Chemical Engineering Journal 172 (2011) 10781082

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Chemical Engineering Journal

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Continuous stirred tank reactor for ethylene oligomerization catalyzed by

NiMCM-41
Michael Lallemand 1 , Annie Finiels, Francois Fajula, Vasile Hulea
Institut Charles Gerhardt, UMR 5253, CNRS-UM2-ENSCM-UM1, Matriaux Avancs pour la Catalyse et la Sant, 8 rue de lEcole Normale, 34 296 Montpellier Cedex 5, France

a r t i c l e

i n f o

Article history:
Received 14 September 2010
Received in revised form 22 June 2011
Accepted 22 June 2011
Keywords:
Catalysis
Continuous reactors
Ethylene oligomerization
Mesoporous materials
Nickel

a b s t r a c t
The performances of Ni-exchanged MCM-41 mesoporous material as catalyst for the ethylene oligomerization were evaluated in a pilot plant equipped with a continuous stirred tank reactor (CSTR). During
the catalytic tests performed at 30 C, without any start-up solvent, over 170 h on stream, the catalyst
was highly active and stable to deactivation. Moreover, the reaction was very selective, resulting mainly
in C4 , C6 , C8 and C10 olens. The CSTR unit described in this article proved to be an effective and useful
tool for performing complex catalytic studies, involving three-phase systems.
2011 Elsevier B.V. All rights reserved.

1. Introduction
The oligomerization of ethylene is an important industrial reaction and represents the primary source of -olens, which are
versatile chemical intermediates for a large number of useful
products (polymers, detergents, petrochemicals, oil additives) and
clean fuels [1,2]. Metal complexes are commonly used as active
and selective homogeneous catalysts for the industrial oligomerization processes [3,4], but research efforts are directed to the
development of heterogeneous processes involving robust and
recyclable catalysts. Thus, supported nickel catalysts, especially Nicontaining zeolites, were widely used as heterogeneous catalysts
in this reaction [59]. Unfortunately, most of solid catalysts suffered a severe deactivation during the oligomerization reaction.
The microporous character of these materials leads to intracrystalline diffusion limitations which results in a rapid enrichment of
polymeric waxes in the micropores [8,9]. One of the approaches to
overcome this problem was the use of catalysts with larger pores,
such as Ni/sulfated-alumina [10] and Ni/amorphous silicaalumina
[11] under mild reaction conditions.
Recently we have reported that Ni-exchanged AlMCM-41
mesostructured materials, with carefully controlled texture and
concentrations of nickel and acidic sites revealed interesting prop-

Corresponding author. Tel.: +33 4 67 16 34 64; fax: +33 4 67 16 34 70.

E-mail address: vasile.hulea@enscm.fr (V. Hulea).
1
Present address: RHODIA SA, Centre de Recherche et Technologie, Laboratoire
de Catalyse Automobile, Ple SILCEA, 52 rue de la Haie-Coq 93308, Aubervilliers,
France.
1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.06.064

erties as catalysts for the ethylene oligomerization performed

in slurry semi-batch mode [1214]. AlMCM-41 belongs to M41S
family, and is characterized by a regular array of unconnected cylindrical mesopores with uniform diameter in the range of 1.510 nm
[15]. It is an amorphous material with acidic properties, due to
the presence of Al atoms. AlMCM-41 can be easily transformed by
exchange with nickel ions into NiMCM-41, which is a bifunctional
catalyst (Ni and acid sites). Working in a batch-type reactor we
have obtained useful information about NiMCM-41 as catalyst for
the ethylene oligomerization. Thus, we have found that the crucial
variables affecting the catalyst activity, as well as the product spectrum, are the pore size of the catalyst, the ratio between the acid
sites and nickel ions and the nature of the Ni species. For instance,
by means of spectral and catalytic measurements it has been established that both Ni+ and dehydrated Ni2+ species (present as charge
compensating cations in the AlMCM-41 framework) are catalytic
sites in the ethylene oligomerization [14].
However, the batch system showed some drawbacks, mainly
generated by the continuous change in the reaction mixture
composition, the catalysts deactivation by the heavy products accumulated in reactor [12] and the reactor volume limitation [16].
In order to overcome these problems and to establish the longer
term behaviour of these catalysts, we have developed a pilot unit
equipped with a continuously operated slurry reactor (CSTR). With
this reactor we are working under steady state, with continuous
feed of ethylene and outlet of products, using a powder catalyst
without binder. A similar reactor was successfully used by Heydenrych et al. [17] in order to obtain the kinetic data for the
ethylene oligomerization process catalyzed by Ni(II)-exchanged
silicaalumina, at 3.5 MPa and 120160 C. The aim of this contri-

