Beruflich Dokumente
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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
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
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.
⁎ 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
Fig. 2 – FT-IR spectra of [Ga]AlY and NH4Y zeolites. Fig. 4 – Effect of temperature on the sulfur adsorption capacity
over the [Ga]AlY (stirring time: 2 h; model fuel 1/adsorbent
(1.72 Å), implying that the Ga atoms have been introduced into weight = 14).
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 adsorption is leveled off after 6 h of the continuous stirring,
analysis showed that the aluminium content decreases from indicating that all adsorption sites have been saturated. The
11.9% for the NH4Y to 8.8% for the [Ga]AlY. While the gallium sulfur content in the effluent after 6 h is about 18.9 μg/g.
content of [Ga]AlY is 4.32%. The results of ICP indicate further With temperature increasing, the adsorption desulfurizai-
that Ga has been substituted into the faujasitic framework. ton of model fuel 1 on [Ga]AlY is improved slightly (sulfur
Fig. 2 shows the FT-IR spectra of [Ga]AlY zeolites and NH4Y. removal from 92% to 97%), and the adsorption capacity
The internal tetrahedral symmetrical stretching shows a blue increased only from 6.4 to 7.0 mg(S)/g adsorbent (Fig. 4).
shift due to the substitution Ga for Al [15]. These results illustrate that the temperature is less important
for the desulfurization performance.
3.2. Effect of stirring time and temperature
3.3. Comparison of adsorption desulfurizaiton on NH4Y
Effect of stirring time and temperature on the sulfur content and [Ga]AlY
and sulfur adsorption capacity over the [Ga]AlY are shown in
Figs. 3 and 4. The results indicate that most of the sulfur Fig. 5 shows the breakthrough curves for the adsorptive
compounds are removed within 20 min at which the sulfur desulfurization of model fuel 1 over the NH4Y or [Ga]AlY. For
adsorption capacity is 5.7 mg(S)/g adsorbent. The sulfur a breakthrough point of 15 μg/g, the breakthrough volume and
adsorption capacity increases only to about 6.8 mg(S)/g breakthrough capacity for the NH4Y at ambient conditions are
adsorbent with increasing time up to 6 h. The sulfur about 2.9 ml/g of adsorbent and 1.0 mg of sulfur/g of
Fig. 3 – Effect of stirring time on the sulfur adsorption capacity Fig. 5 – Breakthrough curves for the desulfurization of model
over the [Ga]AlY (temperature: 60 °C; model fuel 1/adsorbent fuel 1 over NH4Y and [Ga]AlY (ambient conditions; liquid
weight = 14). 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 Fig. 8 – Breakthrough curves for the desulfurization of model
model fuels over (conditions are the same as Fig. 5). fuels over the [Ga]AlY (conditions are the same as Fig. 5).
adsorbent, respectively. While for the [Ga]AlY, these data are Effect of olefin and arenes on the adsorption desulfurization
about 20.1 ml/g of adsorbent and 7.0 mg of sulfur/g of (Fig. 8) demonstrates that [Ga]AlY may form π complexation
adsorbent, respectively, indicating that the adsorptive desul- with benzene and 1,5-hexadiene. Since thiophene has a pair of
furization of the [Ga]AlY has been enhanced pronouncedly. electrons in the plane of the ring, it could be possible to form a
These results can be ascribed to the incorporation of Ga into direct S–M bond and π complexation simultaneously between
zeolite Y leading to an increase of Lewis acid [3] which can the adsorption sites and thiophene. In such case, the adsorp-
enhance the capacity of thiophene. tion of thiophene should be stronger than that of THT because
of the simultaneous involvement of the two types of bonding
3.4. Adsorption desulfurization of different model fuels on interactios. The breakthrough capacity of THT is, however,
[Ga]AlY higher than that of thiophene, which can be attributed to the
different charges on S atom of the sulfur containing com-
The breakthrough curves for the adsorptive desulfurization of pounds. The charges on S atom of thiophene, 4,6-DMDBT and
the different model fuels over the [Ga]AlY are presented in THT, calculated by using density functional theory (DFT), were
Fig. 6. At ambient conditions, the breakthrough capacities for −0.159, −0.214 and −0.298, respectively, implying that the S–M
the adsorption of model fuel 1, 2 and 3 are 7.0, 17.4 and 14.5 mg bond between the adsorption site and thiophene is much
of sulfur/g of adsorbent, respectively. R.T. Yang [10] had found weaker than those between the adsorption sites and THT or 4,6-
that Cu+ and Ag+ zeolite Y adsorbed thiophene derivatives from DMDBT. These results indicate that the S–M interactions
commercial fuels by π complexation. The π complexation could between the adsorption sites and the sulfur containing
be also formed between the Ga3+ and thiophene as the compounds play a more important role on the adsorption
electronic configuration of Ga3+ is the same as that of Cu+. desulfurization than the π complexation interactions. The
Fig. 7 – Effect of stirring time on the outlet sulfur content over Fig. 9 – Breakthrough curves for the desulfurization of model
the [Ga]AlY (conditions are the same as Fig. 3). 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 5
(5) The [Ga]AlY can be regenerated under an atmosphere of [4] J. Dwyer, K. Karim, J. Chem. Soc., Chem. Commun. 14 (1991)
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[5] S. Mikhail, T. Zaki, L. Khalil, Appl. Catal., A Gen. 227 (2002)
original capacity.
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[6] Scoot G. McKinley, Robert J. Angelici, Chem. Commun. (2003)
2620–2621.
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[8] Arturo J. Hernández-Maldonado, Ind. Eng. Chem. Res. 42
(2003) 123–129.
We thank the National Natural Science Foundation of China
[9] Arturo J. Hernández-Maldonado, Frances H. Yang, Gongshin
(No. 20476042) for the financial support.
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.
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