Applied Catalysis A: General 239 (2003) 11–16

Vapour-phase nitration of benzene over superacid

WO3/ZrO2 catalysts
V.V. Brei∗ , S.V. Prudius, O.V. Melezhyk
Institute of Surface Chemistry of the National Academy of Sciences of Ukraine, 17 General Naumova Str., Kyiv 03164, Ukraine
Received 5 February 2002; received in revised form 14 March 2002; accepted 16 May 2002

Abstract
Superacid WO3 /ZrO2 catalysts have been found to show a high activity and stability in the reaction of gas-phase nitration
of benzene with 70% HNO3 . At 170 ◦ C and under atmospheric pressure the yield of nitrobenzene is within 65–80% at 99%
selectivity for mononitrobenzene. The space time yield of nitrobenzene increases with increasing flow rate of reagents and
amounts to 0.64 g/(gcat h).
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Nitration of benzene; Solid superacids; Zirconia; WO3 /ZrO2 , catalyst

1. Introduction Usually super acidic WO3 /ZrO2 systems possess

Nitrobenzene is known to be a starting material
for producing such useful substances as aniline, ben-
zidine, metanilic acid. The commercial production
of nitrobenzene involves nitration of benzene with a
mixture of sulfuric and nitric acids. One of the disad-
vantages of this method is a significant consumption
of sulfuric acid and the necessity of utilizing the
waste acid mixture. In view of this fact, vapour-phase
nitration of benzene with nitric acid over solid acid
catalysts may have much promise. Nowadays studies
have been conducted on the processes of gas-phase
nitration of a number of aromatic compounds [1],
toluene [2], and benzene [1,3–6] using such solid
acids as zeolites and layer aluminosilicates, sulfuric
acid supported on silicas, mixed oxides and superacid
oxide systems including WO3 /ZrO2 .
∗ Corresponding author. Tel.:+38-44-444-82-30;
fax: +38-44-444-35-67.
E-mail address: brei@alfacom.net (V.V. Brei).
a relatively low specific area (30–70 m2 g−1 ) [7–9].
A method has been designed for synthesis of meso-
porous WO3 /ZrO2 with a high specific surface area
(S = 200–300 m2 g−1 ) using polyvinyl alcohol as a
template [10]. The present work is concerned with re-
searches into processes of vapour-phase nitration of
benzene over superacid WO3 /ZrO2 samples synthe-
sised by various methods. For comparison a study is
also made on some other acid oxide materials.
2. Experimental
Synthesis of the first WO3 /ZrO2 sample was per-
formed by improved co-precipitation method [9]. A
2.60 ml of aqueous meta-tungstate solution (contain-
ing 800 mg of W in 1 ml) was added to solution of
ZrOCl2 ·8H2 O (30 g in 300 ml of water). This propor-
tion of reagents corresponds to mass content of WO3
in oxide material of 18.6% (molar ratio W:Zr ≈ 1:8).

