2010 Chinese Journal of Catalysis Vol. 31 No.

10

Article ID: 0253-9837(2010)10-1209-08 DOI: 10.1016/S1872-2067(10)60113-1 Article: 12091216

Para-Xylene Maximization
Part VIII: Promotion of H-ZSM-5 Zeolite by Pt and HF Doping for
Use as Catalysts in Toluene Alkylation with Methanol
Ahmed K. ABOUL-GHEIT1,*, Ateyya A. ABOUL-ENEIN1, Ahmed E. AWADALLAH1,
Salwa A. GHONEIM1, Eman A. EMAM2
1
Process Development Division, Egyptian Petroleum Research Institute, Nasr City, PO Box 9540, Cairo 11787, Egypt
2
Department of Petroleum Refining and Chemical Engineering, College of Petroleum and Mining Engineering,
Suez Canal University, Suez, Egypt

Abstract: Toluene was alkylated with methanol in a flow type reactor at temperatures between 300 and 500 C using H-ZSM-5 zeolite,
0.2%Pt/H-ZSM-5 and hydrofluorinated 0.2%Pt/H-ZSM-5 with HF concentrations of 1.0%, 2.0%, 3.0%, or 4.0%. Pt primarily enhances
toluene conversion, total xylenes production, and p-xylene relative to its thermodynamic equilibrium. As the concentration of HF increases
from 1.0% to 3.0%, the catalyst activity increases because of the increase in the number of acid sites and their strength. Additionally, the
surface area and Pt dispersion also increases. An advantage of increased HF doping is that the formation of voluminous trimethylbenzene
(TMB) byproducts is inhibited. However, at a HF concentration of 4.0%, Al and Si are partially leached and then deposited mostly in the
wider catalytic pores. This was determined by evaluating the pore volume distribution and we determined that reactivity inhibition was ob-
viously present and was due to diffusion restriction.
Key words: methanol; toluene; alkylation; platinum; hydrofluorination; shape-selectivity; ZSM-5
CLC number: O643 Document code: A

There is considerable industrial demand for para-xylene
because it is a raw material in the production of terephthalic
acid, which is a major component in the production of
polyester fibers. Additionally, polyethylene terephthalate
resins, vitamins, and other pharmaceuticals also require
terephthalic acid. The methylation of toluene has been car-
ried out over several acidic zeolites such as ZSM-5, mor-
denite, SAPO-11, and Y zeolites. It has been found that the
catalytic activity and selectivity differs greatly among these
zeolites. Aboul-Gheit et al. [13] investigated the alkylation
of toluene with methanol using H-ZSM-5 zeolite and this
reaction was promoted by a noble metal (Pt) to stabilize and
activate carbonium ion formation, which is necessary for the
alkylation reaction. However, modification of the acidity of
H-ZSM-5 may affect the pore structure of the zeolite and
the co-reactions can be effectively restricted, and the selec-
tivity for para-xylene improved [4,5]. Zhao et al. [6] re-
ported that H-ZSM-5 zeolite loaded with strongly hydro-
genating metals (Pt, Pd, Co, Ni) exhibit excellent stability,
high activity, and p-selectivity.
The modification of H-ZSM-5 using fluoride treatment
has been used to promote acid catalyzed reactions [7]. The
fluoride ion is assumed to replace surface oxide or hydrox-
ide groups and because fluorine is very electronegative, it
polarizes the framework, which increases the acidity and
reactivity of the surface. Because zeolites are inherently
more acidic than aluminas, far fewer reports have appeared
in the literature on the effect of fluoride treatment on zeo-
lites. However, it has been pointed out that fluoride treat-
ment by various means increases both the activity and sta-
bility of some important siliceous zeolites such as ZSM-5.
Becker et al. [8] reported the modification of H-mordenite
with ammonium fluoride solutions and gaseous CHF3. Pat-
ents exist about high-silica pentasil zeolites that exhibit
enhanced Brnsted acidity and therefore improved catalytic
activity after treatment with various fluorine-containing
compounds [9,10]. The hydrofluorination of mordenite has
been reported by Ghosh et al. [11] who found that aqueous
HF treatment of this zeolite results in the leaching of a por-
tion of aluminum under mild conditions. Silicon is leached
under more severe conditions from the zeolite structure as
well.
In this work, 0.2%Pt/H-ZSM-5 doped with 0, 1%, 2%,
3%, and 4% HF was investigated as a catalyst for toluene
alkylation with methanol in a flow reactor at temperatures
of 300500 C to maximize para-xylene formation.

