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Development and Industrial Application of a New Beta Zeolite Catalysts for

the Production of Cumene

Conference Paper · July 1998

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DEVELOPMENT AND INDUSTRIAL APPLICATION OF A NEW β ZEOLITE
CATALYST FOR THE PRODUCTION OF CUMENE

C. PEREGOa, S. AMARILLIa, G. BELLUSSIa, O. CAPPELLAZZOb AND G. GIROTTIc

a EniTecnologie SpA, Via Maritano, 26 I-20097 S. Donato Milanese, Italy

b Centro Ricerche Enichem SpA, Zona Industriale Marinella, I-07046 Porto Torres, Italy
c Enichem SpA, Centro Ricerche di Novara Ist. G. Donegani, Via Fauser 4, I-28100 Novara, Italy

ABSTRACT

A novel cumene process has been developed, using a new proprietary zeolite catalyst (PBE-
1). The process is environmentally sound as it eliminates the drawbacks of the traditional
technologies, based on supported phosphoric acid or AlCl3 (e.g., corrosion, acidic wastes,
exhausted catalyst disposal). The new catalyst is based on the zeolite β, which was selected
among several other zeolites because of its outstanding performances. According to the high
activity and selectivity of the catalyst, the benzene alkylation with propylene is performed in a
liquid-solid reactor, operating under mild conditions. A demonstration on a commercial scale has
been performed at the EniChem's cumene plant in Porto Torres (Italy). During the industrial test
run, superior quality cumene (greater than 99.95 wt-%) has been produced, with better yields
(more than 99.9 wt-%) than that of the traditional supported phosphoric acid catalyst. Moreover
higher catalyst life and productivity has been obtained.

INTRODUCTION

The alkylation of benzene with propylene gives cumene, a very important petrochemical
commodity used for the production of phenol and acetone. Cumene is currently produced using
either supported phosphoric acid (UOP) or AlCl3 (Monsanto) as alkylation catalysts. The
traditional technologies suffer from a variety of drawbacks such as: low yields, environmental
impact, corrosive catalysts and formation of oligomers and other impurities. Various zeolite
catalyst have been proposed as a possible solution to these problems since 1965, but only recently
industrial applications have been announced. Extensive lab scale and pilot plant testing of a
proprietary β zeolite catalyst, developed by ENI's researchers, has resulted in a new zeolitic PBE-
1 catalyst and a new cumene process, which is successfully in operation on industrial scale since
the end of May 1996. In this paper we describe the pathway and the most relevant milestone
achievements to the industrial technology.

CATALYST DEVELOPMENT

In the production of ethylbenzene, by alkylation of benzene with ethylene, the substitution of

the traditional AlCl3 catalyst was already industrially performed with success, using a zeolite
based catalyst. Mobil-Badger first commercialized a process in 1980, using a solid acid catalyst
containing a ZSM-5 type zeolite and operating in gas-phase [1,2].
A further improvement was obtained by Unocal through the application of a Y type zeolite in
the liquid-phase [2,3]. The liquid-phase operation has the advantage of a better thermal control
and longer catalysts life.
Problems related with reactants and products diffusion not allowed the use of ZSM-5 in the
liquid-phase alkylation of benzene with propylene [4]. On the contrary good activity and stability
of a Y type zeolite for the same reaction in liquid-phase was reported [5]. However because of the
higher activity of propylene towards oligomerization and because of the presence of supercages
(12 Å of diameter) in the framework, zeolite Y produces not negligible amount of bulky by-
products.
The peculiar structure of zeolite β allowed to improve the selectivity. In fact while the tri-
dimensional large pore channel system avoid diffusion problems as in the case of zeolite Y, the
absence of supercages avoid the formation of bulkier by-products [6,7]. As a matter of fact,
zeolite β showed better performance than USY, ZSM-5 and phosphoric acid supported on silica
kieselguhr (SKPA) [8].
Although many patents have issued over the last thirty years, only recently the commercial
application of several new processes, operating in liquid-phase and based on zeolite catalysts (e.g.
mordenite, MCM-22, USY) have been announced. Commercial cumene processes have been
developed respectively by Dow [9], Mobil [10], CDTech [11] and UOP [12]. An extensive
comparison among the different zeolite structures has been performed in our laboratories. In the
Table 1 the selectivity's obtained in catalytic tests performed in a continuous flow microreactor
are reported (T=150 °C; P=3.8 MPa; benzene/propylene=7). The selectivity values are compared
at the same conversion level.
Among the zeolites considered (mordenite, MCM-22, ZSM-5, USY, ZSM-12 and β), zeolite
 Zeolite β Mordenite MCM-22 USY ZSM-12 ZSM-5

Selectivity (%)
Cumene/Benzene 95.06 90.11 93.06 83.20 96.44 89.46
Cumene/Propylene 90.49 80.92 86.28 70.40 90.81 79.76
(Cumene+DIPB)/Propylene 99.87 98.61 98.74 98.30 97.32 84.92

Table 1: Cumene selectivity’s obtained with different zeolite catalysts.

