Applied Catalysis B: Environmental 42 (2003) 145–154

Effect of highly reactive sulfur species on sulfur

reduction in cracking gasoline
Francisco Hernández-Beltrán a,∗ , Roberto Quintana-Solórzano a ,
Jaime Sánchez-Valente a , Francisco Pedraza-Archila a , François Figueras b
aInstituto Mexicano del Petróleo, Eje Central L. Cárdenas 152, 07730 México, D.F., Mexico
b Institut de Recherche sur la Catalyse, 2 Avenue A. Einstein, 69626 Villeurbane Cédex, France
Received 29 March 2002; received in revised form 26 August 2002; accepted 28 August 2002

Abstract
Stringent regulations for engine fuels have stimulated R&D work for reducing sulfur in cracked naphtha in the recent years.
In order to progress in this issue information on the effect of the chemistry of sulfur compounds under cracking conditions
is needed. In this work, hexyl-2-thiol was spiked in a gasoil feed and the effect on sulfur in gasoline was studied with an
equilibrium catalyst (Ecat) and a commercial gasoline sulfur reduction additive. Spiked feeds showed lower conversion. The
hexyl-2-thiol mainly produced H2 S and exhibited a competitive reaction with sulfur compounds contained in gasoil. Higher
amounts of sulfur-in-coke were produced with the Ecat-additive blend compared to Ecat thus indicating that the hexyl-2-thiol
adsorbs stronger on the additive which can be due to its Lewis acid properties. While the additive moderates the detrimental
effect of hexyl-2-thiol on the catalyst activity its activity for sulfur reduction in gasoline was constrained.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: FCC; Sulfur in gasoline; Sulfur reducing additive; Thiophene; Benzothiophene; Alkylthiophenes; Sulfur-in-coke

1. Introduction 2005 has been set to 30 ppmw as a refinery average

Sulfur compounds in gasolines contribute to in-
crease SOx emissions in combustion gases produced
by automotive engines and poison the automotive cat-
alytic converters active metals thus lowering their effi-
ciency to reduce atmospheric pollutants such as NOx .
Among the increasingly stringent fuels specifications
that are being imposed in the US by the Tier II reg-
ulations for the following years, the concentration of
sulfur in commercial gasoline is focused with special
care. The upper limit of sulfur in gasoline in US for
∗ Corresponding author. Tel.: +52-3003-8539;
fax: +52-5003-8541.
E-mail address: fjhernan@imp.mx (F. Hernández-Beltrán).
[1–3]. Canada and the European Union have adopted
similar specifications. Moreover, the introduction of
“sulfur free fuels” (<10 ppmw S) have been proposed
in Europe for year 2007 [1,2].
Commercial gasolines are complex blends of
streams and products from several petrochemical and
refining processes. One of the major contributors to
the refinery gasoline pool is the fluid catalytic crack-
ing (FCC) [1] process with 35 vol.% average. The
FCC gasoline contributes to more than 90% to the
total gasoline pool sulfur content [1,3].
The amount and distribution of sulfur compounds
in the cracking products from FCC depends mainly
on the sulfur content and the type of feed [4–6]. Other
variables such as the type of catalyst and the operating

0926-3373/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 3 3 7 3 ( 0 2 ) 0 0 2 3 7 - 0
146 F. Hernández-Beltrán et al. / Applied Catalysis B: Environmental 42 (2003) 145–154

