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a
Process Development Division, Egyptian Petroleum Research Institute, Nasr City, P.O. Box 9540, Cairo 11787, Egypt
b
Petroleum Refining Division, Egyptian Petroleum Research Institute, Nasr City, P.O. Box 9540, Cairo 11787, Egypt
KEYWORDS Abstract H-ZSM-5 zeolite catalysts were doped with 2%, 3% and 4%HF to be used for investi-
HZSM-5; gating their activities and selectivities for xylenes production and for para-xylene maximization at
Disproportionation; temperatures of 300–500 C via toluene disproportionation. This doping caused pore size modifica-
Toluene; tion of the H-ZSM-5 catalyst. The reaction was carried out in a fixed bed flow type reactor. The
Hydrofluorination; ratio of produced para-xylene relative to its thermodynamic composition reached as high as 3.29
Para-xylene at 300 C on the 4%HF doped H-ZSM-5 catalyst although this catalyst possessed the lowest
amount of the largest pores (3.0–5.7 nm) and the smallest pores (0.4–1.7 nm). The overall activities
of the catalysts were decreased with an increase in HF doping because of diffusion restriction. The
kinetics of the reaction were simply treated and found to give Ea and DS* values compatible with the
characterization data of the catalysts.
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Moreover, xylenes isomerize in the zeolitic pores simulta- 20 cm3 min1. The liquid product was collected and analyzed
neously and the products diffuse out of the pores at different by gas chromatography using a column packed with 5% Ben-
rates [14,16,17]. tone-34 plus 5% diisodecyl phthalate supported on Chromo-
The incorporation of fluorine in oxide catalysts enhances sorb-W (Resteck Corp., USA).
their activities for acid catalyzed hydrocarbon reactions [18–
20]. Fluoride ion is assumed to replace surface O or OH; be- 2.3. Temperature programmed desorption of ammonia (TPDA)
cause fluorine is more electronegative than these groups; it re-
places and increases the polarity of the lattice, thereby The TPDA procedure using differential scanning calorimetry
increasing the acidity and activity of the surface. Lok et al. (DSC) for detecting and evaluating the desorption of pre-
[21] have found that the treatment of zeolites with diluted fluo- sorbed ammonia from the catalysts via programmed tempera-
rine gas affected the samples in a manner dependent on the ture increase was carried out in an inert atmosphere [29,30].
severity of fluorination. Becker and Kowalak studied the mod- Accordingly, ammonia was adsorbed on the acid sites of the
ification of H-mordenite with ammonium fluoride solutions catalyst after previous heating in air flow at 500 C for 3 h in
and gaseous CHF3 [22]. The H-ZSM-5 zeolites exhibit en- a silica tube furnace. After cooling to 50 C, ammonia gas flow
hanced Brönsted acidity and therefore improved the catalytic of 50 cm3 min1 was applied over the evacuated catalyst. The
activity after treatment with various fluorine-containing com- DSC measurements were then carried out in a DSC-30 unit
pounds [23–25]. Ghosh and Kydd [26] have found that the of the TA-3000 Mettler system (Germany) using standard Al
treatment of mordenite catalysts with dilute HF (60.25 M) crucibles in a flow of 50 cm3 min1 oxygen-free nitrogen purge
does not damage the zeolitic structure of mordenite. Elemental gas. The DSC conditions were as follows: temperature, 50–
analysis shows that small amounts of fluorine are incorpo- 600 C; heating rate, 5 C/min; sample mass; 10 mg. The
rated, and aluminum is leached from the samples. Treatment desorption enthalpy obtained corresponds to the acid site den-
with more concentrated HF (1.5 M) causes silicon to be re- sity whereas the DSC peak temperature was used to compare
moved from the zeolitic structure and decreases slightly the the acid site strength. Two DSC endothermic peaks appear
size of the unit cell. With larger volumes of more concentrated in each thermogram; the lower temperature peak corresponds
HF, the surface area was found to be substantially reduced. to desorption of the weak acid sites and the higher temperature
The incorporation of small amounts of fluoride enhances both peak corresponds to desorption of the strong acid sites respon-
the Brönsted and Lewis acidity, but in different ways; it en- sible for catalyzing the reaction under study. The higher the
hances strong Lewis acidity and weak Brönsted acidity. desorption peak temperature, the higher the acid site strength.
Recently the authors have investigated the alkylation of toluene
with methanol using hydrofluorinated H-ZSM-5 zeolites [27] and 2.4. Surface analysis
hydrofluorinated Pt/H-ZSM-5 [28] catalysts to maximize para-xy-
lene. In the present communication, disproportionation of toluene
BET total surface area, and total pore volume were determined
on hydrofluorinated H-ZSM-5 zeolite catalysts is studied.
from nitrogen adsorption/desorption isotherms measured at
196 C, using Quatachrome NovaWin2 apparatus. The pore
2. Experimental
width distribution was calculated from these data using the
DFT method.
