Operando spectroscopic identification of the species

VI
involved in ethylene polymerization on Cr /SiO2 Phillips catalyst
A. Piovano,* C. Barzan, L. Braglia, G. A. Martino, C. Lamberti, S. Bordiga, E. Groppo
Department of Chemistry, INSTM and NIS Center, University of Torino, via Quarello 15 A, 10135 Torino, Italy
* Tel: +39 011 670 8373 – Mail: alessandro.piovano@unito.it

THE PHILLIPS CATALYST OPERANDO INVESTIGATION [2]

Phillips catalyst was discovered in 1953 at the

Phillips Petroleum laboratories.

?
PC2H4 = 1 atm
Nowadays Cr based Phillips
catalysts cover more than the
T = 150 °C
50% of the HDPE world
demand. [1]
Global catalyst market for
olefin polymerization CrVI/SiO2

[3]
CrII and CrIII DR UV-Vis-NIR TIME EVOLUTION [2]
CrII disappearance
formation

[5]
Ethylene
Polymerization

Symmetry change: FT-IR oxidized byproducts:

from Td to Oh [4] methylformate [6]

Ethylene [5]
Polymerization

Cr reduction

Cr K-edge XANES

REACTION MECHANISM ACTIVE SITE [2] REFERENCES

CrII + methylformate
* Chem. Rev. 1996, 96, 3327-3349.
Ligands may play a role
[6]
* Tishchenko disproportionation: 2 HCHO → HCOOCH3 in the catalysis!
[1] J. Jansz, in Global PO&E News Analysis, Chemical Market
Resources, Inc., 2015.
[2] C. Barzan, A. Piovano, L. Braglia, G. A. Martino, C. Lamberti,
S. Bordiga, E. Groppo, J. Am. Chem. Soc. 2017, 139, 47,
17064-17073.
[3] B. M. Weckhuysen, I. E. Wachs, R. A. Shoonheydt,
[4] M. Botavina, C. Barzan, A. Piovano, L. Braglia, G. Agostini,
G. Martra, E. Groppo, Catal. Sci. Technol. 2017, 7, 1690-
1700.
[5] E. Groppo, C. Lamberti, S. Bordiga, G. Spoto, A. Zecchina,
J. Catal. 2006, 240, 172-181.
[6] G. Busca, J. Lamotte, J. C. Lavalley, V. Lorenzelli,
J. Am. Chem. Soc. 1987, 109, 5197-5202.