conditions [7] certainly have influence and especially transfer activity. A recent work [5] on the perfor-
they impact on economics. mance of a commercial sulfur reduction additive was
Roughly, up to 55% sulfur feed is converted to H2 S reported. Seemingly a feedstock that produced the
that is associated to the dry gas [7], while 5–10% sul- highest H2 S yield hindered the performance of the
fur feed is found in coke, which is converted to SOx additive which was related to a poisoning effect by
during regeneration of the catalyst [7–9]. Sulfur as H2 S. While the H2 S produced by cracking is associ-
mercaptans, thiophene, alkylthiophenes and benzoth- ated to non-thiophenic compounds we could wonder
iophene are found in cracked gasoline and represent on the role of this type of compounds in the chemistry
5–10% sulfur feed [6,7]. The balance to 100% corre- of sulfur reduction in gasoline. The aim of this work
sponds to sulfur compounds in heavier cuts such light is to contribute to the comprehension of the effect
cycle oil and heavy cycle oil. of highly reactive sulfur compounds by studying the
Stringent specifications that are currently set for cracking of gasoil feed spiked with hexyl-2-thiol and
engine fuels and the shortage of light and sweet using a commercial gasoline sulfur reduction additive
crudes have estimulated R&D work for developing blended with an equilibrium catalyst.
technologies that allow to reduce the sulfur content in
cracked naphtha in the recent years. Cost reduction
of gasoline desulphurization has been a crucial issue 2. Experimental
mainly if hydrogen becomes more expensive. There-
fore, a number of alternative process have been de- 2.1. Catalysts
veloped recently [1,10–15]. Hydrotreating feedstocks
or hydrodesulfurization of heavy fractions of gasoline A sample of equilibrium catalyst (Ecat) from an in-
[1,10] provide flexibility but usually are associated to dustrial FCC unit was used. The catalyst was com-
high capital costs or low return on investments [6]. posed of a rare earth partially exchanged USY zeolite
Extraction–hydrogenation [11], selective oxidation supported on a silica–alumina matrix. Prior to use the
[12], catalytic distillation [13] and selective adsorp- Ecat was sieved to 60–200 ␮m particle size and then
tion [14] are emerging technologies but still far from calcined for 4 h in static air at 550 ◦ C in order to burn
demonstrating their economic advantages. residual coke. Catalyst properties such as the unit cell
While using selective catalysts and/or additives in size (UCS), the total surface area and zeolite surface
the fluid catalytic cracking unit [3,6,15] could be the area (ZSA) were determined by the ASTM-D-3492,
most interesting solution from either the economical ASTM-D-3663 and ASTM-D-4222 methods, respec-
or operational standpoint, to date the commercially tively. These properties are presented in Table 1.
available products can only partially reduce the sul- A commercial gasoline sulfur reduction additive
fur content by 20–30%. This is explained by the fact GSR-1TM provided by Grace Davison was used. The
that the thiophenic compounds and benzothiophene
that represent up to 50–60% of the sulfur content in Table 1
cracked gasoline are aromatic species which are ex- Ecat properties
tremely difficult to react selectively over acid catalysts Properties Value
under the operating conditions of FCC.
RE2 O3 (wt.%) 1.55
In order to progress in this issue the chemistry of
Al2 O3 (wt.%) 32.3
sulfur compounds under cracking conditions must Total specific area (m2 /g) 160.5
be fully elucidated. In spite of the progress made Zeolite 122.9
there are still some unknown aspects on the reac- Matrix 37.6
tion mechanism of the sulfur compounds contained Zeolite/matrix area ratio 3.26
Pore volume (cm3 /g) 0.174
in cracking feedstocks. The reaction kinetics and
Nickel (ppm) 378
mechanism of sulfur compounds typically found in Vanadium (ppm) 1479
cracked gasoline have been recently studied [16,17]. Sodium (wt.%) 0.33
Other studies [5,18–20] pointed out the importance of UCSa (Å) 24.330
catalyst properties specially regarding the hydrogen a Unit cell size.
 F. Hernández-Beltrán et al. / Applied Catalysis B: Environmental 42 (2003) 145–154 147

