Applied Clay Science 44 (2009) 137–143

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / c l a y

Formation of ethyl benzene and styrene by side chain methylation of toluene

over calcined LDHs
R. Manivannan ⁎, A. Pandurangan
Department of Chemistry, Anna University, Chennai-600 025, India

a r t i c l e i n f o a b s t r a c t

Article history: Mg/Al layered double hydroxide (LDH) with various Mg/Al molar ratios 3, 4, 5, 7 and 10 were prepared,
Received 26 June 2008 calcined and characterized by XRD, FT-IR, ICPES and BET surface area analysis. These LDHs were used for side
Received in revised form 17 December 2008 chain methylation of toluene with methanol between 300 and 450 °C. For comparison, Cu/Al, Ni/Al, Co/Al and
Accepted 18 December 2008
Zn/Al LDHs with molar ratio 3 were also prepared. The selectivity of styrene was higher over Mg/Al with low
Available online 31 December 2008
Al content. The selectivity of ethyl benzene was higher at 400 °C. At higher temperature, the side chain
Keywords:
alkylation was favored and the selectivity of nuclear alkylation products such as xylene and mesitylene
Toluene decreased as Mg/Al ratio changes from 3 to 10. The enhanced activity of calcined LDHs is due to the surface
Methylation sites of low (OH− groups), medium (Mg–O pairs), and strong (O2− anions) basicity. The surface concentration
Layered double hydroxide (LDH) of low and medium strength basic sites increased with decreasing Al content. On Mg/Al LDHs, nuclear
alkylation increased with increasing Al content. Substitution of Co2+, Ni2+, Zn2+ and Cu2+ for Mg2+ favored
nuclear alkylation. The selectivity of xylene and mesitylene increased with increase in temperature at a
maximum 400 °C. Mg/Al LDHs were the most LDHs active than other LDHs for side chain methylation of
toluene.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
One of the reasons why the studies of heterogeneous basic
catalysts are not as extensive as those of heterogeneous acidic
catalysts seems to be the requirements for severe pretreatment
conditions for active basic catalysts. The surface is often covered with
carbon dioxide, water, oxygen etc., and shows no activity for base-
catalyzed reactions. In LDHs, desorption of carbon dioxide and water
results in the generation of basic sites in the surface, which act as
catalytically active sites (Cavani et al., 1991; Velu and Swamy, 1994; Di
Cosimo et al., 1998; Obalová et al., 2006, 2007). The interesting
property of the oxides obtained by calcination of LDHs around 400 °C
is the formation of highly active homogenous mixed oxides which are
potentially used as basic catalysts and catalyst supports (Reichle, 1986;
Schaper et al., 1989). These oxides are efficient solid base catalysts for
aldol condensation (Suzuki and Ono, 1988), polymerization of β-
propiolactone (Nakatsuka et al., 1979) and alkene isomerization
(Reichle, 1985). The activity of the catalysts depends strongly on
chemical composition and calcination temperature. Ethylbenzene is
the key intermediate in the manufacture of styrene, which is one of
the most important industrial monomers. In recent years, attention
has been paid to the side chain alkylation of toluene with methanol,
which gives styrene and ethyl benzene. Basic catalysts such as MgO,
⁎ Corresponding author. Tel.: +91 9443953491 (Mobile).
E-mail address: manickam_mani@yahoo.co.in (R. Manivannan).
MgO–TiO2, CaO–TiO2 and TiO2 have been reported to show very little
activity for the side chain alkylation of toluene (Yashima et al., 1970).
Sidorenko et al. (1967) have proposed a reaction scheme in which
methanol is first dehydrogenated to formaldehyde which subse-
quently transforms toluene into styrene. The styrene is hydrogenated
into ethylbenzene. Recently, quantum chemistry has been applied to
the study of heterogeneous catalysis involving side chain alkylation of
toluene (Itoh et al., 1980, 1983) containing acidic and basic sites. The
basic sites activate the carbon atom of the side chain of toluene and
the acidic sites adsorb and stabilize toluene molecules.
2. Experimental
2.1. Catalyst preparation
Mg/Al, Co/Al, Ni/Al, Cu/Al and Zn/Al LDHs precursors were
synthesized by co-precipitation at constant pH (Cavani et al., 1991;
Velu and Swamy, 1994). For Mg/Al LDH, an aqueous solutions
containing 0.09 mol of Mg (NO3)2 .6H2O and 0.03 mol of Al (NO3)2
.9H2O was slowly mixed with a solution of 0.33 mol of NaOH and
0.082 mol of Na2CO3 at 120 °C under vigorous stirring, maintaining the
pH between 7 and 10. The mixture was aged at this temperature for
15 h during stirring. The precipitate was washed several times until
the solution was free of nitrate ions and then dried at 120 °C. The
following LDHs were synthesized by the same procedure: Mg/Al-LDH
with molar ratios of 4, 5, 7 and 10, and M (II)/Al-LDH, where M (II)= Co,
Ni, Cu and Zn with a molar ratio 3.