2.1. Catalysts preparation
Figure 5 X/Xe values during toluene disproportionation for: (4) para-xylene; (h) meta-xylene; (¤) ortho-xylene; using: (a) untreated H-
ZSM-5; (b) H-ZSM-5(2%HF); (c) H-ZSM-5(3%HF); (d) H-ZSM-5(4%HF) catalysts.
kb T DH DS
k¼ e RT e R ð3Þ
h
The Ea values obtained for catalysts doped with 2%, 3%
and 4%HF amount to 17.54, 12.63 and 9.73 kJ mol1, respec-
tively. This sequential decrease of Ea is attributed to a sequen-
tial increase of diffusion restriction in the channels of the
zeolite. The markedly lower value of Ea using the unloaded
H-ZSM-5 catalyst is attributed to the higher value of rate con-
stant of the current reaction both at lower and higher temper-
atures, such that at the higher temperatures the kinetics are
limited by thermodynamic equilibrium (Fig. 6).
Indeed, the Ea values in Table 3 are relatively low, indicat-
ing that the temperature has a modest effect in accelerating the
current reaction. The difference between the catalytic re-
sponses of these three catalysts toward HF doping is very
slight but exhibiting a decreasing trend with increasing HF
concentration in the catalyst. This indicates that the increase Figure 6 Arrhenius plot for disproportionation of toluene using:
of amorphous debris formed via leaching Al and Si in the zeo- (s) untreated H-ZSM-5; (4) H-ZSM-5(2%HF); (d) H-ZSM-
lite composition is slightly effective on the physical structure of 5(3%HF); (m) H-ZSM-5(4%HF) catalysts.
the porous system of these catalysts. The activation entropy
(DS*) values calculated for xylenes production using the
current catalysts show insignificantly different values. In significant molecular restriction during adsorption and reac-
general, these values reflect that this reaction encounters a tion of the activated state in the zeolitic channels.
124 A.K. Aboul-Gheit et al.
[10] M.A. Uguina, J.L. Sotelo, D.P. Serrano, Ind. Eng. Chem. Res.
Table 3 Activation parameters for the disproportionation of 32 (1993) 49–55.
toluene reaction using the current. [11] J. Das, Y.S. Bhat, A.B. Halgeri, Ind. Eng. Chem. Res. 33 (1994)
Catalysts Ea (kJ mol1) DS* (eu) 246–250.
[12] T. Kunieda, J. Kim, M. Niwa, J. Catal. 188 (1999) 431–433.
Untreated H-ZSM-5 4.5 79.86
[13] E.F. Vansant, Pore Size Engineering in Zeolite, Wiley,
H-ZSM-5(2%HF) 17.54 75.45
Chichester, UK, 1990.
H-ZSM-5(3%HF) 12.63 77.59
[14] D.H. Olson, W.O. Haag, ACS Symp. Ser. 248 (1984) 275–
H-ZSM-5(4%HF) 10.37 80.53
307.
[15] W.W. Kaeding, G.C. Basile, M.M. Wu, Cat. Rev. Sci. Eng. 26
(1984) 597–612.
[16] W.W. Kaeding, C. Chu, L.B. Young, S.A. Butter, J. Catal. 69
4. Conclusion
(69) (1981) 392–398.
[17] P.B. Weisz, Pure Appl. Chem. 52 (1980) 2091–2103.
Although the activities of toluene disproportionation reaction [18] A.K. Ghosh, P. Harvey, U.S. Patent, 7, 105, 713 B2 (2006).
decrease with increasing HF doping concentration, the selec- [19] A.K. Ghosh, R.A. Kydd, Catal. Rev. Sci. Eng. 27 (1985) 539–
tivity for para-xylene production increases. HF leaches Al 589.
and Si forming fine debris which is deposited in the wide cat- [20] V.R. Choudhury, Ind. Eng. Chem. Prod. Res. Dev. 16 (1977)
12–22.
alytic pores (3.0–5.7 nm) leading to decrease in the number
[21] B.M. Lok, F.P. Gortsema, C.A. Messina, H. Rastelli, T.P.J.
of wider pores and transferring them to intermediate pores
Izod, ACS Symp. Ser. 218 (1983) 41–58.
of 1.7–3.0 nm width. This pore size modification leads to max- [22] K.A. Becker, S. Kowalak, J. Chem. Soc. Faraday Trans. I (81)
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The 4%HF doped catalyst produces 3.29, 0.27 and 0.31 times [23] R. Le Van Mao, T.S. Le, M. Fairbairn, A. Muntasar, S. Xiao,
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thermodynamic equilibrium values at 300 C. The process ap- [24] J.N. Miale, C.D. Chang, U.S. Patents (a) 4,427,786 (1984), (b)
pears in general to be grouped under pore engineering effec- 4,427,787 (1984), (c) 4,427,788 (1984), (d) 4,427,789 (1984), (e)
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