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INDUSTRIAL ALKYLATION OF AROMATIC HYDROCARBONS

CATALYZED BY NANOSTRUCTURE ZEOLITES: MECHANISMS
AND INTERMEDIATES
INTRODUCTION
In recent years, there have been considerable academic and industrial
research efforts carried out in the field of zeolite catalysis. The word zeolite is
Greek in origin and means boiling stones as natural zeolites visibly losing
water when heated. Today the word, as strictly defined, is reserved for
crystalline aluminosilicate materials (either natural or synthetic). There are
over 720 zeolite materials known at the moment (2003) and the number is
growing. Of this large number of zeolites, only a few have found commercial
application: they are mostly synthetic zeolites and synthetic-analog natural
zeolites. Since zeolites were first used in petroleum processing in the 1950s,
zeolite catalysis has undergone rapid and dynamic advances. The number of
zeolite-related U.S. patents published though 1981 exceeds 5,000 and the
zeolite scientific and technical literature contains over 25,000 articles.
Zeolites are three-dimensional, microporous, crystalline aluminosilicates
with frameworks made of SiO4 and AlO4 tetrahedra (those tetrahedral atoms
are often referred as T atoms). Insertion of trivalent Al3+ in place of
tetrahedrally coordinated Si4+ creates negative charge on the lattice, which is
compensated by extraframework cations. If the charge compensating cation is
H+, a bridged hydroxyl group, (SiO(H)Al), is formed, which functions as a
strong Brnsted acid site. Due to these acid sites, zeolites are solid acids and
are used as catalysts. The catalytic activity of zeolites is often related to
strength of the acid sites, which depends on chemical composition and
topology of zeolite frameworks. There are numerous naturally occurring and

synthetic zeolites. However, most zeolites used commercially are produced

synthetically, each with a unique structure. Zeolites have void and space
(cavities or channels) that can host cations, water or other molecules. The pore
sizes commercially available range from approximately 3 to approximately
8 . Some of the commercial materials are: A, beta, mordenite, faujasite,
ZSM-5, ferrierite.

Faujasite
(FAU)

Mordenite
(MOR)

Channels:
12 (7.4 )

Channels:
12 (6.5 x7.0 )
8 (6.0 x 5.7 )

Beta (BEA)

ZSM-5 (MFI)

Channels:
12(5.5 x 5.5 )

Channels:
10(5.3 x 5.6 )
10(5.1 x 5.5 )

Ferrierite
(FER)
Channels:
10 (4.2 x 5.4 )
8 (3.5 x 4.8 )

Figure 1 Various types of zeolite pores and channels.

A (LTA)
Channels:
8 (4 )