properties of this additive are available elsewhere [5]. and SH2. The hexyl-2-thiol was selected as a sulfur
It essentially contains zinc oxide supported on alumina test molecule because of the facility for analysis by
as described in patent literature [15]. chromatography and its high cracking reactivity that
FTIR-pyridine adsorption was used to determine the produces higher amounts of H2 S. The amount of
types and quantity of acid sites. Pyridine adsorption hexyl-2-thiol added to BASE in order to generate SH1
was made in a Fourier transform infrared (FTIR) spec- and SH2 was 2.72 and 4.69 wt.%, respectively. Ac-
trometer Nicolet model 170-SX. FTIR spectra were cording to the GC analysis (see next section) the sul-
recorded on self-supported wafers which were acti- fur content in SH1 and SH2 was 2.47 and 2.95 wt.%,
vated by outgassing in a pyrex cell, with CaF2 win- respectively, compared to 2.01 wt.% in BASE.
dows, at 400 ◦ C under vacuum (1 × 10−6 Torr). After
this pretreatment, the samples were exposed to 100 ␮l 2.3. Reaction apparatus and products analysis
pyridine at room temperature for 20 min. After pump-
ing out the excess pyridine the infrared spectrum was The catalytic cracking reaction was carried out in an
recorded with the sample temperature fixed at room automated microreaction unit ACE-RTM from Kayser
temperature, 100, 200, 300 and 400 ◦ C. Technology-Xytel Corp, equipped with a fixed fluid
bed reactor. Details on the operating conditions and
2.2. Feedstocks the analytical methods used have been reported else-
where [5]. Basically, the conversion rate was changed
A typical blend of atmospheric and vacuum gasoils by varying the amount of feed fed at constant injec-
from Mexican Isthmus and Maya (70:30 (v/v)) crude tion rate. The catalyst to oil (cat-oil (w/w)) ratio varied
oils was used. This feed was coded as BASE and its between 3 and 7.5. The products obtained in the fixed
properties are reported in Table 2. fluid bed test were grouped in dry gas (H2 , C1 –C2 ),
BASE was spiked with hexyl-2-thiol (Aldrich, LPG (C3 –C4 ), gasoline (C5 + (−221 ◦ C)), light cycle
99% purity) thus producing two feeds coded SH1 oil (221–343 ◦ C), heavy cycle oil (>343 ◦ C) and coke
(deposited on catalyst). Regression analysis of data led
Table 2 to interpolate and compare yields at fixed conversion.
Properties of the BASE feed
The mass balance ranged from 97 to 101 wt.%, other-
Properties Value wise the run was discarded. Plots of product yield as
API 22.94 a function of the cat-oil ratio were drawn. The rela-
tive experimental error in the test was 0.6% for con-
ASTM D-1160 distillation
IBP (◦ C) 226 version, 0.7% for gasoline, 1.3% for LPG and 1% for
5/10 vol.% (◦ C) 322/361 coke and dry gas.
30/50 vol.% (◦ C) 408/432 The analysis of sulfur compounds in the feeds and in
70/90 vol.% (◦ C) 456/494 the liquid product was conducted by Gas Chromatog-
FBP (◦ C) 539
raphy using a 6890 Hewlett Packard GC-SimDis con-
Average boiling temperature (◦ C) 434 figured by Separation Systems Inc., equipped with a
Molecular weight (g/gmol) 387 chemiluminiscence detector Sievers SCD-355 as re-
Conradson carbon (wt.%) 0.11
Refraction index (0/20) 1.5131
ported elsewhere [5]. Details on the sulfur balance and
UOP K Factor 11.75 distribution into the reaction products can be found