Received date: 26 March 2010.

*Corresponding author. Tel: +20-2-22729100; Fax: +20-2-22747433; E-mail: aboulgheit2000@hotmail.com
English edition available online at ScienceDirect (http://www.sciencedirect.com/science/journal/18722067).
1210
1 Experimental
1.1 Catalyst preparation
Sodium ZSM-5 zeolite (Si/Al = 25) in powder form was
kindly supplied by Sd-Chemie AG, Germany. It was trans-
formed to the ammonium form by cation exchange using a
molar solution of NH4NO3 over five repetitions of 8 h each
using fresh solutions of NH4NO3 at 70 C under reflux and
stirring. The zeolite was then separated from the solution,
washed thoroughly with distilled water, dried overnight at
110 C, and calcined at 530 C for 4 h to obtain the
H-ZSM-5 zeolite.
A catalyst containing 0.2%Pt was prepared by impreg-
nating the H-ZSM-5 zeolite with an aqueous solution con-
taining the required amount of chloroplatinic acid
(H2PtCl66H2O). To this was added a small quantity of citric
acid to assist deep Pt penetration into the support [12,13].
The catalyst was dried overnight at 110 C, calcined in a
muffle furnace at 530 C for 4 h in air and then reduced in
the catalytic reactor in a flow of dry hydrogen at 20 cm3/min
for 8 h.
Four hydrofluorinated catalysts, H-ZSM-5 (1%HF),
H-ZSM-5 (2%HF), H-ZSM-5 (3%HF), and H-ZSM-5
(4%HF) were prepared by doping H-ZSM-5 with 1%, 2%,
3%, and 4% HF, respectively, followed by drying overnight
at 110 C and calcination at 450 C for 4 h. These hydro-
fluorinated catalysts were impregnated with an aqueous
solution of H2PtCl66H2O to which was added a small quan-
tity of citric acid as described above. The catalysts were
then washed, dried, calcined, and reduced as above to obtain
the 0.2%Pt/H-ZSM-5(HF) catalysts.
1.2 Alkylation procedure and apparatus
The catalytic runs were carried out at atmospheric pres-
sure in a fixed-bed down-flow reactor. The alkylation runs
were carried out at reaction temperatures between 300 and
500 C, a space velocity of 2.6 h1, and a continuous hydro-
gen flow of 20 cm3/min. One gram of the catalyst powder
was diluted with inert porcelain particles then placed in the
reactor tube. A mixture of methanol and toluene (molar ratio
2.5:1) was fed into the reactor and the product was cooled in
a condenser at 3 C and then passed into a receiver. The
liquid and gaseous products were analyzed by gas chroma-
tography using a column packed with 5% Bentone 34 and
5% diisodecylphthalate supported on Chromosorb W
(Resteck Corp., USA).
Percentage gaseous product = 100 percentage liquid
product. Toluene conversion = (Ti T0)/Ti, where Ti is the
weight of toluene feed to the reactor and T0 is the weight of
unreacted toluene. Para-xylene selectivity = para-xylene
Chin. J. Catal., 2010, 31: 12091216
percentage in product/total xylenes in product.
1.3 Catalyst characterization
The surface properties (area and pore volume distribu-
tion) were determined by conventional BET nitrogen ad-
sorption-desorption using a Quantachrome NovaWin2
(Nova 3200, USA) apparatus. The pore volume distribution
relationships were calculated by applying the DFT differen-
tial method through plotting the pore volume vs. pore width,
as derived from the N2 adsorption-desorption isotherms at
196 C. The catalyst samples were primarily pretreated via
degassing for 18 h at 350 C.
The temperature-programmed desorption of ammonia
(TPDA) procedure using differential scanning calorimetry
(DSC) for detecting and evaluating the desorption of pre-
sorbed ammonia from the catalysts via programmed tem-
perature increase was carried out in an inert atmosphere
[14,15]. Accordingly, Ammonia was adsorbed on the acid
sites of the catalyst after previous heating in air flow at 500
C for 3 h in a silica tube furnace. After cooling to 50 C,
ammonia gas flow of 50 cm3/min was applied over the
evacuated catalyst. The DSC measurements were then car-
ried out in a DSC-30 unit of the TA-3000 Mettler system
(Germany) using standard Al crucibles in a flow of 50
cm3/min oxygen-free nitrogen purge gas. The DSC condi-
tions were as follows: temperature, 50600 C; heating rate,
5 C/min; full scale range, 30 mW; plot, 10 cm; sample
mass; 10 mg.
The desorption enthalpy obtained corresponds to the acid
site density whereas the DSC peak temperature was used to
compare the acid site strength. Two DSC endothermic peaks
appear in each thermogram; the lower temperature peak
corresponds to desorption of weak acid sites that are not
involved in catalysis and the higher temperature peak cor-
responds to desorption of the strong acid sites responsible
for catalyzing the reaction under study. The higher the de-
sorption peak temperature, the higher the acid site strength.
The dispersion of platinum in the support (metal fraction
exposed) was determined by hydrogen chemisorption using
a pulse technique based on that described by Freel [16]. A
specific amount of calcined catalyst was heated in the
chemisorption furnace at 500 C for 1 h in a flow of 50
cm3/min ultrapure hydrogen. The flow was then replaced
with oxygen-free nitrogen at 30 cm3/min for 2 h at 500 C
(degassing). The furnace was shut off and the catalyst was
cooled to room temperature. Hydrogen was then injected
into the nitrogen carrier until saturated (appearance of hy-
drogen peaks equivalent to the complete volume of injected
pulses). Hydrogen uptake was calculated as hydrogen atoms
adsorbed per total metal atoms on the basis of 1:1
stoichiometry [17].
www.chxb.cn Ahmed K. ABOUL-GHEIT et al.: Para-Xylene Maximization-Part VIII: Promotion of H-ZSM-5 Zeolite 1211