M. Lallemand et al. / Chemical Engineering Journal 172 (2011) 10781082

1079

Fig. 1. Experimental CSTR set-up sketch.

bution is to describe this technique and to present the catalytic

behaviour (activity, selectivity and deactivation stability) of the
NiMCM-41 catalyst in the ethylene oligomerization performed
under these conditions.
2. Material and methods
2.1. Synthesis and characterization of catalysts
NiAlMCM-41 (hereafter designated NiMCM-41) was prepared
using NaAlMCM-41 as starting material. NaAlMCM-41 with Si/Al
of 30 and pore size of 3.5 nm was synthesized by autoclaving for
24 h at 125 C. The gel was obtained by mixing NaOH, NaAlO2 ,
CTABr, SiO2 (Aerosil 220V) and water. The calcined NaAlMCM41 was transformed into NH4 AlMCM-41 by ionic exchange with
ammonium nitrate (60 C, 0.25 M nitrate in ethanol, liquid-to-solid
ratio of 50 mL g1 for 4 h; the exchange procedure was repeated
three times). NH4 AlMCM-41 was modied by ionic exchange with
nickel nitrate (60 C, 0.25 M nitrate in ethanol, liquid-to-solid ratio
of 50 mL g1 for 4 h; the exchange procedure was repeated three
times). The resulting samples were calcined for 8 h in an air ow
at 550 C to obtain NiMCM-41. The calcined sample was characterized using elemental analysis and X-ray diffraction (XRD). The
textural characterization was achieved using conventional nitrogen
adsorption/desorption method, with a Micromeritics ASAP 2010
automatic analyzer. The t-plot method was used to calculate the
external surface area. The samples acidity was measured by temperature programmed desorption (TPD) using ammonia as probe
(nitrogen stream, at a heating rate of 10 C min1 in the range of
100650 C).

an electric furnace. The temperature of the reactor is controlled

via a PID temperature controller, and monitored by a thermocouple placed within the reactor (Fig. 1). The liquid phase in which
the catalyst powder is suspended is almost perfectly mixed using
a mechanical agitator with a high speed three-blade impeller. Bafes prevented the formation of a vortex and rotation of the reaction
mixture with the stirrer. When a solvent is used, the liquid ow is
controlled by a HPLC type pump.
Equal ows of ethylene are introduced into reactor through
0.3 cm i.d. tubes at the bottom and the top of the reactor, respectively. The liquid level in the reactor is measured and controlled
using a differential pressure transducer and an automatic valve. A
constant reaction pressure is maintained by using a downstream
back pressure controller. The liquid and gas streams (controlled
by the automatic valve and the downstream back pressure system, respectively) are periodically removed from reactor. The liquid
pass through a 1 m sintered steel lter which prevents the catalyst elimination by the uid stream. In order to prevent the lter
obstruction by the catalyst, the reactor is equipped with two identical tubes/lters, which regularly reverse during the oligomerization
process. The composition of the liquid phase is quantied using
an on-line GC (Varian CP 3800 chromatographs, FID, CP-Sil 5CB
60 m, 0.32 mm capillary column). Gas products pass through a condenser maintained at 10 C and come in a gasliquid separator.
The uncondensed stream is combined with the gas phase and then
analyzed by GC (Varian CP 3800 chromatographs, FID, Poraplot Q
25 m, 0.53 mm capillary column). The CSTR is integrated into a completely automatized micro pilot plant (Fig. 2), designed and made
by VINCI TECHNOLOGY.