0926-860X/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 3 8 3 - 6
12 V.V. Brei et al. / Applied Catalysis A: General 239 (2003) 11–16
The mixed solution was heated to boiling and then a
solution of 5.6 g of urea in 10 ml of water was added.
Then the reaction mixture was boiled under reflux for
6 h and then cooled. After that 11 ml of 12 M ammo-
nia was added to the solution at room temperature (pH
9), the precipitate was filtered off and washed with
water. The product was dried first in stream of hot air
and then for 24 h in drying box at 100 ◦ C. After cal-
cination of the sample at 800 ◦ C for 3 h, its specific
surface area was equal to 40 m2 g−1 .
The second mesoporous sample of WO3 /ZrO2 with
molar ratio W:Zr = 1:4 (WO3 = 32 wt.%) was pre-
pared by the sol–gel method using polyvinyl alcohol
as a template [10]. After calcination at 700 ◦ C, the
specific surface area of such a sample was equal to
270 m2 g−1 , the average diameter of the pores amounts
to 25 Å.
The sample of WO3 /TiO2 with mass content of
WO3 = 15% was prepared by the method of impreg-
nation of titanium dioxide (DuPont; 17 m2 g−1 ) with
a metatungstate solution, then the material obtained
was extruded, dried at 110 ◦ C, heated for 2 h to a tem-
perature of 800 ◦ C and kept stand at this temperature
for 3 h in air.
Zeolite HZSM-5 (Si:Al = 26) sample was pre-
pared with using familiar template method. The con-
centrations of acid sites determined for this sample
by back-titration with n-butylamine adsorbed from
toluene solutions make up 0.35 mmol g−1 . The acidity
of the sample determined by gas-phase adsorption of
Hammett indicators did not exceed H0 = −8.3.
Fumed silica–aerosil (270 m2 g−1 ) was produced
by the experimental plant of the Institute of Surface
Chemistry (Ukraine). The content of silanol groups
was about 0.3 mmol g−1 , acidity of the sample deter-
mined by use of Hammett indicators was characterised
by H0 ≤ 3.3.
UV–VIS reflectance spectra of powdered samples
were recorded by Specord M-40 spectrophotometer
with using MgO as a reference. Adsorption spectra
of the samples were calculated from their diffuse re-
flectance ones according to the Kubelca–Munk func-
tion, F(R) = (1−R)2 /2R.
The acidity of samples was tested in the cumene
dealkylation, using the method of temperature-
programmed reaction (TPR) with mass-spectrometric
control of reaction products [9]. Sequentially in 8 s
the currents of C6 H5 + (77 amu) and C6 H6 + (78 amu)
ions were registered. The formation of benzene was
observed, when the intensity of 78 amu becomes more
than intensity of 77 amu.
Catalytic experiments were performed in a flow
glass reactor with diameter of 0.7 cm with a fixed cat-
alyst bed under atmospheric pressure. The volume of
a catalyst was equal to 1 cm3 . Carrier gas (nitrogen)
was passed through the reactor at a rate of 6 ml min−1 .
Benzene and 70% nitric acid were introduced into
the reactor through capillaries, with their rate of feed
being preliminarily calibrated. The experiments were
conducted at 170 ◦ C, and experiment time was equal
to 5 h as a rule. The reaction products were col-
lected into a special reservoir. The organic fraction
extracted with hexane was put into a weighted beaker
and kept for several hours in air at room temperature
up to a practically complete evaporation of volatile
solvents (benzene and hexane). The experiments con-
ducted showed that the nitration effected with an
excess of benzene (molar ratio C6 H6 :HNO3 > 1,
see Table 1) led to the formation of a hardly volatile
product, its IR spectrum being coincided with that
of pure nitrobenzene and its melting temperature be-
ing equal to 5.4–5.6 ◦ C, close to 5.76 ◦ C for pure
nitrobenzene.
In order to analyse the products, a Hewlett-Packard
G1530A gas chromatograph was used with polyethy-
lene glycol as a stationary phase. The chromatographic
analysis showed that the content of mononitrobenzene
in the nitration products was of 98.2–99.8 wt.%. The
main impurity was benzene (up to 1.7 wt.%). Other ad-
mixtures were negligible (about 10−4 to 10−2 wt.%).
Thus, the nitration under the above-mentioned condi-
tions proceeds selectively with formation of mononi-
trobenzene. However, when nitric acid was present in
an excess, one could observe the formation of prod-
ucts that were solid at room temperature and looked
like a mixture of polynitrobenzenes.
3. Results and discussions
In the XRD patterns of co-precipitated and meso-
porous WO3 /ZrO2 samples calcined at 700–800 ◦ C
predominantly tetragonal phase of ZrO2 was ob-
served. The presence of tetragonal or cubic phase of
ZrO2 is a necessary condition for obtaining superacid
WO3 /ZrO2 materials [7–9].
 V.V. Brei et al. / Applied Catalysis A: General 239 (2003) 11–16
Fig. 1. UV–VIS reflectance spectra of co-precipitated WO3 /ZrO2 (1) and mesoporous WO3 /ZrO2 (2).
The second necessary condition for preparing su-
peracid WO3 /ZrO2 systems is the presence of WO3
clusters of definite optimal size, characterized by the
width of forbidden zone E0 = 3.0–3.2 eV [11]. In
Fig. 1, there are displayed UV–VIS diffuse reflectance
spectra of co-precipitated and mesoporous WO3 /ZrO2
samples. Inflexions of curves in the low-energy re-
gion of the plots indicate the presence of WO3 clus-
ters with the E0 values of 3.0–3.3 eV. These sample
have been tested in the reaction of benzene nitration.
The synthesized WO3 /ZrO2 samples, characterized by
another E0 values, have shown low activity in this
reaction.
The use of the Hammet indicators for evaluation
of the acidity of tungstate-containing zirconia is
complicated by yellow color of calcined WO3 /ZrO2
samples. According to Hino and Arata [12], such
samples are characterized by the value of H0 ≤
−14.5. We have used cumene cracking test-reaction
for estimation of acidity of the samples. In the TPR
spectra for the WO3 /ZrO2 samples a benzene peak
was recorded at 120–130 ◦ C, whereas for a less acidic
WO3 /TiO2 and HZSM-5 samples peaks of benzene
13
release were observed at 160 and at 190 ◦ C, respec-
tively (Fig. 2).
Gravimetric data on desorption of ammonia from
the surface of WO3 /ZrO2 samples allow one to esti-
mate the concentration of acid sites (Fig. 3). The con-
tent of sites that are more acidic than in HZSM-5 (des-
orption of ammonia at temperatures above 290 ◦ C) is
about 0.03 mmol g−1 for co-precipitated sample and
is about 0.12 mmol g−1 for mesoporous WO3 /ZrO2
sample.
As it is evident from Table 1, a repeated running
of the process with the same sample of WO3 /ZrO2
catalyst at closely spaced values of LHSV leads to
a rather small decrease in the yield of nitrobenzene
within 68–77% (cf. experiments #1–2, 8–10, 11–13).
Thus, the catalysts on the base of WO3 /ZrO2 demon-
strate their stability at 170 ◦ C for at least 10 h.
Preliminary reduction of WO3 /ZrO2 to WOx /ZrO2
with hydrogen at 400 ◦ C (experiment #8) does not ex-
ert any substantial effect on its activity. In an oxidiz-
ing medium an oxidation proceeds for clusters WOx
to WO3 . This is proved by change of sample colour
from the initial deep-blue to yellow. It is probable that
14 V.V. Brei et al. / Applied Catalysis A: General 239 (2003) 11–16