β appeared to be one of the most efficient catalyst as it shows the highest overall selectivity
(cumene + DIPB). In fact DIPB (diisopropylbenzenes) can be considered useful by-products,
because they can be recovered by transalkylation with benzene to cumene. Besides a good
agreement was found among the experimental performances and the energy diffusion barriers and
binding energies of cumene and DIPB isomers, in the different zeolite pore structures, evaluated
by molecular mechanics calculations [13].
The zeolite β with a proper composition and morphology has been formulated and shaped into
pellets to obtain the new zeolitic PBE-1 catalyst [14].

PROCESS DEVELOPMENT

Reaction mechanism and kinetics

In order to identify a proper kinetic model of the reactions involved during the alkylation,
several experiments were performed by using a microreactor assembly charged with small
amounts of PBE-1 catalyst (< 0.5 g ), crushed from the extrudates and sieved to particles. By the
dilution with inert material of the same size, isothermal experiments were carried out under
continuous flow. The influence of temperature and feed composition on the reaction rates was
quantified. The kinetic data were first processed with a kinetic model according to a simplified
reaction scheme like that proposed by Harper et al. (Figure 1) for the alkylation catalyzed by
zeolite SK-500 (Y type zeolite) [5].
Though very simple, such a model describes quite well the cumene and DIPB selectivity’s.
The kinetic parameters estimated for PBE-1 are compared with that obtained for zeolite Y in term
of parameter ratio at 150 °C (Table 2). As already evidenced by Harper et al., the selectivity of
DIPB is determined by the rate of dialkylation (k2) and by the rate of transalkylation (k3). PBE-1
shows both a lower dialkylation relative rate (k2/k1) and a lower transalkylation relative rate
(k3/k2) with respect to zeolite Y. Both these results are in agreement with the lower pore openings
and the absence of supercages in zeolite β with respect to zeolite Y. However, under mild
reaction conditions (e.g. 150 °C), the DIPB selectivity is more influenced by the dialkylation than
by the transalkylation. This accounts for the higher cumene selectivity of zeolite β (Table 1).

CH 3 CH CH 3
CH 3 CH CH 3
k1 k2
+ CH 2 CH CH 3
CH 2 CH CH 3
CH 3 CH CH 3
BENZENE PROPYLENE CUMENE DIISOPROPYLBENZENE

CH 3 CH CH 3 CH 3 CH CH 3

k3
+ 2
k4
CH 3 CH CH 3

BENZENE DIISOPROPYLBENZENE CUMENE

Figure 1. Alkylation/transalkylation reaction scheme.

This work Harper et al. [5]

k2/k1 0.54 3.27
k3/k2 *102 1.3 3.6
Table 2: Kinetic parameter ratio at 150°C.

This kinetic model was than upgraded considering also other by-products (e.g. n-
propylbenzene (NPB), propylene oligomers, butylbenzenes). Besides o-, p- and m-DIPB were
considered separately in order to determine the role of the cumene alkylation and of the
consecutive isomerization. In fact, the cumene alkylation is generally accepted to proceed with
the formation of both o- and p-DIPB, being their ratio governed by steric factors. Then o- and p-
DIPB undergoes to other reactions: they isomerize to m-DIPB, which is thermodynamically
favored [13].
Particular attention was also devoted to the mechanism of formation of NPB, as this impurity
heavily affects the quality of cumene because of the difficulty to separe it from cumene. The
formation of NPB during the alkylation catalyzed by zeolites has been reported as secondary
isomerization of cumene [4,13,15] by intermolecular transalkyaltion with benzene [16].
Completely different mechanisms have been proposed in other papers, which reported that the
NPB formation is due to either the formation of small amounts of primary carbenium ion [12] or
the presence of cyclopropane in the propylene feed. Cyclopropane reacts with benzene to form
either cumene or NPB [17]. At any rate, all the authors agreed that the tendency to form NPB
increases with the temperature. In order to evaluate the kinetics of cumene isomerization to NPB
catalyzed by PBE-1, we have performed several experiments with the same procedure already
described for the alkylation. Varying initial cumene concentration in benzene and temperature,
different NPB profiles have been obtained with respect of contact time. During these experiments
also DIPB were formed according to the equilibrium step in the scheme (Figure 1).
The kinetic data of both alkylation and isomerization experiments were well fitted by the
kinetic model obtained introducing the isomerization reaction in the scheme (Figure 1), with the
only exception of NPB. In fact, the molar ratio NPB/cumene in the alkylation experiments at low
contact time, is almost independent of propylene conversion but it depends on temperature as
shown in Figure 2.
Selectivity Ratio
3E-4

