Different support materials for Cr-based Phillips catalyst:

a comparison between alumina and silica

G. A. Martino, C. Barzan, A. Piovano, A. A. Damin, S. Bordiga and E. Groppo
University of Torino, Department of Chemistry, NIS Centre and INSTM, via Quarello 15A, 10135 Torino, Italy

BACKGROUND Cr precursor AIM

TheThisPhillips catalyst is among the most
work is devoted to the study of the role of important Studying of the role of the support in affecting
heterogeneous catalysts
different supports for ethylene
in affecting the polymerization:
catalytic it the catalytic performances of the Phillips
Al2O3 SiO2
accounts for ofabout
performances 50% Phillips
the Cr-based of thecatalyst,
high density catalyst, in particular of Al2O3 compared to
polyethylene (HDPE)ofworld's
and in particular demand. The
Al2O3 compared active
to SiO 2.
phase
SiO2.
is The
constituted
role of thebysupport
a highly dispersed
material chromium
has not been oxide
supported
completelyonclarified
a high surface area catalyst
yet. Phillips material.isAlthough EXPERIMENTAL
amongSiO
porous the most important heterogeneous
2 is the most employed in the industrial
catalystsAlfor ethylene polymerization (around All samples were oxidized in O2 at 650 C, followed by
practice, O
2 3 can also serve as a support. In respect to
50% of HDPE world's demand).has weakly acidic Al-OH reduction in CO at 350 C for 1 hour. After reduction
silica, alumina is crystalline, Crystalline Amorphous
the samples were tested for gaseous ethylene
groups and exhibits a higher surface OH groups
polymerization reaction at room temperature. The
population in the same activation conditions. Both
accessibility of the sites was tested with the use of
factors influence the amount and the properties of the
probe molecules at room temperature.
grafted chromium sites1,2.

Cr/Al2O3 Cr/SiO2
DIFFUSE REFLECTANCE UV-VIS SPECTROSCOPY DIFFUSE REFLECTANCE UV-VIS SPECTROSCOPY
Interaction with CO Interaction with CO
Cr2+6c
Cr3+ 6c
3 types of reduced Cr A single type of highly Cr2+6c Cr2+4c
Cr2+4c
sites are formed, differing uncoordinated reduced
in the oxidation state and Cr site is formed
coordination geometry (Cr2+4c )4.
(Cr3+ 6c, Cr2+ 6c, Cr2+4c ).
Cr2+4c
Cr2+6c
Cr3+6c
Cr2+4c
Only the highly uncoordinated Cr2+4c sites
are accessible to the incoming molecules,
including ethylene. These sites are those
involved in ethylene polymerization

Reactivity with C2H4 Reactivity with C2H4

INFRARED SPECTROSCOPY INFRARED SPECTROSCOPY

CO adsorption CO adsorption CrA
CrB

CO adsorption causes the appearance of :

Pseudo-carbonates are formed during single band: monocarbonyl triplet of bands: CO reduction leads to a clean surface
the CO-reduction step (Al2O3 stabilizes broad: heterogeneity of sites mono and di-carbonyls (SiO2 does not stabilizes CO2 evolved in
the CO2 obtained by reducing at 2200 cm-1 sharp: well defined sites the gas phase during the reduction).
chromates)2. at 2180 cm-1 3

ETHYLENE POLYMERIZATION : KINETICS STUDIES CONCLUSIONS

Alumina stabilizes both Cr3+ and Cr2+ in different coordination,
In accordance with the namely Cr3+ 6c Cr2+ 4c Cr2+ 6c , while silica stabilizes only Cr2+ 4c sites
specialized literature1, Al2O3- Only Cr2+4c sites are active in the polymerization of ethylene.
supported Phillips catalyst The ionicity of the alumina support affects the electronic properties
exhibits a faster kinetics of the Cr2+4c sites.
profile than SiO2 -supported The faster polymerization kinetics for the Cr/Al2O3 system might be
one, i.e. the polymerization explained in terms of the different electronic properties of the
rate develops more rapidly, chromium sites, although an influence of the adsorbed carbonates
but it tends to decay earlier. cannot be excluded.
REFERENCES:
[1] M. P. McDaniel, Adv. Catal., 2010, 53, 123-606.
ACKNOWLEDGEMENTS:
[2] C. Morterra and G. Magnacca, Catal. Today, 1996, 27, 497-532.
We would like to thank Dr. Andriy Budnyk for valuable discussions.
[3] E. Groppo, C. Lamberti, S. Bordiga, G. Spoto and A. Zecchina, Chem. Rev., 2005, 105, 115-183
This work has been supported by the Progetto di Ateneo/CSP 2014 (Torino_call2014_L1_73).
[4] B. M. Weckhuysen, I. E. Wachs and R. A. Shoonheydt, Chem. Rev., 1996, 96, 3327-3349.