0169-1317/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2008.12.017
138 R. Manivannan, A. Pandurangan / Applied Clay Science 44 (2009) 137–143

Table 1
Chemical composition and lattice parameters of M (II)/M (III) CO3 LDHs.

Catalysts M (II)/ Lattice parameters (Å) Specific surface area (m2/g)

M(III)a a c Uncalcined Calcinedb
Mg/Al 3.0 2.71 3.049 23.301 99.5 168.0
Mg/Al 4.0 3.74 3.061 23.609 103.8 172.6
Mg/Al 5.0 4.69 3.092 23.801 88.7 154.8
Mg/Al 7.0 6.46 3.098 23.865 – –
Mg/Al 10.0 8.91 3.108 23.858 – –
Ni/Al 3.0 2.78 3.082 22.969 110.0 189.3
Cu/Al 3.0 2.72 3.058 22.867 119.6 206.4
Co/Al. 3.0 2.69 3.072 22.821 83.0 149.6
Zn/Al 3.0 2.90 3.064 22.769 69.8 106.5
a
ICPES result.
b
Calcined at 450 °C/8 h.

2.2. Characterization

The characterization of LDHs were carried out using ICPES, XRD,

FT-IR and BET surface area measurements.

Fig. 2. PXRD patterns of (a) Ni–Al 3.0, (b) Zn–Al 3.0, (c) Co–Al 3.0 (d) Cu–Al 3.0 LDHs.

2.2.1. Powder X-ray diffraction (PXRD)

The X-ray diffraction (XRD) patterns were recorded using a Philips
X-ray generator (Model PW 1050/81 controlled by a 1710 unit) using
Ni-filtered CuKα radiation, scan speed of 3°/min.

2.2.2. Fourier-transform infrared spectroscopy

FT-IR spectra of these samples from 4000–500 cm− 1 were
recorded in Shimadzu FT-IR spectrometer and Perkin Elmer IR
spectrometer (Model 983G) using KBr pellet technique. The powdered
samples were ground with KBr in the required molar ratio and
pressed into pellets.

2.2.3. BET surface area measurement

The specific surface area was measured by the flow method using
Micromeritics Pulse Chemisorb 2700 instrument.

2.3. Catalytic studies

The vapor phase alkylation of toluene with methanol was carried

Fig. 1. PXRD patterns of (a) Mg–Al 3.0, (b) Mg–Al 4.0, (c) Mg–Al 5.0 (d) Mg–Al 7.0
(e) Mg–Al 10.0 LDHs.
out in a fixed bed down flow type quartz reactor of 8.0 mm I.D and
35 mm length in which a porcelain disc was sintered and sealed in
the middle of the reactor to support the catalyst. 1.5 g of LDHs,
(calcined at 450 °C for 8 h) was packed inside the reactor and
supported by two glass wool plugs, which were surrounded by
ceramic beads to fill the space. Before starting the experiment, the
catalytic materials were activated at 450 °C for 3 h in nitrogen flow
(23 cm3/min) and then heated to the reaction temperature. The
alkylation reaction was carried out using a mixture of toluene and
methanol (molar ratio 1:1), introduced at the top of the reactor by
means of an infusion pump (Electronic Corporation of India) in the
absence of a carrier gas. The liquid products were collected in cold
traps and investigated in a Hewlett Packard 5890A gas chromato-
graph with a 2 m 5% bentone column equipped with a flame ion-
ization detector.
 R. Manivannan, A. Pandurangan / Applied Clay Science 44 (2009) 137–143 139