2 Results and discussion

65
2.1 Toluene conversion 60

55
Traditionally, toluene alkylation is an acid catalyzed reac-

Toluene conversion (%)

tion and, therefore, the acid sites provided by the H-ZSM-5 50
zeolite support in the current catalysts are necessary for 45
carbonium ion formation. However, the use of platinum as
an active metal component dispersed on the catalytic sur- 40
0.2%Pt/H-ZSM-5(4%HF)
face results in alkylation enhancement because it assists the 35 0.2%Pt/H-ZSM-5(3%HF)
stabilization of the carbonium ion that forms on the acid 0.2%Pt/H-ZSM-5(2%HF)
30
sites. This occurs because of a decrease in the rate of the 0.2%Pt/H-ZSM-5(1%HF)
backward decomposition to reform methanol and toluene. 25 0.2%Pt/H-ZSM-5
Untreated H-ZSM-5
Alkylation is enhanced because of the activity of the plati- 20
num atoms which possess vacant electron d-orbitals. 350 300 400 450 500
Aboul-Gheit et al. [3] investigated the performance of a Reaction temperature (oC)
Fig. 1. Toluene conversion during alkylation with methanol using
series of catalysts containing varying Pt content (0.1%,
H-ZSM-5 and 0.2%Pt/H-ZSM-5 treated with HF.
0.2%, or 0.3%) loaded on H-ZSM-5 zeolite for toluene me-
thylation with methanol. Para-xylene production and
catalyst can, therefore, be considered to be the most active.
para-xylene selectivity was found to increase with an in-
The increase in acid concentration increased the acid
crease in the Pt content. Although diffusion restriction in the
strength and this effectively increased the activity towards
catalytic pores of these catalysts increases with an increase
toluene conversion. Furthermore, this increase in acid con-
in the Pt content, the activation energy of toluene methyla-
centration assisted in increasing the dispersion of Pt in the
tion increased and the activation entropy became less nega-
zeolites (Table 1). On the contrary, a further increase in HF
tive. This indicates that activation of the current reaction via
doping to 4% causes a significant decrease in activity at
successive Pt occlusion up to 0.3% over-compensated the
higher temperatures. This can be attributed to the leaching
diffusion restriction effect.
of some structural aluminum and perhaps silicon in the zeo-
HF doping on the zeolite surface is accomplished by
litic structure of H-ZSM-5. The leached materials are de-
modifying the acidity of the catalyst through increasing or
posited in the form of fluoro-alumino and fluoro-silico spe-
decreasing the number of acid sites and/or the acid strength.
cies in the zeolite channels and this causes diffusion restric-
The H-ZSM-5 zeolite is better than the other zeolites be-
tion, which is an effect that appears at higher temperatures
cause of its channel dimension (0.5 nm), which preferen-
since the diffusion rate greatly decreases relative to the rate
tially admits the diffusion and reaction of toluene with ad-
of the chemical reaction at high temperatures so that the
sorbed methanol. This enhances para-xylene selectively by
diffusion process becomes rate controlling. With 4% HF
eliminating the production of ortho- and meta-xylenes be-
acid treatment, the number of acid sites and the Pt disper-
cause they have larger diameters.
sion (Table 1) decreases and the surface area as well as pore
In this work, we determined the extent of H-ZSM-5 zeo-
structure is altered.
lite promotion with 0.2% Pt as well as promotion by 0.2%
The pore volume distribution curves for the untreated
Pt and HF of 1.0%, 2.0%, 3.0%, or 4.0%. Figure 1 shows
H-ZSM-5 zeolite and the 0.2%Pt/H-ZSM-5 catalyst are
that the total conversion of toluene increases by incorporat-
shown in Fig. 2(a). The larger pores have a pore width range
ing 0.2% Pt into the H-ZSM-5 zeolite to a significant extent
at all reaction temperatures but, particularly, at higher tem- Table 1 Ammonia desorption enthalpy (Hdes), peak temperature
peratures between 400 and 500 C. Doping the (Tp), Pt dispersion, and BET surface area (ABET) for the 0.2%Pt/H-
0.2%Pt/H-ZSM-5 catalyst with 1% HF further increased the ZSM-5 catalyst and its hydrofluorinated versions
activity (total conversion) at higher temperatures (450500 TPD of ammonia Pt dispersion ABET/
Catalyst
C). A further increase of HF to 2% resulted in a further Hdes/(J/g) Tp/C (%) (m2/g)
increase in activity particularly in the lower temperature Untreated H-ZSM-5 105.1 380 345
range (300350 C). This change of temperature region 0.2%Pt/H-ZSM-5 78.2 372 67 338
activation can be attributed to the heterogeneous distribution 0.2%Pt/H-ZSM-5(1%HF) 100.5 373 68 345
of the active sites in the catalyst, i.e., Pt sites and acid sites. 0.2%Pt/H-ZSM-5(2%HF) 104.6 376 70 348
0.2%Pt/H-ZSM-5(3%HF) 100.0 378 72 348
However, a further increase in the acid to 3% HF resulted in
0.2%Pt/H-ZSM-5(4%HF) 96.1 381 66 322
a significant increase in activity at all temperatures and this
1212 Chin. J. Catal., 2010, 31: 12091216

0.020
(a) (b)
0.016
Pore volume (cm3/g)

Untreated H-ZSM-5 0.2%Pt/H-ZSM-5(2%HF)

0.012
0.2%Pt/H-ZSM-5 0.2%Pt/H-ZSM-5(3%HF)
0.2%Pt/H-ZSM-5(4%HF)
0.008

0.004

0.000
0 1 2 3 4 5 0 1 2 3 4 5 6
Pore width (nm) Pore width (nm)
Fig. 2. Pore volume distribution by the DFT differential method for different samples.