Iron (ppm) 2.36 also in reference [5]. Sulfur conversion was expressed
Copper (ppm) <0.02 as the percentage of sulfur feed converted to a par-
Sodium (ppm) 0.38 ticular sulfur compound or product cut. The signal
Vanadium (ppm) 0.73
Nickel (ppm) 0.1
produced by the hexyl-2-thiol showed no overlapping
Sulfur (wt.%) 2.03 with signals attributed to other typical sulfur com-
Basic nitrogen (ppm) 400 pounds in cracked gasoline and thus its concentration
Carbon in aromatics (wt.%) 22.5 was easily calculated. This led to exclude the contri-
Carbon in naphthenics (wt.%) 17.0 bution of the hexyl-2-thiol remaining after cracking
Carbon in parafinics (wt.%) 60.5
from the sulfur in the gasoline balance.
148 F. Hernández-Beltrán et al. / Applied Catalysis B: Environmental 42 (2003) 145–154
Runs were duplicated in order to recover spent cat-
alysts to determine the sulfur content in coke using a
LECO SC-4444 analyzer with an IR detector follow-
ing the ASTM-D-1552 method. The sulfur contained
in the gas fraction was estimated by difference be-
tween the sulfur in feed and sulfur in liquid product
and coke, as has been reported [5].
In a first part of the study, a set of four experi-
ments was run: BASE feed with Ecat and Ecat-additive
blends at three levels (5, 10 and 15 wt.%) of additive.
This was equivalent to 0.45, 0.9 and 1.35 g additive in
9 g of total catalyst-additive inventory.
In a second set of experiments, the cracking of feeds
SH1 and SH2 was studied at 520 ◦ C. The performance
of the Ecat and an Ecat-additive (10 wt.%) blend were
compared. Again as in the first series, the cat-oil ratio
was varied (3, 4, 5, 6 and 7.5) in order to modify the
conversion rate.
3. Results and discussion
3.1. Pyridine adsorption on additive and Ecat
It is well documented that pyridine adsorbed over
acidic materials produce absorption bands in the
Fig. 1. FTIR spectra of pyridine adsorbed on (a) additive and (b) Ecat.
FTIR spectrum that are located between 1700 and
1400 cm−1 [21–23]. Absorption bands at 1640, 1540
and 1490 cm−1 are indicative of Brönsted acidity
while bands near 1620, 1580, 1490 and 1450 cm−1
are attributed to coordinately bound pyridine and thus
are indicative of Lewis acid sites. Absorption bands at
1450 and 1540 cm−1 are used for acidity characteri-
zation in acidic materials.
Fig. 1 presents the FTIR spectra for the additive (a)
and Ecat (b). The band at 1450 cm−1 due to Lewis
acid sites was comparatively much more intense in the
additive. This band remained at 400 ◦ C in the additive
while it completely vanished at ca. 200 ◦ C in Ecat.
Compared to Lewis acidity the Brönsted acidity was
much lower either for the additive or Ecat. The band at
1540 cm−1 disappeared already at 100 ◦ C in the addi-
tive while remained at somewhat higher temperature
in Ecat.
These results led to compare the amount of acid sites
in the solids and their relative strength. They clearly
showed that the additive exhibited much higher acid
site density compared to Ecat, the type of acidity being
Lewis of higher strength. The total amount of acid
sites varied between 293 and 70 ␮mol/g in the additive
from 50 to 400 ◦ C while total acidity at 100 ◦ C on the
additive was six-fold that (Brönsted + Lewis) in Ecat.
 F. Hernández-Beltrán et al. / Applied Catalysis B: Environmental 42 (2003) 145–154 149