3. Results and discussion

3.1. Characterization of LDHs

The important characteristics of LDHs calcined at 450 °C are

presented in Table 1. All the synthesized samples exhibited the typical
XRD patterns of the LDH structures (Fig. 1). The samples showed a
sharp and symmetric peaks for (003), (006), (110) and (113) planes at
lower 2θ region and broad asymmetric peaks for (102), (105) and (108)
planes at higher 2θ region, which are characteristic of LDHs (Miyata,
1975; Sato et al., 1988). Samples with 2θ values lying between 0.21 and
0.25, produced best fitting of LDH patterns. The X-ray pattern was
indexed similar to the assignment of Allmann (Allmann, 1970). These
LDHs had rhombohedral R-3m symmetry. The lattice parameters ‘a’
and ‘c’ are calculated from the (003) and (110) reflections by indexing
the peaks as hexagonal crystal system with least square fitting.
The parameters ‘a’ and ‘c’ were around those of Mg/Al-LDHs and
small variations were due to changes of M (II) radii. The ‘a’ and ‘c’
parameters decreased with increasing Al content due to the substitu-
tion of layer Mg2+ ions by smaller Al3+ ions (Di Cosimo et al., 1998).
Sharp reflections were detected for samples with molar ratio 3. All
Fig. 4. FT-IR spectra of (a) Ni–Al 3.0, (b) Co–Al 3.0, (c) Zn–Al 3.0 and (d) Cu–Al 3.0 LDHs.
other samples showed broadened reflections due to smaller crystallite
sizes or less ordered structures (Fig. 2). All the compounds studied in
the present investigation crystallised in the LDH network with the
exception of Cu containing samples. In this case in addition to LDH (Fig. 3) although this band has been also related to the presence of
phase other phases such as malachite [Cu (OH)2 CuCO3] and gerhardite bicarbonate species. In most LDHs three bands were observed around
[Cu (OH)3 NO3] were observed as a consequence the Jahn–Teller effect 1350 cm− 1 (ν3), 850 cm− 1 (ν2) and 650 cm− 1 (ν4). The sharp
in Cu2+ ion (Alejandre et al., 1999). absorption band close to 1365 cm− 1 is due to the asymmetric
In FT-IR analysis, the intense and broad absorption bands due to stretching vibration (ν3) of the interlayer carbonate. In some cases
hydroxyl and water molecules (νOH stretching modes around intense band in the range 1300–1500 cm− 1 is attributed to
3500 cm− 1 and νOH bending mode around 1600 cm− 1) were observed interlamellar carbonate species with a lower symmetry than in the
free CO2−3 anion, which causes the splitting of the degeneracy of the ν3
modes (Hernandez-Morene et al., 1985). Absorption bands at lower
wave numbers are due to other modes of bicarbonate and to metal
oxygen vibration. Thus the IR spectra indicate the presence of strong
hydrogen bonds and intercalated CO2− 3 anions (Hernandez-Morene
et al., 1985; Hansen et al., 1994). The IR spectra of M (II)/AlCO3-LDH
with M (II)/Al molar ratio 3.0 are shown in Fig. 4. Differences between
observed vibrations of carbonate and free carbonate indicate the
perturbation of the anions in the interlayer space. CoAlCO3-LDH
showed the maximum shift in νOH band position to higher wave
number due to the reduced interaction of hydroxyl groups. The νOH
band for NiAl-LDH was observed around 3450 cm− 1 irrespective of the
method of preparation. The appearance of sharp bands for ν3
asymmetric stretching vibrations of CO2− 3 indicated that the symmetry
of the anion was not perturbed, unlike the observation in the case of
Mg/AlCO3− LDH. The bands observed between 800 and 400 cm− 1 are
assigned to lattice vibrations. Rey et al., 1992).