2.3. Oligomerization procedure

2.2. CSTR pilot plant
The CSTR consists of a stainless steel vessel with a nominal
working volume of 500 mL (TOP INDUSTRIES SA), equipped with

2.3.1. CSTR
The ethylene oligomerization was performed at a constant pressure and temperature. During the reaction, the catalyst (5 g of

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M. Lallemand et al. / Chemical Engineering Journal 172 (2011) 10781082

Fig. 3. Powder X-ray diffraction patterns of NiMCM-41 sample.

symmetry (Fig. 3) [18]. This material displayed a reversible nitrogen adsorptiondesorption isotherm of type IV, with a sharp step
at 0.35 p/p0 , characteristic of monodisperse pore size of 3.5 nm
(Fig. 4). The BET surface area was about 1000 m2 g1 , the pore
volume was 0.76 mL g1 and the overall acidity (TPD-NH3 ) was
0.45 mmol NH3 g1 .
3.2. Catalytic ethylene oligomerization

Fig. 2. CSTR pilot plant.

powder, without binder) was suspended in a liquid phase at a stirring speed of 1000 rpm. Prior to each experiment, the catalyst was
thermally activated rst in a tubular electrical furnace (550 C, 8 h,
nitrogen ow) and then in the CSTR (200 C, 3 h, nitrogen ow).
Nitrogen was also used to purge the reactor lines. After the catalyst activation, the reactor was cooled to the desired temperature.
During the catalytic run pure ethylene (quality N25 from Air Liquide) was introduced into reactor at 3 MPa and a constant ow
rate of 12 NL h1 . Gas and liquid streams removed from the reactor
were reduced to atmospheric pressure, measured and analyzed by
on-line GC.
2.3.2. Batch reactor
The oligomerization was performed in a 0.3 L well-mixed gasslurry reactor operating in semi-batch mode [14]. Prior to catalytic
test, the catalyst was thermally activated rst in a tubular electrical furnace (550 C, 8 h, nitrogen ow) and then in the CSTR
(200 C, 3 h, nitrogen ow). The reaction was performed at constant temperature and pressure (3 MPa of ethylene quality N25
from Air Liquide), using 500 mg of catalyst suspended under stirring (1000 rpm) in 68 g of dry oxygen-free n-heptane. At the end
of the experimental test, the autoclave was cooled to 20 C and
the products were collected, weighted and analyzed by GC on a
Varian 3900 chromatograph (FID, DB-1, 60 m 0.32 mm, 3 m lm
thickness).

The performances of NiMCM-41 as catalyst in the ethylene

oligomerization were evaluated using two modes: (i) CSTR, without
initial solvent and (ii) batch reactor, with n-heptane as solvent.
(i) In this experimental mode no initial start-up solvent was
used. At the desired reaction temperature, the reactor containing
the thermally activated catalyst was pressurized with ethylene at
3 MPa (12 NL h1 ), without agitation of the vessel contents. After
several hours, when the liquid level in the reactor (due to oligomer
formation) had become measurable, the agitator was turned on
(1000 rpm). When the reactor was about 70% full the liquid level
controlling valve is activated and periodically, the valve opened to
eliminate the overow in the gas-liquid separator at atmospheric
pressure.
Oligomerization tests were performed at different temperatures
ranging from 30 to 150 C. We discuss in detail the results obtained
at 30 C and 3 MPa, over a period of 170 h time on stream. During the
catalytic test the ethylene conversion was higher than 95% (Fig. 5),
and the production of oligomers was constant indicating that the
catalyst deactivation was insignicant under these reaction condi-

3. Results and discussion

3.1. Catalyst characteristics
NiMCM-41 (0.5 wt% Ni, Si/Al = 30) featured XRD pattern characteristic of a well ordered MCM-41 type material identied by
the (1 0 0), (1 1 0) and (2 0 0) diffraction peaks of the hexagonal

Fig. 4. Nitrogen sorption isotherm at 196 C of NiMCM-1 sample.

