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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-
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2.3.1. CSTR
The ethylene oligomerization was performed at a constant pressure and temperature. During the reaction, the catalyst (5 g of
1080
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
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).
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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
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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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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