Fig. 2. TPR spectra of benzene formation (78 amu) from cumene (77 amu) adsorbed on WO3 /ZrO2 (a), WO3 /TiO2 (b) and HZSM-5 (c)
(b = 10 K/min).

in the presence of water vapours Lewis acid sites on
the surface of unreduced WO3 /ZrO2 transform into
strongly acidic Brönsted sites.
The dependence of the space time yield of ni-
trobenzene (STY) on flow rate of 70% HNO3 is
illustrated in Fig. 4. It is seen that as the flow rate is
raised up to SV=0.5 ml/gcat /h, there is an almost pro-
portional rise in the STY values at the nitrobenzene
yield at the level of 55–80%. The optimum combina-
tion of the catalyst efficiency and nitrobenzene yield
(STY = 0.40 g/(gcat h) at the yield of 66%) is attained
in the case of experiment #5. The co-precipitated
and mesoporous WO3 /ZrO2 samples show close val-
ues of YNB = 75–77% at the same LHSV values
(experiments #1 and 11). Nevertheless, the value of
STYNB for mesoporous sample is greater for 40%
than that for co-precipitated one. The mesoporous
sample has also higher content of strong acid sites
(Fig. 3).
The WO3 /ZrO2 catalysts prepared are characterised
by the nitrobenzene yield at 170 ◦ C within 65–80%. A
similar yield of nitrobenzene (73%) was observed on
the ZrO2 –WO3 composition with high mass content
of WO3 (66%) at 150 ◦ C [4].
For comparison with superacid WO3 /ZrO2 sam-
ples, some other oxide materials were also tested (see
Table 1). The aerosil (H0 ≤ 3.3) showed a low activ-
ity in the reaction with YNB = 7%. It is an expected
result, because a low acidic silanol groups on silica
surface cannot pass the protons to nitric acid (pKa
∼ −2) for the formation of nitronium cations. The
HZSM-5 zeolite (H0 ≤ −8.2) is more active (YNB =
 V.V. Brei et al. / Applied Catalysis A: General 239 (2003) 11–16 15

Fig. 3. Gravimetric curves of ammonia thermodesorption for co-precipitated (1) and mesoporous (2) WO3 /ZrO2 samples.

