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One-step synthesis of cumene from benzene and acetone over a bifunctional

catalyst

Article  in  Catalysis in Industry · October 2015

DOI: 10.1134/S2070050415040133

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ISSN 20700504, Catalysis in Industry, 2015, Vol. 7, No. 4, pp. 282–286. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © O.V. Shutkina, O.A. Ponomareva, I.I. Ivanova, 2015, published in Kataliz v Promyshlennosti.

CATALYSIS IN CHEMICAL
AND PETROCHEMICAL INDUSTRY

OneStep Synthesis of Cumene from Benzene and Acetone

over a Bifunctional Catalyst
O. V. Shutkinaa, O. A. Ponomarevaa, b, and I. I. Ivanovaa, b
a
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
b
Lomonosov Moscow State University, Moscow, 119991 Russia
email: shutkina@ips.ac.ru, oaponomareva@phys.chem.msu.ru, ivanova_ii@ips.ac.ru
Received March 25, 2015

Abstract—The hydroalkylation of benzene with acetone on a bifunctional solid catalyst containing silica
supported copper and beta zeolite is studied. The effects of temperature (100–230°C), pressure (0.1–3 MPa),
and composition of the reaction mixture (benzene : acetone) on the process are revealed. It is shown that
optimal conditions for the reaction are the following: temperature of 150–170°C, pressure of 1–3 MPa, and
(4–9) : 1 molar ratio of benzene to acetone. At 170°C, 1 MPa, and a 9fold dilution of acetone with benzene,
the conversion of acetone is as high as 98% and the yield of the desired products (cumene and diisopropyl
benzenes) is 94%, which is comparable to the parameters of the industrial process of benzene alkylation with
propylene. Using acetone as an alkylating agent instead of propylene makes the proposed hydroalkylation
method more attractive, due to the excess of cheap acetone.

Keywords: cumene, isopropylbenzene, acetone, hydroalkylation of benzene

DOI: 10.1134/S2070050415040133

INTRODUCTION become even more acute with the commissioning of

Nowadays cumene (isopropylbenzene) is produced
via the alkylation of benzene with propylene on
Friedel–Crafts catalysts, kieselguhrsupported phos
phoric acid, or zeolites in petrochemical industry. The
world production of cumene is more than 8 million tons
per year [1], including approximately 600000 tons of
cumene produced in Russia [2]. The sales volume of
cumene was $15.5 billion in 2012, and the contract
values will total $24.1 billion by 2018 [3]. The world
demand for cumene is due to 97% of it being used in
the production of phenol [4]. Phenol itself is a precur
sor for plastics (bisphenol A), phenolformaldehyde
resins, caprolactam, medicines, and so on [5].
Because of the rising demand for such products, the
production of phenol is growing annually by 10% [6].
Acetone is formed as a byproduct of the cumene pro
cess for phenol production (0.62 tons of acetone are
produced for every ton of phenol). However, the mar
ket for acetone is not as wide as that for phenol, and as
the consumption of phenol increases, the problem of
acetone recycling will inevitably reach new levels.
An additional supply of acetone is expected from
the biofuel industry. For instance, the acetone content
in the byproducts of biobutanol synthesis is 45–48%
[7, 8]. An increase in the production of biobutanol will
therefore be accompanied by increased production of
acetone. The problem of acetone overproduction will
new plants for the production of biofuels.
It is therefore important that we develop new high
performance and environmentally friendly processes
to convert acetone into hydrocarbons, which are valu
able petrochemical raw materials. The most promising
way is to use acetone in the production of cumene via
the hydroalkylation of benzene with acetone. This
method of cumene production will allow us to replace
the propylene traditionally used as an alkylating agent
and use propylene for the synthesis of polypropylene,
plastic, rubber, and so on. In addition, the synthesis of
cumene from benzene and acetone will provide an
independent way of cumene synthesis from the avail
ability of propylene, which is produced by the cracking
of crude oil and the pyrolysis of gasoline fractions. This
is of special interest, since our oil reserves are limited.
Cumene can be synthesized from acetone and ben
zene in two or three stages: (1) the hydrogenation of
acetone to isopropanol; (2) the dehydration of isopro
panol to propene; and (3) the alkylation of benzene
with isopropanol or propylene.
There are many studies on each of these stages, but
data on the onestep process of benzene hydroalkyla
tion with acetone are very scarce [9]. The influence of
the process conditions on catalytic performance is
poorly discussed, although it is wellknown that the
process conditions can dramatically change the direc
tion of the reaction.