Table 3
Fixed fluid bed data for Ecat and Ecat-additive blends at 74 wt.%
conversion (C/O, product yields, etc.)
Ecat Additivea (wt.%)

5 10 15

Cat-oil ratio (g/g) 3.68 2.94 3.22 3.89

Coke 5.45 5.48 6.20 6.74
Dry gas 2.16 2.28 2.34 2.40
Hydrogen 0.18 0.16 0.22 0.27
Methane 0.67 0.70 0.73 0.75
Gasoline 47.87 47.91 47.54 47.20
Bottoms selectivity 0.643 0.639 0.647 0.644
Light cycle oil 16.72 16.61 16.82 16.76 Fig. 2. Sulfur (%) from the feed converted for each level of addi-
LP gas 18.51 18.52 17.92 17.66 tive: BASE catalyst (䉬); 5 wt.% (䊏); 10 wt.% (䊉); and 15 wt.%
LP gas olefinicity 0.553 0.552 0.558 0.570 (䉱).
iC4 = /iC4 0.232 0.228 0.237 0.258
a GSR-1TM by Grace Davison. in Fig. 2. The conversion of sulfur feed increased
from 37 to 50 wt.% for the range (73–79 wt.%) of
feed conversion studied. Compared to Ecat, the con-
3.2. Effect of varying amounts of additive version of sulfur feed increased in ca. 3% using the
Ecat-additive blend with 5 and 10 wt.% additive while
Table 3 shows the fixed fluid bed test data obtained it showed no change when the additive percentage was
for Ecat and the Ecat-additive blends at constant 15 wt.%.
74 wt.% conversion of BASE feed. Compared to Ecat The distribution of sulfur throughout the cracking
alone, 5% and 10 wt.% additive decreased the cat- products (gasoline, coke, gas and cycle oils) at 74 wt.%
oil ratio needed to achieve the same conversion rate conversion for Ecat and Ecat-additive blends is pre-
while 15 wt.% additive showed no major difference. sented in Fig. 3a–d. Sulfur in gasoline (Fig. 3a) was
Table 3 shows also that the Ecat-additive blends 3.5% of the sulfur from the feed with Ecat and de-
produced higher yields of dry gas and coke and de- creased to 2.7% sulfur feed with 15 wt.% additive. The
creased LPG, while the gasoline yield and bottoms effect of the additive for sulfur reduction in gasoline
selectivity (defined as light cycle oil/[light cycle oil represented 10–23% depending on the percentage of
+ heavy cycle oil]) showed no major change com- additive used.
pared to Ecat. Within the range of feed conversion While the percentage of sulfur feed for the light
studied the overall coke yield was from ca. 5–8.5 wt.% cycle oil + heavy cycle oil fraction was almost con-
for Ecat to ca. 6–10 wt.% for Ecat-15 wt.% additive stant at 59% (Fig. 3b), very large variations from 6 to
blend. 23% and 15 to 33% of feed sulfur for sulfur-in-coke
These results showed that the additive increased (Fig. 3c) and H2 S (Fig. 3d), respectively were ob-
slightly the feed conversion rate and produced non- served. Higher sulfur-in-coke and lower sulfur as H2 S
selective cracking thus increasing dry gas and coke were observed as more additive was used in Ecat. This
yields. The effect was more important for the high- trend indicates that the additive has a very strong affin-
est percentage of additive used. These trends were ity for retaining sulfur compounds. In this sense, plots
already observed in previous studies [5] and were in Fig. 4a and b clearly show that the percent sul-
explained as an effect of a selective adsorption of fur feed in gasoline decreased at a much slower rate
the heaviest compounds contained in the feed on the than that related to the dry gas with the percent sul-
additive surface, thus allowing better accessibility on fur feed in coke (calculated for runs representing the
the catalyst surface of feed molecules undergoing extreme points in the cat-oil range studied). It is con-
cracking. cluded that the additive converts into coke such sulfur
The percent sulfur from the feed converted as a molecules contained in the feed that otherwise react
function of the overall feed conversion is presented to H2 S.
150 F. Hernández-Beltrán et al. / Applied Catalysis B: Environmental 42 (2003) 145–154

Fig. 3. Distribution of sulfur from the feed converted at 74 wt.% conversion for each level of additive: (a) gasoline, (b) light cycle oil
+ heavy cycle oil, (c) coke, and (d) gases (as H2 S).

