Applied Catalysis A: General 219 (2001) 125129

Catalytic decomposition of cumene hydroperoxide

into phenol and acetone
Rosilda Selvin, G.R. Rajarajeswari,
L. Selva Roselin, V. Sadasivam,
B. Sivasankar, K. Rengaraj
Department of Chemistry, Anna University, Chennai 600025, India
Received 10 November 2000; received in revised form 22 May 2001; accepted 22 May 2001

Abstract
The decomposition of cumene hydroperoxide (CHP) was carried out in a batch reactor over supported solid acid catalysts,
acid-activated montmorillonite K10 (Mont. K10) and metal-ion-exchanged (Mont. K10), at 3060 C. The products were
phenol and acetone. Supported dodecatungstophosphoric acid (DTPA) showed 100% conversion within 5 min at 30 C; the
results obtained over acid-activated (Mont. K10) were also comparable. The type of acidity and the strength were determined.
The correlation of catalytic activity with acidity revealed that both Lewis and Bronsted acid sites promote the decomposition.
The reaction was first-order with respect to CHP. The results indicate that heterogeneous catalysts may be used instead of
sulfuric acid for selective decomposition of CHP into phenol and acetone with 100% conversion. 2001 Elsevier Science
B.V. All rights reserved.
Keywords: Cumene hydroperoxide; Supported reagent; Heteropoly acid; Modified clay; Phenol; Acetone

1. Introduction
The acid-catalyzed decomposition of cumene hydroperoxide (CHP) into phenol and acetone is an important industrial process. Sulfuric acid is used almost
exclusively as a catalyst in the industry. Various Bronsted and Lewis acids in homogeneous systems [13],
cation-exchanged resins in a pseudo-homogeneous
system [4] and zeolites in heterogeneous systems
[5] have been reported for various reactions. The
environmental hazards resulting from the use of conventional acid catalysts in a homogeneous system
Corresponding author.
E-mail address: rengaraj@movemail.com (K. Rengaraj).

can be eliminated by a more effective heterogeneous

catalytic method from the viewpoints of environmental friendliness, ease of separation of products
and ease of regeneration of the catalyst. It is evident
from the literature that supported reagent solid acid
catalysts based on metal chlorides and heteropoly
acids impregnated on inexpensive inorganic oxides
[6,7] and modified montmorillonite K10 (Mont. K10)
[8] catalysts promote various organic reactions. The
present paper is aimed at a systematic investigation of the catalytic activity of transition and inner
transition metal chlorides and dodecatungstophosphoric acid (DTPA) impregnated on supports
such as Mont. K10, silica, titania and MCM-41
(silicious), metal-ion-exchanged Mont. K10 and

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
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R. Selvin et al. / Applied Catalysis A: General 219 (2001) 125129

acid-activated Mont. K10 towards the decomposition

of CHP.

repeated for all other catalysts by maintaining the

required temperature.
2.4. Acidity measurements

2. Experimental
2.1. Chemicals
Zinc chloride, ferric chloride, lanthanum chloride,
cerium chloride, DTPA, CHP (80% in cumene),
cumene and Mont. K10 (Fluka) were commercial
samples and were used without further purification.
MCM-41 (silicious) was prepared according to the
procedure Beck et al. [9] by using sodium metasilicate
as the source for silica.
2.2. Preparation of catalysts
Supported metal catalysts were prepared by wet impregnation method. The solid residue was powdered,
dried and activated at 120 C for 3 h prior to use. Zn2+ ,
Fe3+ , La3+ and Ce3+ exchanged Mont. K10 were prepared by mixing Mont. K10 with each one of the metal
chloride and stirring the mixture for 24 h at room temperature. The clay was then separated, washed well
with doubly distilled water to eliminate chloride ions
and dried in an air oven at 120 C for 3 h. Mont.
K10 was acid-activated by treating independently with
0.31 M hydrochloric acid solutions. DTPA on various supports were prepared by the incipient wetness
method [10].
2.3. Decomposition of cumene
hydroperoxide (CHP)
CHP in cumene was taken in a 100 ml RB provided
with an upright condenser with a guard tube. The RB
flask was immersed on a thermostatic oil bath mounted
on a magnetic stirrer. The reagent was preheated to
the desired temperature and one of the solid catalysts
was added.
The progress of the reaction was monitored by withdrawing samples from the reactor and subjecting them
to gas chromatographic analysis (Hewlett-Packard
5890), using an OV-101 column (length 2 m, i.d.
1/8 in.) and a FID detector. The products were identified and confirmed by GC-MS (varian star 3400 GC
column varian DB-1 megapore). Experiments were

The vapor phase adsorption of pyridine as probe

molecule [11] was adopted to find out the acidity of
catalyst samples. The nature of acid sites was characterized on the basis of IR spectral data of pyridine
adsorbed catalyst samples. The nature and strength of
acidic sites were determined by differential scanning
calorimetric studies.
3. Results and discussion
Under the experimental conditions, CHP decomposed into phenol and acetone over all the catalyst
systems in equimolar quantities. No other product was
obtained. An ionic decomposition mechanism may
be suggested for the decomposition of CHP by solid
acid catalysts, which is analogous to that reported by
Seubold and Vaughan [2].
3.1. Decomposition of CHP over
various catalysts
The effect of important reaction parameters for the
decomposition of CHP was studied and the kinetic
parameters were evaluated on silica impregnated with
ZnCl2 .
The effect of initial concentration of CHP in the
range of 1.313.3 mM in cumene at a constant volume of the reaction mixture (10 ml) was investigated
over 0.5 g of the catalyst at 30 C. The percentage
conversion was found to decrease as the amount of
CHP increased, as shown in Fig. 1. The optimum concentration of CHP was found to be 2.7 mM in 9.5 ml
cumene.
The effect of reaction temperature on the decomposition of CHP (2.7 mM in 9.5 ml cumene) catalyzed by 0.25 g catalyst was investigated in the
temperature range of 3050 C. In general, as the
temperature increased, the decomposition also increased. The experimental data are shown in Fig. 2.
Under these experimental conditions, the reaction
followed first-order kinetics. The plot of ln A/(A X)
versus time at different temperatures gave straight

R. Selvin et al. / Applied Catalysis A: General 219 (2001) 125129

Fig. 1. Effect of [CHP] for conversion by zinc chloride on silica

as a function of time.

