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Alkylation of Toluene with Methanol over Alkali

Exchanged ZSM-5

Article in ChemInform · January 1991

DOI: 10.1016/S0166-9834(00)84108-1

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Applied Catalysis, 68 (1991) 277-284
Elsevier Science Publishers B.V., Amsterdam

Alkylation of toluene with methanol over alkali

exchanged ZSM-5

H. Vinek, M. Derewinskil, G. Mirth and J.A. Lercher*

Institut fiir Physikalische Chemie, Technische Universitiit Wien, Getreidemarkt 9,
A-1060 Vienna (Austria), tel. (+43-222) 58801.4964, fax. (+43-222) 5874835.
(Received 19 July 1990, revised manuscript received 19 September 1990)

Abstract

The catalytic activity was investigated of a series of alkali exchanged and alkali impregnated ZSMd
zeolites in the alkylation of toluene with methanol. The variations of the rate of the reaction were
concluded to be governed mainly by the concentrations of protonated methanol molecules and of ad-
sorbed toluene. The active sites were concluded to be weak Bmnsted acid sites, present as a result of
lattice defects. The alkali cations were not active in the alkylation reaction. They do, however, influence
the acid strength of the weak acid sites. Because of this influence, the concentration of methoxonium
ions and hence the rate of alkylation decreases from LiZSM-5 to CsZSM-5.

Keywords: toluene alkylation, zeolites, acid sites, alkali ZSM-5.

INTRODUCTION

In recent years the alkylation of toluene by methanol over ZSM-5 zeolites

has been the subject of frequent investigations. One factor that stimulated this
interest was that the production of p-xylene is economically rewarding [I];
another is that the distribution of the resulting xylenes may characterize the
steric constraints encountered by the reaction products in the zeolite channels
[2-61.
Postsynthesis treatment [l-4,7,8] as well as modified synthesis conditions
were reported to cause a drastic difference in the selectivities in the alkylation
of toluene with respect to the values expected from thermodynamic equilib-
rium values. In particular, the postsynthesis treatment with phosphorus [7,8]
and boron [1,10,11 ]compounds were used extensively to enhance the selectiv-
ity to p-xylene in processes producing or converting xylenes. Two factors have
been invoked to explain this selectivity: (i) the increase of the steric con-

‘Permanent address: Institute for Catalysis and Surface Chemistry, Polish Academy of Sciences,
ul. Niezapominajek, 30-239 Krakov, Poland.

0166-9834/91/$03.50 0 1991 Elsevier Science Publishers B.V.

278

straints within the zeolite channels, and (ii) a decrease of the acid strength of
the material.
In contrast to the significant work on the effects governing the selectivity of
the alkylation reactions, less attention has been paid to investigate the type
and the role of active sites in the catalysis of the alkylation of aromatic mole-
cules. For faujasite samples, in the presence of acidic protons, alkylation of the
aromatic ring was observed, while alkylation of the side chain was observed
when only alkali cations were present in the zeolite [12-141. The formation of
ethylbenzene from toluene and methanol was correlated with the dehydroge-
nation of methanol [ 141, the resulting formaldehyde being a key intermediate
in the side chain alkylation. Preliminary studies revealed, however, that ethyl-
benzene was not formed over alkali exchanged HZSM-5.
In this communication we report the conversion of toluene and methanol
over a series of alkali exchanged and alkali impregnated ZSM-5 zeolites. Our
main interest is in the characterization of the nature of possible active sites in
the molecular sieves and their impact on activity and selectivity.

EXPERIMENTAL

Catalysts and reagents

The ZSM-5 samples were synthesized as described in [ 151. No crystalline

material other than ZSM-5 was detected by XRD. After synthesis the material
was calcined in air at 873 K to remove the organic template. Subsequently, the
samples were ion exchanged four times at 368 K in 0.1 M solutions of ammo-
nium chloride and the appropriate alkali nitrates. After the exchange proce-
dure the samples were washed with distilled water and dried in air at 393 K for
6 h. The silicon-to-aluminum ratio was 36, corresponding to 2.6 aluminum
atoms per unit cell of the zeolite. The degree of ion exchange of any of the
alkali cation forms was better than 85%, the difference being Na+ cations.
Electron microscopy showed that the size of the crystals was smaller than one
micrometer and that these crystals formed larger agglomerates. NaZSM-5 and
KZSM-5 produced according to this procedure were subsequently washed with
0.012MNaOH (KOH) and 0.1 Msodium acetate (potassium acetate) solution,
dried and calcined at 773 K for one hour.