3.2. Methylation of toluene

Calcined Mg/Al LDHs yielded exclusively side chain alkylated

products, while Co, Ni, Cu and Zn containing hydrotalcites gave side
chain as well as nuclear alkylated products.

Table 2
Methylation of toluene: effect of reactant feed ratio on conversion and selectivity.

Catalyst Feed Toluene conversion Product selectivity

ratio (wt.%) (wt.%)
Ethylbenzene Styrene Xylene
MgAl-3.0 1:1 48.7 31.9 6.8 8.1
2:1 36.4 24.4 4.7 4.2
3:1 22.1 16.2 3.6 1.1
Fig. 3. FT-IR spectra of (a) (a) Mg–Al 3.0, (b) Mg–Al 4.0, (c) Mg–Al 5.0 (d) Mg–Al 10.0
LDHs. Temperature: 350 °C WHSV: 1.33 h− 1.
140 R. Manivannan, A. Pandurangan / Applied Clay Science 44 (2009) 137–143

Table 3
Effect of calcined LDHs in product distribution and conversion.

Catalysts Toluene Conversion Product yield (mol%)

(wt.%) Ethylbenzene Styrene Xylene Mesitylene
MgAl-3.0 36.4 22.3 9.6 3.0 –
MgAl-4.0 34.7 19.2 12.0 2.1 –
MgAl-5.0 28.1 14.6 11.3 1.2 –
MgAl-7.0 21.0 10.2 9.1 – –
MgAl-10.0 17.6 7.0 8.9 – –
CoAl-3.0 26.0 15.8 – 8.7 –
NiAl-3.0 31.5 14.2 – 15.4 1.1
CuAl-3.0 34.8 16.3 – 13.6 –
ZnAl-3.0 22.7 16.8 – 5.7 –
MgO 10.6 7.9 2.1 – –

Temperature: 300 °C.

Toluene:methanol: 1:1.
Catalyst weight: 1.5 g.
Flow rate: 2 ml/h.

formation of side chain alkylated products and the nuclear alkylated

products decreased. The toluene conversion and selectivity was
maximum at a toluene to methanol feed ratio of 1:1.

3.4. Effect of temperature on toluene conversion

The conversion of toluene increased with increasing temperature

Fig. 5. Methylation of toluene: effect of temperature on toluene conversion.
3.3. Effect of reactants ratio
The conversion decreased with increase in feed ratio (Table 2) due
to the reduced availability of the alkylating agent. As a result, the
from 300 to 400 °C, then decreased (Fig. 5). Even though conversion of
toluene was higher over Ni and Cu containing LDH and the selectivity
of ethyl benzene was lower. Nuclear alkylation was more favorable
than side chain alkylation over Co, Ni, Zn and Cu-LDHs (Fig. 6).
The product distribution was shown in Table 3. Over Co, Ni, Cu, and
Zn LDHs, the nuclear alkylated products such as xylene and
mesitylene were the major components with an appreciable amount
of ethyl benzene by side chain alkylation. With Mg/Al LDHs ethyl
benzene and styrene were the major products formed by side chain
alkylation of toluene.
Typical isomer distribution in the methylation of toluene with
methanol is given in Table 4. At 300–450 °C, alkylation of toluene is
normally considered to follow the ordinary Friedel–Crafts mechanism,
that is direct ortho–para attack of the alkylating agent on the benzene

Table 4
Effect of temperature on isomer distribution of xylene.