of 2.25.7 nm in the as-synthesized H-ZSM-5 zeolite and gion (0.32.7 nm) have the highest values. This is evidently
they are larger than those in the 0.2%Pt/H-ZSM-5 catalyst. attributed to the filling of most of the large pores by the
There is no significant difference between the volume dis- debris formed through the highly activated leaching of Al
tribution of the fine pores in the 02.2 nm width range. Ob- and Si at the highest HF concentration (4%).
viously, the larger pores of the unloaded zeolites are more The behavior of xylenes production (Fig. 3) shows some
unoccupied. similarity to the behavior of the other products during tolu-
Figure 2(b), on the other hand, shows that the pore vol- ene conversion (Fig. 1) with respect to the modifications
ume distribution curves obtained for the catalysts containing applied in this work, i.e., the incorporation of 0.2%Pt and
0.2%Pt/H-ZSM-5 treated with 2% and 3% HF exhibit simi- doping with HF from 1% to 4%.
lar behavior and they match those shown in Fig. 2(a). Also, Apart from the main intended reaction, i.e., the alkylation
the 1% HF treated 0.2%Pt/H-ZSM-5 catalyst (not shown in of toluene to produce xylenes (ortho-, meta-, and para-xy-
Fig. 2(b) to exclude overlap and complexity) gives more or lene), we found that physically larger products such as
less similar behavior to the 2% and 3% HF treated catalysts. trimethylbenzenes (TMB) and smaller products such as
Nevertheless, for the 0.2%Pt/H-ZSM-5 catalyst treated with benzene and hydrocarbon gases were obtained. Benzene
4% HF significantly different behavior is evident. For this formation, however, is insignificant at yields up to 3.9% at
catalyst, the large pores in the distribution curve (in the 500 C over the hydrofluorinated catalysts. Benzene is
range 2.75.5 nm) have the lowest values among all the HF formed by toluene hydrodealkylation and methane is also
treated catalysts (almost zero) whereas the finer pores re- produced (Eq. (1)). Moreover, the disproportionation of two
molecules of toluene produces one benzene molecule and
50 one xylene molecule (Eq. (2)).
0.2%Pt/H-ZSM-5(4%HF)
0.2%Pt/H-ZSM-5(3%HF) CH3 CH3
45 0.2%Pt/H-ZSM-5(2%HF)
0.2%Pt/H-ZSM-5(1%HF) + CH3OH + H2O (1)
Total xylenes in product (%)

0.2%Pt/H-ZSM-5
40
Untreated H-ZSM-5 CH3
CH3 CH3
35
2 + (2)

30 CH3

25 2.1.1 Side reactions during toluene methylation

20 In this work, we used unloaded H-ZSM-5 as a catalyst

300 350 400 450 500 and ethylbenzene does not form whereas on 0.2%Pt/H-
Reaction temperature (oC) ZSM-5 and its hydrofluorinated versions, ethylbenzene is
Fig. 3. Total xylenes in the products during the alkylation of toluene obtained in trace amounts. Moreover, ethyltoluenes are ob-
with methanol using H-ZSM-5 and 0.2%Pt/H-ZSM-5 treated with the tained over all catalysts in larger quantities than ethyl ben-
HF. zene, which can be attributed to the initial formation of
www.chxb.cn Ahmed K. ABOUL-GHEIT et al.: Para-Xylene Maximization-Part VIII: Promotion of H-ZSM-5 Zeolite 1213

ethylbenzene in significant quantities and then rapid alkyla- between ethylene and toluene will then produce ethyltolu-
tion to ethyltoluene. The side chain alkylation of toluene to ene [21] (Eq. (3)).