2E-4
Figure 2.
NPB/Cumene
1E-4 selectivity ratio.
T=130 °C T=150 °C

0 20 40 60 80 100
Propylene Conversion (%)

This behavior can not be explained by assuming that the formation of NPB is only due to a
consecutive isomerization of cumene. It is necessary to admit that NPB is also formed by a
primary alkylation of benzene. As the cyclopropane contained in the propylene used in our
experiments (<10 ppm) does not account for our results, it was adopted the reaction scheme in
Figure 3.
A reaction mechanism assuming the formation of small but significant amount of primary
carbenium ion by the activation of propylene with an acidic zeolite is quite reasonable. In fact the
difference in enthalpy of activation for the formation of n-propyl cation and isopropyl cation
evaluated for a faujsite acidic site (6 kcal/mol. [12]) is much lower than that reported for the gas-
phase (16 kcal/mol). The n-propyl to isopropyl cation equilibrium ratio estimated with the former
difference [12] is consistent with the NPB/cumene obtained in our experiments. The NPB
 CH 3 CH CH 3 CH 2 CH 2 CH 3
k1 k5
+ CH 2 CH CH 3

BENZENE PROPYLENE CUMENE n-PROPYLBENZENE

k6 k4 CH 2 CH CH 3

CH 2 CH 2 CH 3 CH 3 CH CH 3

CH 3 CH CH 3
n-PROPYLBENZENE DIISOPROPYLBENZENE

Figure 3. Alkylation/isomerization reaction scheme.

kinetic data were well fitted by the kinetic model obtained according to the above reaction
scheme (Figure 3).

Catalyst decay and regeneration

A fixed bed reactor assembly was used to study the catalyst decay, under accelerated
conditions ( WHSV up to 160 h-1). After decay the catalyst need to be regenerated by a proper
heat treatment in air. By this operation the carbonaceous deposits burn off, recovering the
catalytic activity. In the laboratory fixed bed reactor five cycles of accelerated decay, followed by
regeneration were performed. The 6th accelerated decay test resulted in a catalyst life of only 5%
lower, with respect to the PBE-1 fresh catalyst.

Pilot Plant Tests

The process information obtained at the laboratory scale were consolidated at a pilot plant
scale, before proceeding on the industrial applications. An extensive program of pilot plant
testing was designed to demonstrate the stable operation of the PBE-1 catalyst using commercial
benzene and propylene feedstocks. Under a selected set of operating parameters a life tests were
performed: during 4000 h of time on stream the propylene conversion was always complete and
no significant decay was detected.
INDUSTRIAL TEST RUN

On the basis of the above results an industrial test run has been performed in the EniChem's
cumene plant in Porto Torres, Sardinia. A reactor of 36 m3 of volume has been charged with the
zeolitic PBE-1 catalyst and operated at the optimized conditions starting since the end of May
1996. The performance evaluated over two years of operation is meeting the expectations in
every respect. The new zeolitic PBE-1 catalyst produces cumene with superior quality (greater
than 99.95 wt-%) and better yields (more than 99.9 wt-%) compared to the traditional SKPA
catalyst. Besides the new catalyst allows an increase of cumene productivity per hour of around
30-40%, with the same reactor volume. Over two years of operation the global productivity of the
catalyst is more than 5 times the SKPA one. Until May 1998 no regeneration has been performed.
The new technology has been extended to another reactor since the beginning of 1997,
confirming the outstanding performance.

CONCLUSION

A novel cumene process has been developed, using a new zeolitic catalyst (PBE-1). The
catalyst is based on the zeolite β. A demonstration on a commercial scale has been performed at
the EniChem's cumene plant in Porto Torres. The main features of the new process are:
- high product yield;
- high product quality;
- high catalyst life;
- capacity expansion of existing SKPA units (30-40 %);
- environmentally sound.

Acknowledgments

The authors are in debted to Mr. M. Fais, Mr. A. Lay, Dr. D. Rancati and Dr. M. Schenato of
Enichem S.p.A. for the invaluable contribution during the start up and the operation of the
industrial test runs. The authors wish also to thank EniTecnologie S.p.A. and Enichem S.p.A. for
the permission to publish this work.
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