Catalytic measurements

All catalytic experiments were carried out in continuous flow mode at a total
pressure of 1 bar. Between 0.05 and 0.1 g of catalysts and a partial pressure of
toluene of 25 mbar and of methanol of 35 mbar (1.9.10-” mol/h) were typi-
cally used. The catalysts were activated at 773 K for 1 h in flowing nitrogen.
The reactants were supplied by saturating the nitrogen carrier gas with toluene
 279

and methanol. The reactor effluents were injected into the GC column (5% SP
1200/5% Bentone 34) via a six-port valve. A Perkin Elmer F-11 gas chroma-
tograph with FID was used for analysis.

Gravimetric measurements

The adsorption capacity for toluene was determined at equilibrium pres-

sures between 10m3and 1 mbar. Prior to adsorption measurements the zeolite
was heated at 873 K for one hour in vacuum (lo-” mbar).

RESULTS

The specific rates (normalized to the unit cell) of all samples investigated
are compiled in Table 1. At a reaction temperature of 523 K the activity of the
zeolites decreased by two orders of magnitude from HZSM-5 to CsZSM-5. At
773 K this difference in the specific rates was only one order of magnitude. In
contrast, samples washed (at ambient temperature) with sodium hydroxide or
sodium acetate showed activities which were at least a factor of fifty lower than
those determined for the ion exchanged ZSM-5.
With ion exchanged samples, the energies of activation was 50 kJ mol-l for
HZSM-5 and varied between 61 and 65 kJ mol- ’ for the alkali exchanged sam-
ples, indicating similar rate determining steps. For a given sample the selectiv-
ity to m-xylene increased with reaction temperature and conversion. At reac-
tion temperatures below 523 K and low conversion ( < 1%) m-xylene was not
observed, indicating that it was a secondary product. Both, p- and o-xylene are
primary products. The lack of m-xylene as primary product may be charge
induced [ 101. The increase of the concentration of m-xylene at 773 K from
CsZSM-5 to HZSM-5 indicates an increase in the activity towards isomeriza-
Lion of the primary xylenes formed. Similarly the variations of the selectivity
towards p-xylene can be described as a combination of two reactions. On the
one hand (seen mainly for the less active samples) 9the selectivity to p-xylene
increases as the reaction temperature increases due to the diffusional separa-
tion of the xylene isomers. On the other hand, p-xylene is consumed for sec-
ondary isomerization to m-xylene with increasing temperatures (increasing
conversion), which causes a decrease of the selectivity top-xylene at high tem-
peratures for LiZSM-5 and HZSM-5 (i.e., for the most active samples). o-
Xylene selectivity decreased with increasing reaction temperature for all sam-
ples investigated. Note that for HZSM-5, o-xylene seemed to be more reactive
than p-xylene. This indicates a longer residence time of o-xylene than of p-
xylene.
280

TABLE 1

Alkylation of toluene with methanol

Catalyst Temp. Conv. Spec. rate Xylene isomer composition

(K) (mol-%) (mol/UCs) (mol-%)