-
-
ethylbenzene is ruled out because it requires basic catalysts H2O H2 O
2CH3OH CH3OCH3 CH2 = CH2 (3)
[18].
The gaseous product yields range between 3.0%6.6% on
A more undesired product is the heavy alkylated fraction
H-ZSM-5 at temperatures from 300500 C and between
formed by the further alkylation of xylenes in the product
6.2% and 9.5%, respectively, on the 0.2%Pt/H-ZSM-5 cata-
(TMBs). The yield of TMBs can be as high as 16% at 400
lyst and vary by 0.6% over the other 0.2%Pt/H-ZSM-5
C on the unloaded zeolite. These high yields shift to 450
(HF) catalysts.
C when using the 0.2%Pt/H-ZSM-5 catalyst. TMBs are
formed by excessive alkylation during xylene production on
2.2 Para-xylene selectivity of the catalysts
all the catalysts studied without significant differences at
low temperatures (300350 C). This indicates that this
Figure 5 shows that the 0.2%Pt/H-ZSM-5 catalyst has the
reaction is not significantly dependent on the modifications
lowest selectivity for para-xylene production among all
we applied to H-ZSM-5 (Pt or Pt-HF combination) at lower
current catalysts. However, the unloaded catalyst
temperatures. However, at higher temperatures (400500
(H-ZSM-5) has higher selectivity than the platinized cata-
C) the increase in HF concentration on shape selectivity is
lyst, which indicates that it has a faster para-xylene trans-
more obvious during TMB production. In this temperature
formation compared to the other xylenes. This behavior
range (Fig. 4), the activities of the catalysts for TMB pro-
shows that Pt does not act as a shape selective promoter for
duction decrease as follows: 0.2%Pt/H-ZSM-5 > 0.2%Pt/H-
para-xylene formation. This may also imply that the Pt in
ZSM-5(1%HF) > 0.2%Pt/H-ZSM-5(2%HF) > 0.2%Pt/H-
this catalyst was mostly distributed over the external surface
ZSM-5(3%HF) > 0.2%Pt/H-ZSM-5(4%HF). Evidently, the
of the zeolite rather than being dispersed throughout the
increase in HF concentration results in more debris deposi-
channels of the zeolite (internal surface). This is because
tion in the zeolitic channels and a greater restriction on
high Pt dispersion in the channels should have increased the
TMB formation is a consequence. This is a clear example of
shape selectivity of the 0.2%Pt/H-ZSM-5 catalyst and con-
shape selective reactions in modified zeolites.
sequently the para-xylene selectivity should have increased
The gaseous products include hydrocracked C1C5
because of the incorporation of Pt instead of having de-
molecules. Ring opening reactions can take place at low
creased.
levels in the lower temperature region since the benzene
The benefit of an increase in para-selectivity by HF addi-
ring can be hydrogenated at these temperatures to cyclopar-
tion to 0.2%Pt/H-ZSM-5 is obvious by considering the cor-
affin (exothermic reaction) and then they are opened and