M. Lallemand et al. / Chemical Engineering Journal 172 (2011) 10781082

1081

notably change for 8 h time on stream. Under these conditions, the

productivity was about 2.9 goligomer gcatal 1 h1 . Note that this value
is limited by the rate ow of ethylene.
(ii) Oligomerization test was also carried out in a 0.3 L wellmixed three-phase reactor operating in batch mode, at 30 C and
3 MPa, using the same catalyst. The activity for the rst hour
of reaction was 6.7 goligomer gcatal 1 h1 , but a severe deactivation of the catalyst was observed after several hours. Thus, the
average activity evaluated for 3 h of time-on-stream was about
3.5 goligomer gcatal 1 h1 . According to these data, the average productivity in oligomerization for the third hour of reaction was less
than 1 goligomer gcatal 1 h1 . After one hour of reaction only butenes
(80%) and hexenes (20%) were obtained as oligomers. But the product distribution changed with time-on-stream. Thus, after 3 h of
reaction about 25% of oligomers were C8+ olens.
Based on both present and previous results [1214] we can
examine the catalyst behaviour under different oligomerization
conditions. Two types of mechanisms could be taken into account.
The rst one is based on the coordination chemistry on nickel sites
and the second one is based on the acid catalysis. As previous
reported [14], the nickel sites consist in Ni+ or dehydrated Ni2+
ions. The acidity is provided by the aluminum atoms present in the
solid framework. The amount of the acid sites (measured by ammonia TPD) was 0.45 mmol g1 . The nickel ions act as active sites for
both the initial dimerization of ethylene, yielding 1-butene, and
further oligomerization reactions involving 1-butene-ethylene, 1hexene-ethylene, . . . couples (Scheme 1). In this scheme only Ni+
was considered among the nickel species.
Additionally, over acid sites, the C4 and C6+ olens can be
consumed through double bond isomerisation and dimerization
reactions, leading to the formation of octenes or higher olens,
respectively. The acid-catalyzed transformation of olens is a classic example of carbenium ion chemistry [19]. Generally, tertiary
cations could be formed by rapid reaction of the initially formed
sec-alkyl cations with olen molecules to yield branched dimmers and oligomers. The present and the previous results obtained
over Ni-MCM-41 catalyst [12] support these statements. Thus, the
C4 C6 oligomers are mainly linear isomers, but a drastic decrease
of the proportion of linear isomers is observed in the case of C8+
oligomers. This is a proof that the higher oligomers are mainly
formed via acid catalyzed reactions involving C4 and C6 primary
olens.
The heavy branched hydrocarbons accumulated in the batch
reactor may strongly adsorb on the catalyst surface being the most
probably responsible for the catalyst deactivation. On the other
hand, taking into account the favourable effect of the temperature
on the acid-catalyzed reactions involving C3+ olens [20,21], we
can explain the dependence between the hydrocarbon selectivity
and reaction temperature presented in Fig. 6.

Fig. 5. Ethylene conversion over NiMCM-41; T = 30 C, P = 3 MPa.

Fig. 6. Effect of the reaction temperature on the oligomer distribution; P = 3 MPa.

tions. On the other hand, the reaction was highly selective, resulting
mainly in C4 , C6 , C8 , C10 and C12 olens. No alkanes and odd carbon
number olens were identied in the product mixture. The near
Schulz-Flory-type oligomer distribution (56% butenes, 24% hexenes, 10% octenes, 6% decenes and 4% dodecene) did not change
during the 7 days of reaction.
As expected, the selectivity towards the different hydrocarbon
groups strongly depended on reaction conditions. In Fig. 6, the Cn
distribution is plotted against the reaction temperature. It is evident that over all catalysts, particularly at a lower temperature,
C4 olens are the main oligomerization products. On the contrary,
at higher temperatures, the oligomerization was mainly directed
towards the formation of C6 and C8 or C10 olens. We note that
during each run carried out at 70, 100 or 150 C, the ethylene conversion was more than 95% and the product distributions did not

1-Linear olefins

H+

Ni+

O
Si

O
Si

Linear and branched

heavy olefins

C=C-(C-C) n

(n+1) C=C

O
Al

O
Si

Si

O
Al

Si

Scheme 1. Main reaction pathways of the reaction of ethylene over Ni-exchanged MCM-41 (n 1).

Si

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M. Lallemand et al. / Chemical Engineering Journal 172 (2011) 10781082

4. Conclusions
The present experimental results conrm the remarkable activity of the Ni-exchanged mesoporous materials with MCM-41
topology as catalyst for the ethylene oligomerization. Additionally, the tests performed in a continuous stirred tank reactor clearly
show that the Ni-exchanged MCM-41 catalyst is also highly stable
to deactivation. For example, in the oligomerization process carried out at 30 C and 3 MPa, in a solvent free system, during 170 h
on stream, the ethylene conversion was higher than 95%. On the
other hand, the reaction was highly selective, resulting olens with
a Schulz-Flory-type distribution. At temperatures higher than 70 C
the oligomerization was mainly directed towards the formation of
C6 C10 olens.
The CSTR unit developed in our laboratory proved to be an
effective and useful tool for performing complex catalytic studies,
involving three-phase systems. The use of this system enables the
measurement of longer term reaction behaviour, under conditions
close to those encountered in large-scale reactors.
Acknowledgment
Part of this work was nancially supported by the Languedoc
Roussillon Region (France).
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