282
 ONESTEP SYNTHESIS OF CUMENE FROM BENZENE AND ACETONE
This work is devoted to the study of the onestep
process of benzene hydroalkylation with acetone over
a bifunctional catalyst system and the influence of
temperature, pressure, and composition of the reac
tion mixture. Silicasupported copper, which can
selectively hydrogenate acetone to isopropanol in the
presence of benzene, was selected as the hydrogenat
ing component of the catalyst [10]. BEAtype zeolite,
a stateoftheart industrial catalyst for the alkylation
of benzene with propylene, was selected as an acidic
component.
EXPERIMENTAL
Commercially available betazeolite (BEA), pro
vided by Zeolyst (SiO2/Al2O3 = 25), was used as zeolite
component. To obtain the Hform of zeolite, the
NH4form of a sample was calcined in a flow of mois
turefree air at 550°C for 6 hours. To obtain the hydro
genating component of the catalyst, 0.5–1.0 mm frac
tions of silica gel were subjected to incipient wetness
impregnation with an aqueous solution of Cu(NO3)2
(assuming 11 wt % metal in the sample), left wet for a
day, and then dried for 3 hours in an oven at 100°C.
The sample was then oxidized in an air flow at 450°C
for 4 hours and reduced in a hydrogen flow at 250°C
for 4 hours. A bifunctional catalyst containing the
hydrogenating and alkylating components was desig
nated as Cu/SiO2–BEA.
Benzene hydroalkylation with acetone was studied
in the continuousflow mode. The catalytic reaction
was carried out in the gas–liquid mode after diluting
the reaction mixture (2 mL/h) with nitrogen
(15 mL/min) in the temperature range of 100–230°C
at pressures ranging from 0.1 to 3 MPa, weight hourly
space velocity (WHSV) 2.8 g/(gcat h), and at molar
ratios of [n(C3H6O) + n(C6H6)] : n(H2) = 1 : 1.2 and
n(C6H6) : n(C3H6O) = (1–9) : 1.
A portion of the catalyst was loaded into a reactor
with a capacity of 25 mL. The catalystcontaining
reactor was placed into a furnace, whose temperature
was remained constant within ±1°C using a tempera
ture controller (Termodat). Nitrogen and hydrogen
were fed into the system using a gas flow regulator
(Brooks). The raw materials for the reaction (a mix
ture of two components) was supplied to the reactor by
a pump (Unisit). All of the catalysts were pretreated
before feeding in the raw materials. The reactor tem
perature was first raised to 350°C over 40 minutes in a
stream of nitrogen (30 mL/min). The temperature of
350°C was then maintained for 20 minutes in the
stream of nitrogen. Finally, the temperature was low
ered to the reaction temperature and a stream of
hydrogen (15 mL/min) was fed into the reactor. After
15 minutes, the raw materials for the reaction were fed
in and the stream of hydrogen was brought to the
required level. The reaction products were separated
CATALYSIS IN INDUSTRY Vol. 7 No. 4 2015
283
into liquid and gas by a separator. The samples were
taken and analyzed by gasliquid chromatography on
a Kristall 2000M chromatograph equipped with a
flameionization detector and a quartz capillary col
umn coated with SE30 phase. Products were identi
fied via gas chromatography–mass spectrometry on a
Thermo DSQII device in combination with a Trace
GC gas chromatograph equipped with a quartz capil
lary column coated with DB5 phase.
The catalytic properties of the samples were char
acterized in terms of acetone conversion, selectivity,
and the yield of cumene. Since an excess of benzene
was usually present in the initial mixture, the conver
sion was calculated on the basis of the alkylating agent.
The acetone conversion (%) was calculated using
the formula
K = (mr/ms ) × 100,
where mr is the mass of the reacted acetone and ms is
the mass of the supplied acetone.
The selectivity of product i formation (wt %) was
determined as
Si = (mi/Σmi) × 100,
where mi is the mass of the ith product of the reaction
formed with the participation of acetone molecules.
The yield of the ith product of the reaction (wt %)
was calculated using the formula
Bi = K × Si/100.
RESULTS AND DISCUSSION
The synthesis of cumene (isopropylbenzene) via
benzene hydroalkylation with acetone can be sche
matically represented as
O
+ + H2 + H2O.
The temperature, pressure, and ratio of reaction
mixture components were varied in the experiments to
estimate the effect of reaction conditions on catalytic
process performance.
Effect of Temperature
The temperature of the hydroalkylation of benzene
with acetone was varied in the range of 100–230°C at
a pressure of 3 MPa and the following molar ratio of
the reactants: n(C3H6O) : n(C6H6) : n(H2) = 1 : 9 : 12.
It was found that the temperature had a significant
impact on both conversion and selectivity (Table 1),
but no appreciable effect on the stability of the catalyst
was observed. The figure shows the typical depen
dences of the parameters of benzene hydroalkylation
with acetone on the time on stream (TOS). The figure
demonstrates the stability of the catalyst during the
reaction.
284 SHUTKINA et al.