Catalysts Temperature Product yield

(°C) (mol%)
o-xylene m-xylene p-xylene
MgAl-3.0 300 2.3 – 0.7
350 3.4 1.3 3.4
400 5.7 3.1 4.8
450 4.5 2.3 3.2
CoAl-3.0 300 3.0 1.2 4.5
350 2.8 5.4 8.4
400 2.5 8.9 11.6
450 1.3 7.0 9.9
NiAl-3.0 300 3.6 1.9 9.9
350 3.2 6.2 15.5
400 2.3 13.6 22.3
450 1.2 11.5 18.4
CuAl-3.0 300 3.3 1.8 8.5
350 3.1 5.6 13.2
400 3.0 10.9 20.2
450 2.2 6.0 9.3
ZnAl-3.0 300 2.8 – 2.9
350 2.6 3.2 10.5
400 0.8 12.4 20.4
450 – 7.5 9.3

Toluene:methanol = 1:1.
Catalyst weight: 1.5 g.
Fig. 6. Methylation of toluene: effect of temperature on yield of ethylbenzene. Flow rate: 2 ml/h.
 R. Manivannan, A. Pandurangan / Applied Clay Science 44 (2009) 137–143 141

Fig. 9. Methylation of toluene: effect of temperature on yield of mesitylene.

Fig. 7. Methylation of toluene: effect of temperature on yield of styrene.
ring followed by positional isomerization producing the thermody-
namically favoured meta-isomer. Increasing the temperature between
300 and 400 °C, the total yield as well as m-xylene formation
increased. This may be due to the isomerization of o- and p-xylene at
higher temperature. Mg/Al-LDHs resulted in greater o-xylene forma-
tion while other LDHs gave p-xylene in excess at low temperatures.
With rising temperature (i.e., at 350 °C and 400 °C), the formation of
m-xylene increased and of the p- and o- isomer decreased.
mesitylene (Fig. 9) decreased from Mg/Al molar ratio 3 to 10. On Mg/
Al-LDH and the formation of xylene and mesitylene decreased. Thus
Mg/Al LDH with molar ratio 3.0 exhibited maximum catalytic activity
(Table 3). For comparison, MgO had very low activity at all
temperatures studied. On pure MgO, strong basic sites consist
predominantly of O2− anions. The high activity of LDH is due to the
surface sites of low (OH− groups), medium (Mg–O pairs), and strong
(O2− anions) basicity. The surface concentration of low and medium
strength basic site increases with decreasing Al content in the
samples.

3.5. Mg/Al-CHT 3.6. Influence of other M (II) ions

Calcined Mg/Al LDH showed the maximum conversion at 400 °C.
The conversion decreased in the order Mg/Al = 3 N 4 N 5 N7 N10. The
selectivity of styrene was higher over Mg/Al-LDHs with low Al
content. Selectivity of ethylbenzene formation was higher at 400 °C.
The selectivity of styrene decreased with increase in temperature
(Fig. 7). At higher temperature, due to side chain alkylation, the
selectivity of nuclear alkylation products such as xylene (Fig. 8) and
In Table 3 selectivity towards the side chain and nuclear alkylated
products and conversion for various calcined M (II) LDHs were given.
Substitution of Mg2+ favored nuclear alkylation. The selectivity of
xylene and mesitylene increased with increasing temperature with
maximum at 400 °C (Figs. 8 and 9). The overall catalytic activity and
selectivity depend on the acidity and basicity, specific surface area and
reaction condition (Velu and Swamy, 1994; Velu and Swamy, 1996; Di
Cosimo et al., 1998; Dumitriu et al., 1999; Jyothi et al., 2000; Sanchez
Valente et al., 2000). The basicity of calcined LDHs decreased in the
order Mg N Co N Cu N Ni N Zn.

3.7. Acid-base properties and catalytic activity

Since the alkylation of toluene with methanol is essentially a acid-

base reaction, the difference in activity and product selectivity could
be explained on the basis of difference in acid-base properties of the
catalysts. However, there is a continuous debate on the correlation
between acid-base properties and product selectivity. Alkylation of
aromatic hydrocarbon over acidic zeolites leads to alkylation of the
ring, while basic zeolites catalyse side chain alkylation (Pines and
Arrigo, 1957). Itoh et al. (1980) using quantum chemical calculations,

Table 5
Decomposition of cyclohexanol over M (II)/M (III) LDHs.