127

Fig. 3. Kinetics plot for the conversion of CHP catalyzed by zinc

chloride on silica.

lines passing through the origin, indicating that the

decomposition reaction followed first-order kinetics
with respect to CHP, as shown in Fig. 3. The natural
logarithm of rate constants plotted against reciprocal of absolute temperature gave a straight line.
The activation energy of the reaction was calculated
as 23.9 kJ/mol.

3.2. Decomposition of CHP on zinc chloride

impregnated on various supports

Fig. 2. Effect of temperature for the conversion of CHP by zinc

chloride on silica.

Fig. 4. Conversion of CHP by zinc chloride on various supports

as a function of time.

The catalyst samples (each 0.5 g) of ZnCl2 impregnated on various supports (2 mM/g loading) such as
(Mont. K10), titania and MCM-41 were tested at 30 C.
The results are shown in Fig. 4.

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R. Selvin et al. / Applied Catalysis A: General 219 (2001) 125129

Table 1
Catalytic activity of impregnated/ion-exchanged Mont. K10 for the conversion of CHP
Impregnated metal chloride
ZnCl2
FeCl3
CeCl3
LaCl3

Conversion of CHP (%)

Ion-exchanged metal ion

Conversion of CHP (%)

100
66
48
36

Zn2+

80
92
100
95

Fe3+
Ce3+
La3+

Table 2
Percentage conversion of CHP on various catalysts
Support material

Acid activation

Mont. K10
Mont. K10
Mont. K10
Mont. K10
Mont. K10
Titania
Silica
MCM-41

0.3 M
0.5 M
0.7 M
1.0 M

Impregnated
with

Conversion
(%)

DTPA
DTPA
DTPA
DTPA

100
100
100
100
95
100
100
100

HCl
HCl
HCl
HCl

tested for their activity. In each case, 2.7 mM of CHP

in 9.5 ml cumene was used over 0.5 g catalysts at
50 C for 30 min. The results are shown in Table 1.
3.4. Acid-activated Mont. K10 and
supported DTPA catalysts
The results obtained for the activity of acid-activated
Mont. K10 (0.3, 0.5, 0.7 and 1 M) and DTPA impregnated on various supports (Mont. K10, silica, titania
and MCM-41) are presented in Table 2.

3.3. Metal chloride impregnated/exchanged

Mont. K10

3.5. Correlation of catalytic activity

and surface acidity

Each metal chloride (ZnCl2 , FeCl3 , LaCl3 and

CaCl3 ) impregnated on Mont. K10 and Mont. K10
exchanged with Zn2+ , Fe3+ La3+ and Ca3+ were

Mont. K10 carries weak acid sites and Bronsted acid sites (Table 3). Acid activation of Mont.
K10 enhanced the strength of Bronsted acid sites as

Table 3
DSC and FT-IR data for pyridine adsorbed catalysts
Catalyst

Peak temperature ( C)
HPY

LPY

H (exo) (J/g)
BPY

IR frequency (cm1 )
HPY

Mont. K10

LPY

BPY

1441
1637
122

425

1597
1543
1494

ZnCl2 /Mont. K10

138.2
Mont. K10-0.3 M HCl
Mont. K10-0.5 M HCl
Mont. K10-0.7 M HCl
DTPA/SiO2 (40 wt.% loading

382

122
115.8
123
104.5

205

430

489
490
409

48
47.2
34

441

462

1449

1637

1608

1543
1636
1636
1635
1636

1490

1490

1449
1543
1637

DTPA/MCM-41 (40 wt.% loading)

99.1

208

443

1808

1490

1449
1543

R. Selvin et al. / Applied Catalysis A: General 219 (2001) 125129

indicated by the shift in peak temperature for the desorption of pyridine from 424 to 489 C in DSC thermograms. It is supported by the IR absorption band
at 1637 cm1 , which indicates the presence of strong
Bronsted acid sites. The results obtained are in accordance with the literature reports that strong Bronsted
acid sites are active for CHP decomposition [5]. Acid
treatment replaces the interlamellar cations with protons and also leaches out Al3+ ions from the octahedral
layers. The protons exchanged for the interlamellar
ions and the leached hydrated alumina occupying the
cation-exchange sites contribute to the enhanced acidity [12]. Impregnation of DTPA on silica and MCM-41
created a higher density of strong Bronsted acid sites
(vide H values, Table 3). These Bronsted acid sites
facilitated CHP decomposition reaction. Impregnation
of ZnCl2 on Mont. K10 created Lewis acidity which
also helped the decomposition of CHP, as supported
by the reports in [3].

4. Conclusions
The study of decompositions of CHP over the various catalysts leads to the following conclusions: all
the catalysts under study were active and their activity
was comparable. They exhibit maximum selectivity
for the formation of phenol and acetone. Both Lewis

129

and Bronsted acid sites favor the decomposition of

CHP. The reaction follows first-order kinetics with
respect to CHP. These solid acid catalysts are potential substitutes for sulfuric acid at the industrial level
for the above reaction.
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