Table 1. Parameters of benzene hydroalkylation with acetone over the Cu/SiO2–BEA catalyst at different temperatures,
at 3 MPa, WHSV 2.8 h–1, a molar ratio n(C3H6O) : n(C6H6) : n(H2) = 1 : 9 : 12, and TOS 300 min

Temperature, °C
Parameter
100 130 150 170 200 230

Acetone conversion, % 60.1 80.0 96.0 98.3 97.7 95.7

Yield, wt %
C3H6 8.7 13.2 0.7 0.7 0.8 0.8
isopropanol 22.0 1.8 0.1 0.2 0.2 0.3
diisopropyl ether 15.9 0.3 0.0 0.0 0.0 0.0
mesityl oxide 0.5 0.0 0.0 0.0 0.0 0.0
cumene 12.3 58.9 81.7 83.9 82.9 76.7
tertbutylbenzene 0.0 0.8 0.8 1.8 4.0 7.4
diisopropylbenzenes 0.2 4.1 11.4 10.2 6.4 6.0
other 0.7 1.0 1.4 1.5 3.4 4.4

The conversion of acetone at temperatures of 100–
130°C does not exceed 80% because of kinetic limita
tions. At a temperature of 100°C, the cumene yield is
only 12.3% and significant amounts of isopropanol,
diisopropyl ether, and propylene are present among
the reaction products because of the small contribu
tion of the alkylation reaction. The content of acetone
hydrogenation products decreases, owing to the alky
lation reaction with increasing temperature. As a
result, the yields of cumene and diisopropylbenzenes
(DIPBs) reach 83.9% and 10.2% at 170°C, respec
tively. The further rise of temperature to 200–230°C
results in the increased amount of alkylaromatic side
products and decrease of the yields of cumene and
DIPS. This is explained by increased contribution of
the molecules formed from benzene and the products
of acetone condensation at the elavated temperatures.
These results concide with the data of Cunningham
et al. [11], who showed that the percent amount of
acetone condensation products grows as well with
temperature rising from 175 to 240°C, and these prod
ucts, along with propylene, can act as alkylating
agents. Based on these results, it may be concluded the
preferred temperature for the hydroalkylation of ben
zene with acetone is 170°C.
Effect of Pressure
A series of experiments with the pressure was varied
over the range of 0.1–3.0 MPa was performed at a
temperature of 170°C and a molar ratio of n(C3H6O) :
n(C6H6) : n(H2) = 1 : 9 : 12. The results (Table 2) indi

% Acetone conversion
100

80
Selectivity to cumene
60

40

20 Selectivity to diisopropylbenzenes
0
1 2 3 4 5 6
Time, h

Dependence of the parameters of the hydroalkylation of benzene with acetone on TOS under the following conditions: Cu/SiO2–BEA
catalyst; 230°C; 3 MPa; WHSV 2.8 h–1; and a molar ratio n(C3H6O) : n(C6H6) : n(H2) = 1 : 9 : 12.