relation between para-selectivity and temperature over the
further hydrocracked. However, at much lower tempera-
lower temperature range (Fig. 5). Here, para-xylene selec-
tures, methanol undergoes a bimolecular dehydration pro-
tivity follows the order 0.2%Pt/H-ZSM-5(1%HF) < 0.2%Pt/
ducing dimethylether which again undergoes unimolecular
H-ZSM-5(2%HF) < 0.2%Pt/H-ZSM-5(3%HF) < 0.2%Pt/H-
dehydration and this results in ethylene [19,20]. A reaction
42
24 0.2%Pt/H-ZSM-5(4%HF) 0.2%Pt/H-ZSM-5(4%HF)
0.2%Pt/H-ZSM-5(3%HF) 40 0.2%Pt/H-ZSM-5(3%HF)
0.2%Pt/H-ZSM-5(2%HF) 0.2%Pt/H-ZSM-5(2%HF)
38
20 0.2%Pt/H-ZSM-5(1%HF) 0.2%Pt/H-ZSM-5(1%HF)
Selectivity for p-xylene (%)

0.2%Pt/H-ZSM-5 36 0.2%Pt/H-ZSM-5
TMB in products (%)

Untreated H-ZSM-5 Untreated H-ZSM-5

34
16
32

12 30

28
8 26

24
4
22
300 350 400 450 500 300 350 400 450 500
Reaction temperature (oC) Reaction temperature (oC)
Fig. 4. Trimethylbenzenes in the product during toluene alkylation Fig. 5. Para-xylene selectivity during the alkylation of toluene with
with methanol using H-ZSM-5 and 0.2%Pt/H-ZSM-5 treated with HF. methanol using H-ZSM-5 and 0.2%Pt/H-ZSM-5 treated with HF.
1214 Chin. J. Catal., 2010, 31: 12091216

ZSM-5(4%HF). the X/Xe ratio for ortho-xylene is the highest for the other
Moreover, para-xylene selectivities depend on the reac- xylenes and ranges between 1.26 and 1.71 whereas the
tion temperature; at higher temperatures, physical rather para-xylene ratio ranges between 1.18 and 1.28 and for
than chemical effects are accelerated when using the 2% meta-xylene, the ratio is as low as 0.570.80; i.e., the order
HF, 3% HF, and 4% HF containing catalysts. Furthermore, of these ratios decreases as follows:
the para-selectivity of 0.2%Pt/H-ZSM-5(4%HF) decreases ortho-xylene > para-xylene > meta-xylene (I)
greatly at temperatures higher than 350 C and it is the least The thermodynamic equilibrium distribution of the three
selective at 500 C. This is attributed to an attack on isomers of xylene at different temperatures in the range
H-ZSM-5 because of the higher HF concentration, which 300500 C is given in Table 2 and these values are taken
causes significant dealumination that seriously decreases the from Taylor et al. [22].
proton acidity and in addition leads to the deposition of
excessive fluoro-alumino and fluoro-silico species (debris) Table 2 Thermodynamic equilibrium values of para-, meta-, and
in the channels of the zeolite as mentioned above. This is ortho-xylenes at different temperatures
evident by the large drop of para-xylene selectivity from X/Xe
Product
39.2% at 300 C to 29.5% at 400 C over the 4%HF con- 300 C 350 C 400 C 450 C 500 C
taining catalyst. p-Xylene 23.88 23.73 23.55 23.37 23.19
m-Xylene 53.65 52.98 52.42 51.94 51.56
2.3 Para-xylene production relative to the o-Xylene 22.47 23.29 24.03 24.69 25.25