3.3. Spiked feeds

The fixed fluid bed test data at 74 wt.% conver-

sion over Ecat are presented in Table 4. Compara-
tively, higher cat-oil ratios were required with spiked
feeds in order to produce the same feed conversion.
The coke yields were comparatively higher with feeds
SH1 and SH2 in 23 and 28%, respectively referred to
BASE. Less impact in the dry gas yield with 10 and
14% increase, respectively was observed. The gasoline
yield roughly decreased by 2% while the LPG yield

Table 4
Products yield (wt.%) for BASE and synthetic feeds at 74 wt.%
conversion
BASE SH1 SH2

Cat-oil ratio (g/g) 3.68 4.89 4.69

Coke 5.44 6.71 6.97
Dry gas 2.16 2.38 2.46
Hydrogen 0.18 0.21 0.19
Methane 0.67 0.75 0.77
Gasoline 47.9 47.0 46.9
Bottoms selectivity 0.643 0.638 0.627
Light cycle oil 16.72 16.60 16.29
LP gas 18.51 17.91 17.67
LP gas olefinicity 0.552 0.556 0.546
Fig. 4. Sulfur (%) from the feed in (a) gasoline, and (b) sulfur (%)
iC4 = /iC4 0.232 0.237 0.230
from the feed in dry gas, as a function of sulfur (%) feed in coke.
 F. Hernández-Beltrán et al. / Applied Catalysis B: Environmental 42 (2003) 145–154 151

Table 5
Products yield (wt.%) for BASE and synthetic feeds at 74 wt.%
conversion with catalyst and 10 wt.% of additive
BASE SH1 SH2

Cat-oil ratio (g/g) 3.23 3.89 3.98

Coke 6.21 6.59 6.77
Dry gas 2.34 2.29 2.45
Hydrogen 0.22 0.22 0.22
Methane 0.73 0.75 0.77
Gasoline 47.54 46.93 47.30
Bottoms selectivity 0.647 0.633 0.639
Light cycle oil 16.81 16.46 16.62
LP gas 17.91 18.09 17.47
LP gas olefinicity 0.557 0.558 0.557
iC4 = /iC4 0.237 0.241 0.242

was lower in 3–4.5% for SH1 and SH2, respectively.

