F U EL P RO CE S S IN G TE CH N O L O GY 8 9 ( 2 0 08 ) 1–6

w w w. e l s e v i e r. c o m / l o c a t e / f u p r o c

Deep desulfurization by selective adsorption on a heteroatoms

zeolite prepared by secondary synthesis

Ke Tang, Li-juan Song, Lin-hai Duan, Xiu-qi Li, Jian-zhou Gui, Zhao-lin Sun⁎
College of Petrochemical Engineering, Liaoning University of Petroleum & Chemical Technology, Fushun 113001, Liaoning Province, PR China

AR TIC LE I N FO ABS TR ACT

Article history: Gallium atoms have been introduced into the framework of Y zeolite by treating the zeolite
Received 8 December 2006 with an aqueous solution of ammonium hexafluoro gallate. Desulfurization of various
Received in revised form 28 May 2007 model fuels containing about 500 μg/g sulfur were studied over the synthesized Y zeolite
Accepted 13 June 2007 ([Ga]AlY) with a liquid hourly space velocity of 7.2 h− 1 at ambient conditions. The sulfur
adsorption capacity was 7.0, 14.5, and 17.4 mg(S)/g adsorbent for thiophene, 4,6-
Keywords: dimethyldibenzothiophene (4,6-DMDBT), and tetrahydrothiophene (THT), respectively.
Isomorphous substitution The charges on S atom in thiophene, 4,6-DMDBT and THT, calculated by using density
Heteroatom zeolite functional theory (DFT), are −0.159, −0.214 and − 0.298, respectively, implying that the S–M
DFT bond between the adsorption sites and thiophene is much weaker than that between the
Model fuels adsorption sites and THT or 4,6-DMDBT.
Adsorption desulfurization © 2007 Elsevier B.V. All rights reserved.

1. Introduction that remain in the transportation fuels are mainly benzothio-

Heteroatom-substituted zeolites have been received increas-
ing interest recently. It has been shown that the introduction
of different heteroatoms into the framework of zeolites leads
to different catalytic and adsorption properties. The heteroat-
om zeolite is usually synthesized by using hydrothermal
crystallization which have some disadvantages. In 1985,
Deceased et al. [1] firstly reported that Si atom was incorpo-
rated into faujastic framework by applying the isomorphous
substitution method using NH4SiF6 solution to improve the
acidities, adsorption and catalytic properties of the deal-
uminated products. Recent years, some heteroatoms such as
Ti, Te, Cr, Zr, Ga [2–4] have been incorporated into the
framework of zeolites by using this secondary synthesis
technique.
Since sulfur in transportation fuels remains a major source
of air pollution, the sulfur concentration in the transportation
fuels should preferably be ultra-low. The sulfur compounds
phene, dibenzothiophene, and their derivatives due to the
hydrodesulfuriaztion (HDS) process is less effective for these
derivatives. Adsorption desulfurization is a new and highly
efficient method to remove sulfur compounds from the
transportation fuels. In addition, adsorption desulfurization
can be accomplished relatively at lower pressure and
temperature even at ambient conditions. Some kinds of
adsorbents have been reported for the removal of sulfur
compounds from the diesel fuel, gasoline, jet fuel or model
fuels. Many works have focused on the porous materials such
as charcoal [5], mesoporous SBA-15 [6], metal cation ex-
changed microporous zeolites [7–12] and transition metal
compound supported on a porous silica gel [13]. But adsorp-
tion desulfurization by using heteroatom zeolite has not been
reported. In this paper, the introduction of heteroatom
gallium into the framework of a Y zeolite by the isomorphous
substitution method has been reported and the desulfuriza-
tion of various model fuels containing about 500 μg/g sulfur

⁎ Corresponding author. Tel.: +86 413 6860048; fax: +86 413 6860658.
E-mail address: zlsun@lnpu.edu.cn (Z. Sun).