thermodynamic equilibrium
All the catalysts under study show an increase in
para-xylene production relative to the thermodynamic equi-
librium, i.e. X/Xe (Fig. 6), where X is the percentage of the
individual xylenes in the total xylenes produced on a given
catalyst and at a given temperature. Xe is the thermodynamic
equilibrium value of the xylene isomer at the same tem-
perature. Using unloaded H-ZSM-5 as a catalyst (Fig. 6),
Evidently, more than half the thermodynamic equilibrium
product is composed of meta-xylene whereas approximately
one quarter of this equilibrium is composed of the or-
tho-isomer and the other quarter by the para-isomer. The
most popular xylene isomer in the petrochemical industry is
para-xylene whereas the least desired xylene is
meta-xylene. Therefore, it is economically important to
convert meta-xylene to para-xylene via hydroisomerization.

1.8

1.6 Untreated H-ZSM-5 0.2%Pt/H-ZSM-5 0.2%Pt/H-ZSM-5(1%HF)

1.4 (1)
(2) (1)
1.2 (2)
(1)
(3)
X/Xe

1.0
(3)
0.8 (3) (2)
0.6

0.4
1.8
0.2%Pt/H-ZSM-5(2%HF) 0.2%Pt/H-ZSM-5(3%HF) 0.2%Pt/H-ZSM-5(4%HF)
1.6 (1)
(1) (1)
1.4

1.2
X/Xe

(2) (2) (2)

1.0
(3) (3)
0.8 (3)

0.6

0.4
300 350 400 450 500 300 350 400 450 500 300 350 400 450 500
Temperature (oC) Temperature (oC) Temperature (oC)
Fig. 6. X/Xe values at different reaction temperatures. (1) p-Xylene; (2) o-Xylene; (3) m-Xylene.
www.chxb.cn Ahmed K. ABOUL-GHEIT et al.: Para-Xylene Maximization-Part VIII: Promotion of H-ZSM-5 Zeolite 1215

Wei [23] calculated the molecular diameter of the xylene -7.4

isomers and found that both ortho- and meta-xylenes have 0.2%Pt/H-ZSM-5(4%HF)
-7.6 0.2%Pt/H-ZSM-5(3%HF)
almost equal diameters while para-xylene has a signifi- 0.2%Pt/H-ZSM-5(2%HF)
cantly smaller diameter. Accordingly, the order of the X/Xe -7.8 0.2%Pt/H-ZSM-5(1%HF)
values in Fig. 6 is not in accordance with Weis molecular 0.2%Pt/H-ZSM-5
-8.0 Untreated H-ZSM-5
diameter values because:
ortho-xylene meta-xylene > para-xylene (II) -8.2