The bottoms selectivity (light cycle oil/[light cycle oil
+ heavy cycle oil]) which leads to qualify the activity
to heavy fractions cracking was slightly lower while
no major changes in LPG olefinicity (the relative C3 =
and C4 = content) were observed.
The Ecat-additive blend exhibited a similar trend
in catalytic activity and product distribution (Table 5)
as previously observed but with much lower intensity.
The coke yield increased only in 6 and 9% for SH1,
SH2, respectively while the dry gas, LPG and gasoline
yields showed only slight differences.
Calculation from product analysis showed that more
than 95 wt.% hexyl-2-thiol reacted in the fixed fluid
Fig. 5. Sulfur (%) from the feed in gasoil at 74 wt.% conversion
bed test. Due to the acidic nature of the catalyst and re- using BASE feed and spiked feeds: (a) light cycle oil + heavy
action conditions it was expected that the hexyl-2-thiol cycle oil, (b) gasoline, (c) coke; dark bars: Ecat alone; light bars:
increased the C3 ’s yields due to the hexyl substitu- Ecat-additive (10 wt.%) blend.
ant undergoing cracking according to the well known
mechanism of ␤-scission in the carbocation chem-
istry [24]. However, no changes in LPG yield or the BASE. Sulfur in cycle oils from BASE increased
olefinicity ratio were observed thus leading to exclude slightly when the additive was used. This trend was
a major contribution from this reaction either in Ecat or already reported [5] and attributed to the formation
the Ecat-additive blend. By contrast, the hexyl-2-thiol of alkyl-benzothiophenes by the additive. However,
increased significantly the coke make (Tables 4 and 5) the additive showed a different effect with spiked
thus indicating a great tendency to promote dehydro- feeds. With SH2 a reduction from 71 to 68% of
genation. feed sulfur in cycle oils was observed while essen-
Fig. 5a–c show the sulfur distribution in the crack- tially no effect on sulfur reduction was observed for
ing products (at 74 wt.% feed conversion) produced SH1.
from BASE and the spiked feeds with Ecat and the The percentage of sulfur feed going into gasoline
Ecat-additive blend. The percentage of sulfur feed increased from 3.5% with BASE to 4.0 and 4.2% with
in cycle oils (light cycle oil and heavy cycle oil) SH1 and SH2, respectively (Fig. 5b). Gasoline sulfur
was higher with spiked feeds (Fig. 5a) compared to reduction due to the additive was equivalent to 20%
152 F. Hernández-Beltrán et al. / Applied Catalysis B: Environmental 42 (2003) 145–154
for BASE while it decreased to 12% with SH1 and
was negligible with SH2.
The percentage of sulfur feed in coke almost dou-
bled in Ecat with spiked feeds compared to BASE
(Fig. 5c). However, this represented only a small per-
centage of sulfur produced from hexyl-2-thiol. The
amount of sulfur as hexyl-2-thiol that was injected in
the fixed fluid bed tests trough the spiked feeds de-
pended on the cat-oil ratio and varied between 8.4
and 36.2 mg S for cat-oil = 7.5 and 3, respectively.
The sulfur recovered in coke varied between 2.7 and
4.6 mg S for the same cat-oil range. The difference of
this sulfur-in-coke to the one produced with BASE
(2.1–2.6 mg S) led to calculate that a maximum of
10.5% sulfur from the hexyl-2-thiol ended up associ-
ated to coke in Ecat.
The additive increased further the percentage of
feed sulfur deposited in coke. In this case, the amount
of sulfur-in-coke at cat-oil = 3 and feed SH2 in-
creased from 4.3 mg S for Ecat to 7.2 mg S for the
Ecat-additive blend which is equivalent to 8% incre-
mental over Ecat alone.
The hexyl-2-thiol exhibited a detrimental effect on
the catalyst activity. The results led us to conclude
that a competitive reaction between hexyl-2-thiol
and heavier sulfur molecules contained in the gasoil
takes place. The hexyl-2-thiol actually decreased the
conversion of other sulfur molecules thus increasing
the sulfur content in cycle oils (Fig. 5a). The smaller
molecule size of hexyl-2-thiol compared to bulkier
sulfur molecules found in the gasoil feed could ex-
plain this behavior.
The additive helped to mitigate the poisoning ef-
fect the hexyl-2-thiol had over the catalyst but with
a detrimental effect upon its activity for sulfur reduc-
tion. The positive effect of the additive on the catalyst
activity was clearly observed with the Ecat-additive
5 wt.% blend while for higher percentages of additive
the conversion dropped probably due to dilution of the
catalyst.
H1 MASNMR studies [25] showed that the adsorp-
tion of H2 S over alumina can occur either in asso-
ciative or dissociative forms, the latter taking place
over coordinatively unsaturated Al sites—strong acid
pairs. The adsorption of hexyl-2-thiol on Ecat could
take place over zeolite extraframework aluminum or
alumina contained in the catalyst matrix with impli-
cations over the Ecat activity. It has been suggested
that Lewis sites are responsible for initiating crack-
ing reactions [26]. Assuming that the hexyl-2-thiol
molecule adsorbs on Lewis acid sites on Ecat it would
very probably hinder the catalyst activity and paral-