0378-3820/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2007.06.002
2 F U EL P RO CE S SI N G TE CH N O L O G Y 8 9 ( 2 00 8 ) 1–6

Table 1 – Composition of model fuels used 2.3. Adsorbent characterizations

No. Concentration (μg/g) Sulfur
content The XRD patterns were acquired on a D/Max-RD type
Thiophene THT 4,6- 1,5- Benzene (μg/g) diffractometer system (Rigaku, Japan) equipped with mono-
DMDBT hexadiene
chromatic CuKα radiation.
1 1312.5 – – – – 500 The IR was performed on a spectrum™ GX IR spectrometer
2 – 1375 – – – 500 (Perkin-Elmer, USA) using the nujol mull or KBr method.
3 – – 3312.5 – – 500
The sulfur content of model fuels was measured by the
4 – 1375 – 500 – 500
WK-2D coulombmeter (Jiangfen Electroanalytical Instrument
5 – 1375 – – 500 500
Co., Ltd, China).
The metal content of [Ga]AlY and NH4Y was measured by a
MS X7 type inductively coupled plasma spectrometer (Thermo
over the synthesized Y zeolite was studied at ambient Elemental, USA).
conditions.
2.4. Adsorptive desulfurization

2. Experimental The adsorption experiments were carried out by using static

stirring or in a fixed-bed flow reactor. For the static adsorption
2.1. Model fuels studies, the model fuels and adsorbents were conducted with
a mass ratio of 14:1 in a flask with a magnetic stirrer. After
In order to investigate which kinds of interactions, the direct stirring certain time, the adsorbents were separated by
S–M interactions or π-complex formation, are involved in the filtration and the sulfur content of the treated model fuels
adsorption of thiophenic sulfur compounds on the synthe- was measured by the WK-2D coulombmeter.
sized Y zeolite, several kinds of model fuels containing known The adsorptive desulfurization was also performed using a
amounts of thiophene, THT or 4,6-DMDBT as sulfur com- flow apparatus. A thin layer of glass fiber was used as the guard
pounds in n-nonane with a total sulfur concentration of bed that supported the adsorbents of the main bed. The
500 μg/g were prepared. The composition of the model fuels adsorbents were packed in a quartz tube with an internal
was summarized in Table 1. diameter of 6 mm and length of 350 mm. The volume of the
adsorbent bed was about 0.23 ml. The model fuel was fed into
2.2. Adsorbent preparation the column using a piston pump. The fuels after treatment were
collected periodically and analyzed using the method men-
Zeolite Y used in this study was synthesized by adding tioned above. The breakthrough volume and breakthrough
NaOH, NaAlO2 and silica gel at a stoichiometry of 4.3Na2O: capacity were calculated from the breakthrough curves consid-
Al2O3:10SiO2:200H2O with vigorous agitation. The synthesis ering the breakthrough point of 15 μg/g.
gel was decanted into a teflon-lined autoclave and left to age
at 25 °C for 24 h. The autoclave was then heated to 100 °C to
promote crystallization for 24 h. The sample was afterward 3. Results and discussion
washed with doubly distilled water, dried and the zeolite Y
with a Si/Al molar ratio of 2.45 was obtained. An aqueous 3.1. Adsorbent characterizations
solution of NH4Cl (2M) was used to the ion-exchange of the
zeolite Y to obtain NH4Y zeolite. The cell parameter of [Ga]AlY, determined by XRD using the
The synthesis of [Ga]AlY zeolite could be refered to internal standard method, is 24.756 Å and that of NH4Y is
literature [4,14]. The NH4Y zeolite was stirred with ammoni- 24.685 Å as the result of replacing Al–O (1.69 Å) with Ga–O
um acetate solution (1 mol/L). The slurry (5 g zeolite to 50 ml
solution) was then heated to the reaction temperature (75 °C)
and the solution of gallium nitrate and ammonium fluoride
was added over a period of 3–5 h.
The products were filtered and washed in an ammonium
sulphate solution (1.5 mol/L) at 80 °C for 1.5 h using a ratio of