Catalysts Cyclohexanol Product selectivity

conversion (wt.%)
Cyclohexene Cyclohexanone
MgAl-3.0 37.6 14.3 85.7
MgAl-4.0 36.1 13.8 86.2
MgAl-5.0 34.0 10.9 89.1
MgAl-7.0 28.2 6.3 93.7
MgAl-10.0 21.4 1.3 98.7
CoAl-3.0 39.3 34.1 65.9
NiAl-3.0 50.4 92.8 7.2
CuAl-3.0 52.2 95.6 4.4
ZnAl-3.0 36.5 21.3 78.7

Temperature: 300 °C.

Catalyst weight: 1.5 g.
Fig. 8. Methylation of toluene: effect of temperature on yield of xylene. Flow rate: 2 ml/h.
142 R. Manivannan, A. Pandurangan / Applied Clay Science 44 (2009) 137–143

Table 6 basic sites and the aromatic ring adsorbed on acidic sites. As the
Effect of methanol and formaldehyde on the yield of ethylbenzene and styrene. strength of basic sites increases, the extent of side chain alkylation of
Catalysts Methanol Formaldehyde toluene also increases yielding ethyl benzene and styrene.
Ethylbenzene Styrene Ethylbenzene Styrene The increase in selectivity for side chain alkylated products
(mol%) (mol%) (mol%) (mol%) depended on the Mg/Al ratio. Low Al content (Mg/Al N 5.0) favored
MgAl-3.0 22.3 9.6 14.9 11.8
the side chain alkylated products, but decreased the toluene
MgAl-4.0 19.2 12.0 13.7 12.5 conversion. The addition of small amounts of Al strongly increased
MgAl-5.0 14.6 11.3 9.4 12.0 the surface density of acid base sites. The activity decreased in samples
MgAl-7.0 10.2 9.1 5.2 10.1 with low Al content due to the formation of amorphous Al–O phases
MgAl-10.0 7.0 8.9 4.6 9.8
that partially covered Mg–O pairs and decreased the concentration of
CoAl-3.0 15.8 – 10.0 2.1
NiAl-3.0 14.2 – 6.1 – surface O2− anions (Di Cosimo et al., 1998). At higher Al contents
CuAl-3.0 16.3 – 8.9 – (5.0 N Mg/Al) the density of basic sites increased because the Al3+
ZnAl-3.0 16.8 – 7.5 – cations in MgO lattice created a defect in order to compensate the
Temperature: 300 °C. positive charge and the adjacent oxygen anions became coordina-
Toluene: Methanol = 1:1. tively unsaturated.
Catalyst weight: 1.5 g. On Mg/Al LDHs, the nuclear alkylation increased with increasing Al
Flow rate: 2 ml/h.
content. At Mg/Al ratios 3 and 4 relatively high density of Al–O pairs is
present and lower and medium strength basic sites Al3+–O2− pairs do
not contribute much to the surface basicity. In contrast both Mg2+ and
suggested that the co-operative action of acid and base sites is very Al3+ cations provide Lewis acidic sites.
important in the side chain alkylation. We tried to determine the
basicity of calcined samples by a titration technique as described in 4. Conclusion
and investigated the acid-base properties of LDHs for the reaction
with cyclohexanol. The dehydrogenation activity of cyclohexanol into We reported the alkylation of toluene with methanol over calcined
cyclohexanone was correlated with basic sites and the dehydration LDHs. Optimum condition for the yield of ethyl benzene by side chain
into cyclohexene in the presence of acidic sites (Jyothi et al., 2000; alkylation of toluene with methanol was 300 °C and WHSV 1.33 h− 1.
Sanchez Valente et al., 2000; Bezouhanova and Al-Zihari, 1991). Mg/Al-LDH yielded mainly ethyl benzene and styrene by side chain
It can be detected when Mg/Al LDHs were used, although the solid alkylation, while the other LDHs mainly gave nuclear alkylated
possess acidic–basic sites due to overall basicity of the solids, products viz., xylene and mesitylene. Calcined Mg/Al-LDH was the
cyclohexanone were formed predominantly than cyclohexene most active catalyst for the side chain methylation of toluene under
(Table 5). The higher selectivity of cyclohexene in the case of Mg/Al– the chosen conditions.
3.0 LDH compared to other LDHs indicated the higher acidity of this
catalyst which can be attributed to the dissolution of more amount of References
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