lely increasing the coke make. It could be suggested
that the hexyl-2-thiol preferentially adsorbs over the
additive compared to Ecat due to the higher density
and strength of Lewis acid sites of the former.
The hexyl-2-thiol could dissociate either in (a) RS−
+ H+ or (b) SH− + R+ (R = C6 H13 ). The former
would explain the increase in coke make and sulfur-in-
coke while the latter explains the increase in H2 S and
thus it would be the preferred one. Contribution of
(a) needs to be suppressed in order to progress in the
performance of sulfur reduction materials. Further
studies are necessary in order to elucidate the adsorp-
tion mode of hexyl-2-thiol and other reactive sulfur
species over alumina based catalysts.
Several mechanisms could account for the increase
in sulfur in gasoline observed with spiked feeds. A di-
rect contribution of hexyl-2-thiol can be ruled out since
the balance calculation excluded it. Thus, the conver-
sion of thiophenic compounds in the gasoline could be
hindered due to the competitive adsorption of hexyl-2-
thiol and coke poisoning over the acid sites in the
catalyst. Another possibility is that olefins produced
during the cracking reactions could react further with
H2 S and generate thiophenic compounds as already
suggested [16,17]. Because of the secondary charac-
ter of this reaction the thiophenic compounds would
increase at higher feed conversion. Since this was not
the observed trend we can conclude that at least this
reaction is not dominant. However, it is possible that
hexyl-2-thiol reacts by cyclization-dehydrogenation
thus producing C2 alkylthiophene. This implies that
the adsorption form a) RS− + H+ occurs. Analysis
of the distribution of thiophenic product showed that
in fact, the increase of the sulfur content in gasoline
was mostly due to C1 –C2 thiophene (Fig. 6).
Likely, a much lower gasoline sulfur reduction ac-
tivity was obtained with the additive when a Maya
gasoil was reacted over the Ecat (10%) additive blend
compared to a sweeter gasoil blend [5]. This effect
was related to a poisoning effect of H2 S that was pro-
duced in higher proportion with Maya gasoil. Addi-
tive pre-sulfiding with H2 S produced the complete loss
of activity for sulfur reduction thus supporting this
conclusion.
 F. Hernández-Beltrán et al. / Applied Catalysis B: Environmental 42 (2003) 145–154
Fig. 6. Sulfur (%) from the feed converted into alkylthiophenes as
a function of percent feed converted: (a) C1 -alkylthiophenes, (b)
C2 -alkylthiophenes. (䊏) BASE, (䊉) SH1 (䉱) SH2; full symbols:
Ecat alone, void symbols: Ecat-additive (10 wt.%) blends.
Nevertheless, the results obtained in this work sug-
gest that there is another possibility for explaining the
higher amounts of sulfur-in-gasoline produced from
Maya gasoil. Non-thiophenic sulfur molecules con-
tained in higher amounts in such a feed could pro-
duce the same effect as observed with hexyl-2-thiol in
the present case. Therefore, while the H2 S effect still
remains, the presence of non-thiophenic sulfur com-
pounds in the feed could affect negatively by increas-
ing the coke make, lowering the catalyst activity and
increasing the sulfur in gasoline as already reported
[5]. In line with this, the additive performance is con-
strained as well.
4. Conclusions
Our results showed that a reactive sulfur molecule
such as hexane-thiol hinders the conversion of sul-
153
fur compounds contained in a gasoil. The main ef-
fect is to poison the catalyst activity and thus to in-
crease the sulfur content in gasoline and cycle oils. The
zinc–alumina sulfur reduction additive moderates such
an effect. Due to its Lewis acidity properties the addi-
tive selectively adsorbed the hexyl-2-thiol molecule.
The cracking activity of the catalyst-additive system
improved but the particular activity of the additive for
sulfur removal from gasoline was constrained.
This work led to add knowledge on the reaction pat-
tern of sulfur compounds during gasoil cracking. The
effect produced by the hexyl-2-thiol in spiked feeds
studied here could be extrapolated to non-thiophenic
molecules contained in industrial feeds, like those
derived from Maya crude oil. Non-thiophenic com-
pounds could be responsible for reducing the activity
of cracking catalysts and to increase the coke make.
Moreover, it could be suggested that some of the
adsorbed species produced thiophenic compounds in
the gasoline range.
Our results point out that designing selective ma-
terials for sulfur reduction in cracking gasoline needs
to consider properties that could hinder the formation
of sulfur species by cyclization–dehydrogenation re-
actions from thiols and mercaptanes.
Acknowledgements
The authors are indebted to the Maya Crude Oil
Research Program (Instituto Mexicano del Petroleo),
project D.01024, for financial support. We thank Dr. E.
Lopez Salinas for reviewing the manuscript and fruit-
ful discussions. We deeply acknowledge J. Navarrete
and R.I. Conde for running FTIR experiments.
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