solid to solution of 1:10. The washing process was repeated to
remove the fluoride. The products were then dried at 100 °C
and calcined at 500 °C for 5 h to remove the adsorbed water
before using in the adsorption experiments.
NH4Y zeolite is used as the support to obtain GaF3–NH4Y.
NH4Y zeolite and GaF3 are mixed and pestled uniformly. After
calcined at 400 °C for 12 h, GaF3–NH4Y is obtained.
The regenerative way of [Ga]AlY zeolite are as follow.
Firstly, the second-hand [Ga]AlY zeolite is sweeped under an
atmosphere of air at 300 °C, followed by reactivation under
nitrogen at 350 °C. Fig. 1 – XRD spectra of [Ga]AlY and NH4Y zeolites.
 F U EL P RO CE S S IN G TE CH N O L O GY 8 9 ( 2 0 08 ) 1–6
Fig. 2 – FT-IR spectra of [Ga]AlY and NH4Y zeolites.
(1.72 Å), implying that the Ga atoms have been introduced into
the framework of Y zeolite. The XRD pattern of [Ga]AlY agrees
well with that of raw material NH4Y, as shown in Fig. 1,
indicating that the crystallinity of [Ga]AlY keeps unchanged. ICP
analysis showed that the aluminium content decreases from
11.9% for the NH4Y to 8.8% for the [Ga]AlY. While the gallium
content of [Ga]AlY is 4.32%. The results of ICP indicate further
that Ga has been substituted into the faujasitic framework.
Fig. 2 shows the FT-IR spectra of [Ga]AlY zeolites and NH4Y.
The internal tetrahedral symmetrical stretching shows a blue
shift due to the substitution Ga for Al [15].
3.2. Effect of stirring time and temperature
Effect of stirring time and temperature on the sulfur content
and sulfur adsorption capacity over the [Ga]AlY are shown in
Figs. 3 and 4. The results indicate that most of the sulfur
compounds are removed within 20 min at which the sulfur
adsorption capacity is 5.7 mg(S)/g adsorbent. The sulfur
adsorption capacity increases only to about 6.8 mg(S)/g
adsorbent with increasing time up to 6 h. The sulfur
Fig. 3 – Effect of stirring time on the sulfur adsorption capacity
over the [Ga]AlY (temperature: 60 °C; model fuel 1/adsorbent
weight = 14).
3
Fig. 4 – Effect of temperature on the sulfur adsorption capacity
over the [Ga]AlY (stirring time: 2 h; model fuel 1/adsorbent
weight = 14).
adsorption is leveled off after 6 h of the continuous stirring,
indicating that all adsorption sites have been saturated. The
sulfur content in the effluent after 6 h is about 18.9 μg/g.
With temperature increasing, the adsorption desulfurizai-
ton of model fuel 1 on [Ga]AlY is improved slightly (sulfur
removal from 92% to 97%), and the adsorption capacity
increased only from 6.4 to 7.0 mg(S)/g adsorbent (Fig. 4).
These results illustrate that the temperature is less important
for the desulfurization performance.
3.3. Comparison of adsorption desulfurizaiton on NH4Y
and [Ga]AlY
Fig. 5 shows the breakthrough curves for the adsorptive
desulfurization of model fuel 1 over the NH4Y or [Ga]AlY. For
a breakthrough point of 15 μg/g, the breakthrough volume and
breakthrough capacity for the NH4Y at ambient conditions are
about 2.9 ml/g of adsorbent and 1.0 mg of sulfur/g of
Fig. 5 – Breakthrough curves for the desulfurization of model
fuel 1 over NH4Y and [Ga]AlY (ambient conditions; liquid
hourly space velocity: 7.2 h− 1).
4 F U EL P RO CE S SI N G TE CH N O L O G Y 8 9 ( 2 00 8 ) 1–6
Fig. 6 – Breakthrough curves for the desulfurization of different
model fuels over (conditions are the same as Fig. 5).
adsorbent, respectively. While for the [Ga]AlY, these data are
about 20.1 ml/g of adsorbent and 7.0 mg of sulfur/g of
adsorbent, respectively, indicating that the adsorptive desul-
furization of the [Ga]AlY has been enhanced pronouncedly.
These results can be ascribed to the incorporation of Ga into
zeolite Y leading to an increase of Lewis acid [3] which can
enhance the capacity of thiophene.
3.4. Adsorption desulfurization of different model fuels on
[Ga]AlY
The breakthrough curves for the adsorptive desulfurization of