Para Meta Ortho

HZSM-5 773 34 9.8.lo-” 32 49 19

673 22 6.2*10-” 40 41 19
573 8.1 3.1*10-” 51 20 29
523 6.3 1.0*10-3 46 14 40
473 1.8 1.70 10-4 41 0 50
LiZSM-5 773 18 4.0.10-3 35 40 25
673 9.2 1.9a10-3 35 30 35
573 2.1 2.5*10-4 37 25 38
523 1.2 1.5*10-4 40 9 51
473 0.4 1.4*10-” 49 0 51
NaZSM-5 773 11 3.2-10-3 44 34 22
673 4.1 9.8*10-” 42 31 27
573 1.5 2.1*10-* 32 29 39
523 0.8 3.7* 10-5 53 0 47
KZSM-5 773 7.7 1.8*10-3 44 27 29
673 2.7 4.7. 1o-4 41 27 32
573 0.9 4.9.10-5 54 0 46
523 0.1 1.1.10-5 51 0 49
RbZSM-5 773 2.5 4.5*10-4 37 28 35
673 1 9.4.10-4 35 26 38
573 0.3 2.00 10-5 49 0 51
523” - 5.6*10-” - - -
CsZSM-5 773 2.4 4.4010-4 39 28 33
673 0.9 1.3.10-4 36 26 38
573 0.3 1.8* 1O-5 53 0 47
523” - 5.1.10-6 - - -
NaZSM-5/NaOH 713 0
NaZSM-5/NaAc 773 0.58 2.4*10-5

“Extrapolated values.

DISCUSSION

The sequence of possible reaction steps of alkylation of toluene by methanol

is given in Fig. 1. In agreement with earlier papers we suggest that the surface
reaction proceeds in three steps: (i) formation of a methoxonium ion, (ii)
reaction between the methoxonium ion and toluene, (iii) donation of a proton
from the positively charged xylene to the zeolite. In general, the rate determin-
ing step is assumed to be the second [ 16,17 7. This is supported in our case by
the similar energies of activation of the reaction.
If these arguments are valid, the rate of the reaction should be controlled by
 281

0 0
CH3OH + H ZEOLITE -- CH30Hp + LEOLITE

CH3 CH3

.,“..‘..
0 ‘., 0
+ CH30H2 _ ZEOLITE + HP0
0

-:-I----: \
H
CH3

Fig. 1. Schematic representation of the reaction mechanism proposed.

the concentrations of the methoxonium ions and the adsorbed toluene. While
the adsorption capacity of the zeolites was approximately equal for all samples
investigated, the concentration of the methoxonium ions depends on the avail-
ability and the strength of protons in our samples. Pn a previous paper [ 181 we
pointed out that, depending upon the reaction temperature, strong and weak
Bronsted acid sites may form a source of protons The near absence of catalytic
activity of the sodium hydroxide (potassium hydroxide ), and sodium acetate
(potassium acetate) washed samples indicates that alkali cations are unable
to polarize methanol sufficiently to generate methoxonium ions or methyl car-
benium ions (see Table 1). The catalytic activity of the ion exchanged samples
must thus be attributed to the weak Bronsted acid sites present in these ma-
terials because of lattice defects. Although these sites can be ion exchanged
[ 191 with alkali cations, we think that most of these weak acid sites became
hydrolyzed during the washing procedure of our samples. Note that weak acid
sites are more susceptible to hydrolysis than strong ones. Since we used a com-
mon batch of samples the average concentration of these sites should be ap-
proximately equal for all samples investigated. The difference in the activity
observed between LiZSM-5 and CsZSM-5 is thus best explained on the basis
of the chemical influence of the alkali cation upon these weak acid sites.
Support is given to this explanation by the substantial increase of the rate
of the alkylation with increasing electrostatic potential of the exchangeable
cations (see Fig. 2 ). The increase of the acid strength shifts the equilibrium in
282

1.6E-04 Li
w
1.4E-04

1.2E-04

1 .OE-04

spec. rate
8.OE-05
(mol/(UC.s))
f

Na
4.OE-05
1 a

0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7

e/r of the cation

Fig. 2. Dependence of the rate of alkylation at 523 K upon the electrostatic potential (e/r) of the
cation.

