In: Clay: Types, Properties and Uses ISBN 978-1-61324-449-4

Editors: J. P. Humphrey and D. E. Boyd 2011 Nova Science Publishers, Inc.

Chapter 16



PILLARED CLAYS AS GREEN
CHEMISTRY CATALYSTS: APPLICATION
TO WASTEWATER TREATMENT


C. B. Molina, J. A. Casas, A. H. Pizarro,
and J. J. Rodriguez
Universidad Autnoma de Madrid, Madrid, Spain


ABSTRACT

Clay minerals have received considerable attention in the last years because of their
environmental compatibility, low cost, high selectivity, reusability and operational
simplicity. Porosity and stability of these materials are improved by pillaring, which leads
to materials known as pillared clays (PILC). These materials show increased surface area,
pore volume, thermal and mechanical stability and, depending on the pillars, improved
catalytic activity compared to the parent clays, making them suitable catalysts and
adsorbents. The interest for pillared clays has suffered a dramatic increase in the last
years in a great part due to their potential applications as catalysts. The metals
incorporated in the pillared clay structure are crucial and make them suitable for a
number of different applications, most of them belonging to the named green
chemistry. This chapter shows an overview of the different reactions performed using
pillared clays as catalysts, focusing on those addressed to the abatement of water
pollutants. In this way, pillared clays have been tested as catalysts for the treatment of
wastewater containing different types of contaminants. Among them, the treatment of
chlorophenols-bearing effluents has been investigated. Chlorophenols (CPs) are among
the most concerning pollutants in industrial wastewater and contaminated groundwaters,
being highly resistant to biodegradation. Their removal or conversion into
environmentally harmless species is a current need. From a chemical point of view, they
can be removed by oxidative or hydrogenation treatments. Our research group has been
working within the last decade on the use of catalysts based on pillared clays for both
processes, specifically catalytic wet peroxide oxidation (CWPO) and catalytic
hydrodechlorination (HDC). Both CWPO and HDC have advantages and drawbacks. In
this chapter we summarize the main results from our work including a comparison with
those reported by other authors.
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C. B. Molina, J. A. Casas, A. H. Pizarro et al.

436
1. INTRODUCTION

Clays and Pillared Clays

The term clay has been used to either indicate fine particles with a grain size less than 2
m or minerals belonging to the clay minerals group (Velde, 1992). Currently clays are
important materials with a great number of applications in ceramics, oil drilling and metal and
paper industry. They are used as adsorbents, decoloration agents, ion exchangers and
molecular sieve catalysts (Fowden et al., 1984), being efficient and relatively cheap solid acid
catalysts for liquid phase processes. Two broad classes of clays may be identified (Reichle,
1986): cationic clays (or clay minerals), widespread in nature, and anionic clays (or layered
double hydroxides (LDHs)), more rare in nature and usually synthesized at laboratory and
industrial scales in an easy and inexpensive way (Trifiro and Vaccari, 1996). Cationic and
anionic clays may be considered promising substitutes for catalysts manufacture due to their
high versatility, easily manipulated properties and low cost, with a great number of
possibilities for technological upgrading of these materials (Vaccari, 1999).
Clay minerals ability to exchange interlayer cations has attracted great interest for their
use in industrial applications. These materials possess negatively charged alumino-silicate
layers with small cations in the interlayer space to balance the charge. For the application as
molecular sieve catalyst a group of expandable clays known as smectites is usually employed.
To modify the clay structure, different compounds have been used to intercalate between the
clay layers with the aim of increasing the pore size. The first authors to report the
intercalation of organic compounds into the structure of clay minerals were Barrer and
Macleod (1955) whom synthesized materials able to be used as adsorbents, fillers and
thickeners. The main drawback of these products, as those authors recognized, was their
decomposition at relatively low temperatures, causing the pillared clay structure to collapse,
thus not being useful as catalysts. The crisis in the oil industry promoted searching for new
materials with relatively wide pores able to process the large crude oil molecules. Also
inorganic polyoxocations can be intercalated by ion exchange (Figure 1). Their calcination
makes the hydrated polyoxocations dehydrate and dehydroxylate then reacting to form rigid
and thermally stable oxide species, named pillars, which prop apart the clay layers and
prevent their collapse, leading to the materials known as pillared clays (PILC). The
introduction of inorganic pillars increases microporosity, providing a greater specific surface
area and contributes to the material resistance and stability (Thomas and Thomas, 1997).
Thus, materials of high thermal and hydrothermal stability can be prepared with high porosity
and surface area within 200-500 m
2
/g. Their porous structure is influenced by the number and
size of the pillars in the interlayer space, which is affected by the cation exchange capacity of
the original clay mineral and the charge of each individual polyoxocation. Requisites for
pillared clays are negligible adsorption of the pillaring agent on the external surface and
pillaring of essentially all clay sheets (Kloprogge, 1998). The main applications reported for
this kind of materials have been their use in heterogeneous catalysis (Purnell, 1990) including
reactions of environmental interest, as well as thermal insulators, pigments, electrodes and
membranes. Nowadays, the interest for pillared clays lies on their properties as catalysts,
production of fine chemicals and selective adsorbents for molecular preparations,
environmental remediation and pollution control (Gil et al., 2010).
Pillared Clays as Green Chemistry Catalysts

437

Figure 1. Pillaring procedure.
Aluminium is one of the cations most commonly used to build-up the pillars of the
structure, yielding pillared clay materials (Al-PILCs) with thermal and mechanical stability
(Pinnavaia et al., 1984). They were first synthesized by Johansson (1960). After him, different
authors reported their synthesis in several research papers (Brindley and Sempels, 1977) and
patents (Vaughan et al., 1979, 1981a, 1981b), leading to materials with high thermal stability
(up to 500C) and high basal spacing (17-18 ). Maximum interlayer distances can be
obtained when the so-called Keggin type [AlO
4
Al
12
(OH)
24
(H
2
O)
12
]
7+
cation (Figure 2) is
present in the Al-containing intercalating solution (Gil et al., 1994). This hydroxypolycation
consists of a central tetrahedral aluminium cation surrounded by twelve edge-linked
octahedraelly coordinated aluminium cations (Johansson, 1962). The main properties of
alumina-pillared clays, such as textural, structural and catalytic properties, depend on the
structure and composition of the aluminium hydroxypolycations in the intercalating solution,
the method of introduction into the layered clay, the degree of isomorphous substitution and
the chemical composition and crystallinity of the layered clay (Gil et al., 2000; 2008).


Figure 2. Keggin cation structure (Pinnavaia et al., 1984).
Other cations able to yield hydroxypolycations are Zr, Cr, Fe (Caizares et al., 1999) or
Ti (Valverde et al., 2002). In the case of Zr, its solution chemistry is fairly complex but the
zirconyl ion is mainly found as Zr
4
tetramer (Figure 3) with the structural formula
[Zr
4
(OH)
8
(H
2
O)
16
]X
8
12 H
2
O (Johnson and Kraus, 1956). Four Zr ions are located in the
corners of a slightly distorted square linked by OH bridges placed above and below the plane
of that square. The solution of these tetrameric species becomes acidic upon hydrolysis.





d
001
X
-
+ + + +
X
-
X
-
Al
+7
13
H
2
O
H
2
O
H
2
O
H
2
O
Al
+7
13
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
X
-
Al
2
O
3
Al
2
O
3
Ionic
exchange
Calcination
-Pillaring


Al

OH