the different model fuels over the [Ga]AlY are presented in
Fig. 6. At ambient conditions, the breakthrough capacities for
the adsorption of model fuel 1, 2 and 3 are 7.0, 17.4 and 14.5 mg
of sulfur/g of adsorbent, respectively. R.T. Yang [10] had found
that Cu+ and Ag+ zeolite Y adsorbed thiophene derivatives from
commercial fuels by π complexation. The π complexation could
be also formed between the Ga3+ and thiophene as the
electronic configuration of Ga3+ is the same as that of Cu+.
Fig. 7 – Effect of stirring time on the outlet sulfur content over
the [Ga]AlY (conditions are the same as Fig. 3).
Fig. 8 – Breakthrough curves for the desulfurization of model
fuels over the [Ga]AlY (conditions are the same as Fig. 5).
Effect of olefin and arenes on the adsorption desulfurization
(Fig. 8) demonstrates that [Ga]AlY may form π complexation
with benzene and 1,5-hexadiene. Since thiophene has a pair of
electrons in the plane of the ring, it could be possible to form a
direct S–M bond and π complexation simultaneously between
the adsorption sites and thiophene. In such case, the adsorp-
tion of thiophene should be stronger than that of THT because
of the simultaneous involvement of the two types of bonding
interactios. The breakthrough capacity of THT is, however,
higher than that of thiophene, which can be attributed to the
different charges on S atom of the sulfur containing com-
pounds. The charges on S atom of thiophene, 4,6-DMDBT and
THT, calculated by using density functional theory (DFT), were
−0.159, −0.214 and −0.298, respectively, implying that the S–M
bond between the adsorption site and thiophene is much
weaker than those between the adsorption sites and THT or 4,6-
DMDBT. These results indicate that the S–M interactions
between the adsorption sites and the sulfur containing
compounds play a more important role on the adsorption
desulfurization than the π complexation interactions. The
Fig. 9 – Breakthrough curves for the desulfurization of model
fuel 1 over (ambient conditions).
 F U EL P RO CE S S IN G TE CH N O L O GY 8 9 ( 2 0 08 ) 1–6
steric hinderation of the methyl groups of 4,6-DMDBT is also
less important compared with the S–M interactions, which can
be justified by the fact that the adsorption rate of 4,6-DMDBT is
faster than that of thiophene (Fig. 7).
3.5. Effect of olefin and arenes on the adsorption
desulfurization
Fig. 8 showed breakthrough curves for desulfurization of
model fuels containing THT on the [Ga]AlY at ambient
conditions. Pronounced effect of 1.5-hexadiene or benzene
on the breakthrough capacity of THT can be found. Compared
with the adsorption capacity of model fuel 2, adsorption
capacity of model fuel 4 and 5 decreased remarkably (5.4 and
7.4 mg of sulfur/g of adsorbent, respectively), indicating that
1.5-hexadiene or benzene may also occupy some adsorption
sites by forming π complexation with the adsorption sites.
3.6. Effect of liquid hourly space velocity (LHSV)
Fig. 9 shows the results collected at three different LHSV of
11.4, 7.2 and 2.5 h− 1. The breakthrough capacities are 3.0, 7.0
and 6.8 mg of sulfur/g of adsorbent, respectively. The lower
breakthrough capacity obtained at a LHSV of 11.4 h− 1 com-
pared to those obtained at the LHSV of 7.2 and 2.5 h− 1 can be
ascribed to the lower residence time of 5 min instead of 0.14
and 0.4 h. It is worth noting that the breakthrough capacities at
7.2 and 2.5 h− 1 are nearly equivalent, implying that the
residence time for a LHSV of 7.2 is adequate.
3.7. Comparison of GaF3–NH4Y and [Ga]AlY
At ambient conditions and a LHSV of 7.2 h− 1, the breakthrough
curves for the adsorptive desulfurization of model fuel 1 over
the GaF3–NH4Y and the [Ga]AlY are shown in Fig. 10. The
breakthrough volume and breakthrough capacity for the GaF3–
NH4Y are about 3.8 ml/g of adsorbent and 1.3 mg of sulfur/g of