T
4.5

4.0

3.5

3.0
I
2.5 --
molec. / W.
2.0 --

0.0 i- i- + + -t
l-iZSM5 LiZSM5 NaZSlW5 KZSMS CsZSM5 NaZSMS/ NaZSM5/
NaOH NaAc

Fig. 3. Concentration of toluene adsorbed on alkali exchanged and alkali impregnated ZSM-5 after
equilibration at 10-l mbar and 308 K.

eqn. (1) of Fig. 1 to the right and vice versa. ecause we know that the con-
centrat~~~ of toluene adsorbed was a~~~ox~~ate~~ equal on alilsamples inves-
tigated (see Fig. 3 ), we propose that the ~o~ce~t~~t~o~ of ~etbox~~i~~ ions
decreased from EiZSM-5 to CsZSM-5, causing the observed decrease in the
rate of the reaction.
 283

While we cannot completely rule out that there are no residual strong
Bronsted acid sites present in our samples, we should emphasize that we have
no evidence of their existence from all previous characterizations [20,21]. Note
that, in principal, however, the proposed chemical effect would also apply for
strong Bronsted acid sites.
All changes in the selectivities can also be explained by the presence of weak
acid sites the strength of which depends subtly upon the electronegativity of
the cation present. As we pointed out above, all secondary reactions gain in
importance as the acid strength of the cations increases; i.e. from CsZSM-5 to
LiZSM-5, the selectivity to m-xylene (secondary product) increased, the se-
lectivity to o-xylene decreased, and that to p-xylene increased for the less ac-
tive samples, while it passed a maximum for the more active ones. Note that
these secondary reactions require the presence of protons and cannot be cat-
alyzed with polarization or hydride abstraction by alkali cations [18]. There
seems to be no effect of the size of the cation and the only parameters governing
the observed selectivities are the concentration and strength of the protons in
these samples.

ACKNOWLEDGEMENT

This work was supported by the Fonds zur Fiirderung der wissenschaftlichen
Forschung under contracts P5757 and P7312.

REFERENCES

W.W. Kaeding, U.S. Patent 4 067 920 (1978).

W.W. Kaeding, C. Chu, L.B. Young, B. Weinstein and S.A. Butter, J. Catal., 67 (1981) 159.
W.W. Kaeding, C. Chu, L.B. Young and S.A. Butter, J. Catal., 69 (1981) 392.
L.B. Young, S.A. Butter and W.W. Kaeding, J. Catal., 76 (1982) 418.
P.B. Weisz, Pure Appl. Chem., 52 (1980) 2091.
E.G. Derouane, Stud. Surf. Sci. Catal., 5 (1980) 5.
J. Nunan, J. Cronin and J. Cunningham, J. Catal., 87 (1984) 17.
J.C. Vedrine, A. Auroux, P. Dejaifve, V. Ducarme, H. Hoser and S. Zhou, J. Catal., 73 (1982)
147.
9 W. Holderich, W.D. Mross and M. Schwarzmann, Ger. Offen. DE 3 243 520 (1982).
10 M.B. Sayed and J.C. Vedrine, J. Catal., 101 (1986) 43.
11 G. Coudurier and J.C. Vedrine, Stud. Surf. Sci. Catal., 28 (1986) 643.
12 H. Itoh, T. Hattori, K. Suzuki and Y. Murakami, J. Catal., 79 (1983) 21.
13 J.M. Garces, G.E. Vrieland, S.I. Bates and F.M. Scheidt, Stud. Surf. Sci., 20 (1985) 67.
14 P.E. Hathaway and M.E. Davis, J. Catal., 119 (1989) 497.
15 R.G. Argauer and G.R. Landolt, U.S. Patent 3 702 886 (1972).
16 D. Bethel1 and V. Gold, Carbonium Ions - An Introduction, Academic Press, London and
New York, 1967, p. 178.
17 H. Vinek, G. Rumplmayr and J.A. Lercher, J. Catal., 115 (1989) 291.
18 H. Vinek and J.A. Lercher, J. Mol. Catal., (1990) in press.
284

19 A.W. Chester, Y.F. Chu, R.M. Dessau, G.T. Kerr and G.T. Kresge, J. Chem. Sot. Chem.
Comm., 5 (1985) 289.
20 M. Derewinski, J. Haber, J. Ptaszynski, J.A. Lercher and G. Rumplmayr, Stud. Surf. Sci., 28
(1986) 975.
21 J.A. Lercher, G. Warecka and M. Derewinski, Proc. 9th Int. Congr. Catal., The Chemical
Institute of Canada, Ottawa, 1988, p. 364.

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