lnk
The order of xylene isomers according to their shape se-
-8.4
lectivity, i.e., according to their molecular diameter favora-
bility is as follows: -8.6
para-xylene > ortho-xylene meta-xylene (III)
-8.8
Hence, correlation of (I) and (III) shows that the unloaded
H-ZSM-5 cannot be considered as a shape selective catalyst 1.4 1.5 1.6 1.7 1.8
(103/T)/K1
to maximize para-xylene production since ortho-xylene is
more selectively formed than para-xylene. Fig. 7. Arrhenius plot for the alkylation of toluene with methanol
using the untreated and hydrofluorinated 0.2%Pt/H-ZSM-5 catalysts.
Using the 0.2%Pt/ H-ZSM-5 catalyst (Fig. 6), the effect
of incorporating platinum in the zeolite is evident because
Applying absolute reaction rate theory, k is related to the
para-xylene is selectively formed over the other xylenes.
activation enthalpy, H, and the activation entropy, S as
The X/Xe ratio for para-xylene is 1.071.31, for or-
in Eq. (5):
tho-xylene is 0.841.36, and for meta-xylene is 0.711.01.
k T H / RT S / R (5)
The ortho-/para-privilege over the meta-directing privilege k= b e e
h
is evident over the lower temperature region (< 400 C).
The activation entropy (S) values (Table 3) are similar
The hydrofluorination of 0.2%Pt/H-ZSM-5 has a positive
(71.0 to 72.4 e.u.) for the catalyst containing
effect on improving the para-xylene selectivity relative to
0.2%Pt/H-ZSM-5 and those doped with 1.0% to 3.0% HF.
the thermodynamic equilibrium and the increase in HF
However, the unloaded and the highly doped
concentration from 1% to 4% results in an increased in the
(0.2%Pt/H-ZSM-5(4%HF)) catalysts show higher negative
X/Xe values particularly at lower temperatures (Fig. 6).
entropy changes (74.7 to 75.8 e.u.) (Table 3). The ran-
However, formation of the ortho- or meta-xylene isomers
domness for the H-ZSM-5 can be attributed to Al(OH)x spe-
was mostly found to fall below the equilibrium values and
cie deposition on the internal surface of H-ZSM-5 after the
ortho-xylene surpasses the meta-isomer particularly in the
synthesis. However, for the 4% HF doped catalyst the ran-
lower temperature region. This behavior is in accordance
domness can be attributed to the debris deposited after Al
with the para-xylene shape selectivity. However with re-
and Si leaching with higher concentrations of HF.
spect to the two more voluminous isomers, which possess
equal diameters the ortho-directing reaction is evidently
Table 3 Activation parameters for the alkylation of toluene with
more mechanistically favorable compared to the meta-di- methanol using the studied catalysts.
recting one.
Catalyst Ea103 (J/mol) S*/(e.u.)
Unloaded H-ZSM-5 11.0 74.7
2.4 Kinetics of toluene alkylation with methanol
0.2%Pt/H-ZSM-5 17.1 72.0
0.2%Pt/H-ZSM-5(1%HF) 18.7 71.0
From the reaction data of total xylene in Fig. 3, the reac- 0.2%Pt/H-ZSM-5(2%HF) 15.4 72.4
tion rate constant, k, was calculated according to the simple 0.2%Pt/H-ZSM-5(3%HF) 17.6 71.5
first order flow reactor equation: 0.2%Pt/H-ZSM-5(4%HF) 11.9 75.8
F 1 WHSV 1 (4)
k = ln = ln
W 1 x 3600 1 x The Ea values are in accordance with the S values since
Where F is the rate of feed injection (cm3/s), WHSV is the lower values were obtained using untreated and 4% HF
weight hourly space velocity (h1), W is the catalyst weight containing zeolite indicating a higher diffusion limit for the
(1 g) and x is the wt% of total xylenes in products. reaction.

The activation energy (Ea) for the alkylation reaction us- 3 Conclusions
ing the current catalysts was calculated using the tradition-
ally accepted Arrhenius equation and k values were obtained The promotion of H-ZSM-5 with 0.2% Pt and HF at
(Fig. 7). concentrations between 1% and 3% is found to be effective
1216
for the alkylation of toluene with methanol to xylenes by
increasing the number of acid sites and the acid strength
while inhibiting the side reaction of TMB formation by in-
creasing the shape selectivity of the catalysts. However,
increased hydrofluorination by 4% HF decreased the acidity
and altered the surface area and pore volume distribution of
the zeolites. As a result, significant diffusion restriction oc-
curs by the deposition of fluoro-alumino- and fluoro-silico-
debris in the larger pores and cavities of the zeolites in the
4% HF doped catalyst. A comparison of the activities of
unloaded H-ZSM-5 and 2%Pt/H-ZSM-5 demonstrates the
efficient role of Pt in activating and stabilizing the car-
bonium ion formed on the acid sites. This work also shows
that the acid sites created by doping with HF enhance the
dispersion of Pt, which induces further activation.
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