adsorbent, which are much smaller than those for the [Ga]AlY.
These findings can be attributed to the different conditions of
the gallium in GaF3–NH4Y and [Ga]AlY.
Fig. 10 – Breakthrough curves for the desulfurization of model
fuel 1 over (conditions are the same as Fig. 5).
5
Fig. 11 – Breakthrough curves for the desulfurization of model
fuel 1 over fresh and regenerated [Ga]AlY (adsorbent
regenerated in air at 300 °C for 3 h, followed by reactivation in
nitrogen at 350 °C for 2 h. Conditions are the same as Fig. 5).
3.8. Regeneration of [Ga]AlY
Fig. 11 shows breakthrough curves after the [Ga]AlY adsorbent
was regenerated. The regenerated adsorbent recovered almost
all of the original capacity. For this case, the observed
saturation capacity is about 17.1 ml/g of adsorbent and
6.0 mg of sulfur/g of adsorbent, which is only a 15% reduction
from the original capacity. Regeneration under air returned
the adsorbent capacity to the original capacity, indicating that
the adsorbed thiophene molecules are eliminated through
combustion.
4. Conclusions
(1) Gallium atoms have been introduced into the frame-
work of Y zeolite. The cell parameter of [Ga]AlY
increases from 24.685 Å of NH4Y to 24.756 Å.
(2) At ambient conditions, the breakthrough capacity
for the adsorption of thiophene, THT and 4,6-DMDBT
are 7.0, 17.4 and 14.5 mg of sulfur/g of adsorbent,
respectively. The charges on S atom of thiophene,
4,6-DMDBT and THT, calculated by using density func-
tional theory (DFT), are − 0.159, − 0.214 and − 0.298,
respectively. Implying that the S–M bond between
the adsorption site and thiophene is much weaker
than that between the adsorption site and THT or
4,6-DMDBT. These results indicating that the S–M in-
teractions between the adsorption sites and the sulfur
containing compounds play a more important role on
the adsorption desulfurization than the π complexa-
tion interactions.
(3) Effect of olefin and arenes on the adsorption desulfur-
ization are notable. This is because 1.5-hexadiene or
benzene can occupy some adsorption sites by forming π
complexation.
(4) The influence of LHSV on the breakthrough capacity is
evident when the LHSV is higher than 7.2 h− 1.
6 F U EL P RO CE S SI N G TE CH N O L O G Y 8 9 ( 2 00 8 ) 1–6
(5) The [Ga]AlY can be regenerated under an atmosphere of
air. The regenerated adsorbent recovers about 85%
original capacity.
Acknowledgements
We thank the National Natural Science Foundation of China
(No. 20476042) for the financial support.
REFERENCES
[1] D. Breck, G.W. Skeels, Silicon substituted zeolite
compositions and process for preparing same. U.S. Patent,
4503023 (1985).
[2] Y. Tang, J.S. Xu, Z. Gao, Chem. J. Chin. Univ. 11 (12) (1990)
1317–1321 (in Chinese).
[3] Z.L. Xu, Y.Z. Zhang, L.B. Zheng, J. Mol. Catal. (China) 6 (4) (1992)
271–278 (in Chinese).
[4] J. Dwyer, K. Karim, J. Chem. Soc., Chem. Commun. 14 (1991)
905–906.
[5] S. Mikhail, T. Zaki, L. Khalil, Appl. Catal., A Gen. 227 (2002)
265–278.
[6] Scoot G. McKinley, Robert J. Angelici, Chem. Commun. (2003)
2620–2621.
[7] AbuBakr S.H. Salem, Ind. Eng. Chem. Res. 33 (1994) 336–340.
[8] Arturo J. Hernández-Maldonado, Ind. Eng. Chem. Res. 42
(2003) 123–129.
[9] Arturo J. Hernández-Maldonado, Frances H. Yang, Gongshin
Qi, Ralph T. Yang, Appl. Catal., B Environ. 56 (2005) 111–126.
[10] Ralph T. Yang, Arturo J. Herández-Maldonado, Frances H.
Yang, Science 301 (2003) 79–81.
[11] S. Velu, X.L. Ma, C.S. Song, Ind. Eng. Chem. Res. 42 (2003)
5293–5304.
[12] X.L. Ma, S. Velu, J.H. Kim, C.S. Song, Appl. Catal., B Environ. 56
(2005) 137–147.
[13] X.L. Ma, L. Sun, C.S. Song, Catal. Today 77 (2002) 107–116.
[14] R. David, K. Khalid, D. John. U.S. Patent 5238675 (1993).
[15] R.R. Xu, W.Q. Pang, Chemistry—Zeolites and Porous
Materials, Science Press, Bei Jing, 2004, pp. 173–174,
(in Chinese).