and Ga/alumina) in reducing gasoline sulfur. As shown in
Table 3, sulfur content of gasoline fraction was 656 ppm with
base catalyst and it was reduced to 474 ppm by Ti additive, to
543 ppm by Zn additive, and to 455 ppm by Ga additive. This
relates to 31% reduction in sulfur by Ga additive, 17% reduction
by Zn additive and 28% reduction by Ti additive. It is known
that Lewis acidity is responsible for reduction of sulfur.
Gallium provides stronger Lewis acidity than Zn and Ti and
hence its sulfur reduction ability was higher than Zn and Ti. It
Fig. 3. Gasoline sulfur content vs. percent conversion for Catalyst A, com-
mercial-blend, Zn-blend, and Zn–Ga-blend.
 M.A.B. Siddiqui et al. / Applied Catalysis A: General 303 (2006) 116–120 119

Table 3
Total gasoline sulfur and concentration of sulfur species (ppm) at 70% conversion
Base Ti-additive Zn-additive Ga-additive
Total gasoline sulfur (ppm) 656 474 543 455

Sulfur species (ppm)

Saturates 44 18 28 18
Thiophene (Th) + C1-Th 56 62 61 62
C2-thiophenes 44 42 47 41
C3-thiophenes 68 42 48 39
C4-thiophnes 170 34 89 61
Total C2–C4 thiophenes 282 118 184 141
Benzothiophene (BT) 288 272 269 272
%Reduction
Total gasoline sulfur (ppm) Base 28 17 31
Sulfur species (ppm)
Saturates Base 58 35 58
Thiophene (Th) + C1-Th Base 11 8 10
C2-Th Base 3.2 6.9 5.2
C3-Th Base 38 29 43
C4-Th Base 80 48 64
Total C2–C4-Th Base 58 35 50
Benzothiophene (BT) Base 5.5 6.6 5.6

was reported [8] that Lewis acid sites are located on alumina but
they are rendered active in the presence of Zn. Higher sulfur
reduction ability with Ga could be attributed to the existence of
Ga in tetrahedral coordination over the alumina sites [18],
which renders alumina sites more active.
3.3. Sulfur species
Different sulfur species present in FCC gasoline cut of
221 8C, were lumped into four groups [13]:
(1) saturates;
(2) thiophene (Th) + C1-thiophene;
(3) C2–C4 thiophenes (ethyl–butyl thiophene);
(4) benzothiophene.
Mercaptans, sulfides, disulfides and tetrahydrothiophene
comprise the group of saturates. C2–C4 thiophenes and benzo-
thiophene comprise a major portion of FCC gasoline sulfur. Th
and C1-Th are present in lower amounts. These groups of sulfur
species had different responses with the increase of conversion,
as shown in Fig. 4.
The concentration of saturates (Fig. 4A) decreased with
increased conversion while concentration of thiophene + C1
thiophenes (Fig. 4B) and benzothiophene (Fig. 4D) increased
with increased conversion.
As seen from Fig. 4B, concentration of thiophenes and
C1-thiophenes was higher when additive was used compared to
when no additive was used. Additive dealkylated C2–C4
thiophenes to thiophenes and C1-thiophenes, which could not
be saturated and cracked to H2S as fast as they were formed.
Generally, concentration of C2–C4 thiophenes (Fig. 4C)
increased and then decreased with increased conversion. C2–
C4 thiophenes were formed by dealkylation of side chains of
higher alkyl thiophenes and these were then further dealkylated
to C1-thiophenes. At lower conversion, rate of formation of
C2–C4 thiophenes was higher than the rate of its subsequent
dealkylation to C1-thiophenes, hence concentration of C2–C4
thiophenes increased. At higher conversion, rate of second step
of dealkylation seemed to be higher and hence C2–C4
thiophenes decreased. This behavior seems to that of a primary,
unstable product [15].
Table 3 lists concentration and percent reduction achieved at
a constant conversion of 70%, for base-catalyst and base-
catalyst-additive blends. About 60% of saturates were reduced
by Ti additive and Ga additive. Reduction of C2–C4 thiophenes
was highest with Ti additive (reduced by 58%) compared to
35% and 50% reduction by Zn and Ga additives, respectively.
Among C2–C4 Th, reduction of C4-Th (48–80%) was the
highest compared to C2-Th (3–5%) and C3-Th (29–43%). In
fact with Zn additive C2-Th content increased. Probably, alkyl
thiophenes are dealkylated sequentially, first C4-Th is
converted to C3-, C2-Th is converted to C2-Th and finally
C2-Th is converted to Th and C1-Th. With Zn additive, this
sequence did not go to completion and hence C2-Th content
was higher. Another reason for higher C2-Th content would be
deep cracking of heavier components, but no evidence was
gathered for either case.
Benzothiophene was the most difficult to remove. Only 5%
reduction in benzothiophene was achieved with all the three
additives. Benzothiophene undergoes mainly alkylation reac-
tions and yields heavier sulfur compounds that do not belong to
the gasoline range [16].
Thiophene + C1 thiophenes group was the least reactive. In
fact, its concentration increased with all three additives.
Probable reaction sequence for sulfur reduction involves [19]:
120 M.A.B. Siddiqui et al. / Applied Catalysis A: General 303 (2006) 116–120

Fig. 4. (A–D) Gasoline sulfur species concentration vs. percent conversion for Catalyst A, commercial-blend, Zn-blend, and Zn–Ga-blend.

(1) dealkylation of C2–C4 thiophenes to thiophenes + C1 in conducting this work. Analysis of sulfur done by Mr.
thiophenes; Khurshid Alam of KFUPM is also acknowledged.
(2) saturation of thiophene + C1 thiophene;
(3) cracking to H2S.
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