Table 1
Data on vapour-phase nitration of benzene at 170 ◦ C
No. Catalyst LHSV (ml/(cm3cat h)), C6 H6 :HNO3 Ya (%) STYb
SV (ml/(gcat h)) (molar ratios) (g/(gcat h))
C6 H6 HNO3

1 Co-precipitated WO3 /ZrO2 (1.80 g) 0.3 (0.17) 0.1 (0.06) 2.16 77 0.09
2 Sample after the previous ex- 0.3 (0.17) 0.1 (0.06) 2.16 70 0.08
periment (repeatedly)
3 Co-precipitated WO3 /ZrO2 (1.99 g) 0.3 (0.15) 0.2 (0.10) 1.08 80 0.15
4 Repeatedly 0.3 (0.15 0.1 (0.05) 2.16 65 0.05
5 Co-precipitated WO3 /ZrO2 (1.95 g) 1.1 (0.56) 0.6 (0.31) 1.32 66 0.40
6 Co-precipitated WO3 /ZrO2 (2.04 g) 0.8 (0.39) 0.5 (0.25) 1.15 69 0.32
7 Repeatedly 1.6 (0.79) 0.9 (0.44) 1.28 54 0.51
8 WOx /ZrO2 , (1.85 g) 0.3 (0.16) 0.1 (0.05) 2.16 75 0.10
9 Repeatedly 0.3 (0.16) 0.1 (0.05) 2.16 72 0.10
10 Repeatedly 0.4 ((0.22 0.2 (0.11) 1.44 74 0.135
11 Mesoporous WO3 /ZrO2 (1.16 g) 0.3 (0.26) 0.1 (0.09) 2.16 75 0.13
12 Repeatedly 0.4 (0.34) 0.1 (0.09) 2.88 68 0.14
13 Repeatedly 0.4 (0.34) 0.1 (0.09) 2.88 68 0.14
14 Mesoporous WO3 /ZrO2 (1.32 g) 1.9 (1.44) 0.9 (0.68) 1.52 40 0.64
15 WO3 /TiO2 (1.30 g) 0.4 (0.31) 0.2 (0.15) 1.44 25 0.07
16 HZSM-5 (0.60 g) 0.3 (0.5) 0.2 (0.33) 1.08 14 0.08
17 Aerosil A-300 (0.30 g) 0.4 (1.33) 0.2 (0.67) 1.44 7 0.07
a Yield of nitrobenzene in terms of the consumed HNO3 .
b The space time yield of nitrobenzene (g/(gcat h)).
16 V.V. Brei et al. / Applied Catalysis A: General 239 (2003) 11–16
Fig. 4. Space time yields (g/(gcat h)) of nitrobenzene for co-precipitated WO3 /ZrO2 (䊏) and mesoporous WO3 /ZrO2 (
).
14%). The WO3 /TiO2 system demonstrates the ac-
tivity with YNB = 25%, but its result is lower than
that of WO3 /ZrO2 . Besides, of significance is also the
fact that when these oxide materials are tested, one
can observe a formation of nitrogen dioxide at the re-
actor outlet, what is in contrast to the situation with
WO3 /ZrO2 .
The observed decrease in catalytic activity in the
order of WO3 /ZrO2 > WO3 /TiO2 > HZSM-5 >
SiO2 correlates with that in acidic strength of their
B-sites. It is agreed with the familiar mechanism for
nitration of aromatics. The strong B-sites with H0 >
−10 are necessary for an effective formation of inter-
mediate NO2 + ions from nitric acid.
4. Conclusions
The acidity of oxide materials is an important
factor that controls the yield of nitrobenzene in the
process of vapour-phase benzene nitration. The su-
peracid WO3 /ZrO2 systems demonstrate a high activ-
ity (YNB = 65–80%) and selectivity (up to 99.8%) in
this reaction at 170 ◦ C.
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