CATALYSIS IN INDUSTRY Vol. 7 No. 4 2015

 ONESTEP SYNTHESIS OF CUMENE FROM BENZENE AND ACETONE 285

cate a significant change in process performance with Table 2. Parameters of benzene hydroalkylation with ace
increase of pressure favoring bimolecular reactions. tone over the Cu/SiO2–BEA catalyst at different pressures,
at 170°C, WHSV 2.8 h–1, a molar ratio n(C3H6O) : n(C6H6) :
Large amounts of unreacted propylene, mesityl n(H2) = 1 : 9 : 12, and TOS 300 min
oxide, mesitylene, tbutylbenzene, isobutylene, and
acetic acid are found among reaction products. The Pressure, MPa
acetic acid alongside with isobutylene is probably Parameter
formed during the decomposition of highly reactive 0.1 1 3
diacetone alcohol or mesityl oxide, both of which are
products of acetone condensation. Raising the pres Acetone conversion, % 33.9 98.0 98.3
sure to 1 MPa affects both the hydrogenation of ace
tone to isopropanol and its subsequent alkylation. This Selectivity, wt %
results in raising the conversion of acetone from ≈34 to C3H6 48.0 0.8 0.7
almost 100% and reducing the amounts of propylene
and isopropanol from 48% to less than 1% in the reac C4 gases 8.2 0.8 0.8
tion products as the pressure is raised from 0.1 to
3 MPa. isopropanol 0.0 0.1 0.2

The values of acetone conversion (≈97%) and the acetic acid 5.3 0.0 0.0
selectivity to cumene (≈86%) and DIPBs (≈11%) are
mesityl oxide 0.6 0.0 0.0
close at 1 and 3 MPa. Since raising pressure from 1 to
3 MPa does not result in significant changes in the cumene 23.8 85.1 85.4
main parameters of the process, subsequent experi
ments were carried out at 1 MPa pressure. mesitylene 4.7 0.0 0.0
tertbutylbenzene 7.4 1.4 1.8
Effect of Composition of Reaction Mixture diisopropylbenzenes 1.5 10.9 10.4
The molar ratio of benzene to acetone from one to other 0.6 0.8 0.7
nine was varied to determine the influence of process
parameters on reaction mixture composition. The
data given in Table 3 indicate that a high content of Table 3. Parameters of benzene hydroalkylation with
acetone in the mixture leads to large amounts of pro acetone over the Cu/SiO2–BEA catalyst at different
pylene and isopropanol in products. The percentage of molar ratios n(C3H6O) : n(C6H6), at 170°C, 1 MPa,
tri and diisopropylbenzenes among the alkylaromatic WHSV 2.8 h–1, a molar ratio of [n(C3H6O) + n(C6H6)] :
compounds (20.7%) at 4fold dilution of acetone with n(H2) = 1 : 1.2, and TOS 300 min
benzene is higher than that at 9fold dilution (11.8%).
The selectivities to mono, di, and triisopropylben Molar ratio n(C3H6O) : n(C6H6)
zenes upon the 4 and 9fold dilution of acetone with Parameter
benzene are almost equal 97%, and are in good agree 1:1 1:4 1:9
ment with the published data for the alkylation of ben
Acetone conversion, % 77.3 96.5 98.0
zene with isopropanol [12–14].
Yield, wt %
Thus, the hydroalkylation of benzene with acetone
over a catalyst containing 11Cu/SiO2 and BEA zeolite C3H6 35.3 0.5 0.8
should be performed under the following conditions: C4 gases 0.2 0.3 0.8
170°C; 1 MPa; n(C3H6O) : n(C6H6) : n(H2) = 1 : 9 : 12;
and WHSV 2.8 h–1. Wherein the yield of cumene is isopropanol 11.1 0.1 0.1
83.4% at the 98.0% conversion of acetone. The cata acetic acid 3.2 0.0 0.0
lyst was stable under these conditions during the whole
experiment (5 hours). C6H12 0.3 0.0 0.0

It is worth noting the proposed method for the syn cumene 21.2 75.3 83.4
thesis of cumene (the hydroalkylation of benzene with tertbutylbenzene 0.0 0.4 1.4
acetone), under the mentioned above conditions and
the industrial way for preparing cumene via the alkyla diisopropylbenzenes 5.3 18.5 10.7
tion of benzene with propylene are comparable in triisopropylbenzene 0.5 1.2 0.6
terms of the yield of main product, i.e., cumene (see
Table 4). other 0.1 0.2 0.2

CATALYSIS IN INDUSTRY Vol. 7 No. 4 2015

286 SHUTKINA et al.

Table 4. Comparison of the parameters of the two methods REFERENCES

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The authors thank the Russian Science Foundation
for the financial support (grant no. 142300094). Translated by Yu. Modestova

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