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ples already exist and rapid growth is expected in the near future, both in new

plants and in retroﬁ tted current ones.

The ammoxidation of (substituted) alkylaromatics, with or without heteroatoms,

is also a well established reaction of interest for the production of ﬁ ne and specialty

chemicals. Although commercial, the number of processes is still limited. However,

there is a growing interest in new market areas such as China, and new processes

may be expected in the near future.

The ammoxidation process could be also used in the conversion of less - conven-

tional molecules. Various examples are discussed in detail, and it can be remarked

that owing to the relatively limited research effort, there is still a relatively large

degree of possible improvement. The need for more reproducible results in some

cases is also stressed. Nevertheless, this ﬁ eld could offer new interesting com-

mercial opportunities.

Although still limited, there is also some interest in using biomass - derived raw

materials (bio - ethanol, glycerine) in ammoxidation processes. These processes

could be of value only in the context of valorization of side streams in bio - reﬁ nery

plants. However, owing to the growing interest in the latter, it may be expected

that some opportunities will arise for the ammoxidation of biomass - derived side -

products in the near future.

This overview of the catalysts and catalytic processes of vapor - phase ammoxida-

tion has brieﬂ y summarized the state of the art and some perspectives in the ﬁ eld,

although it was not possible to present a comprehensive review owing to the very

large volume of literature and patents that has appeared in recent years. In some

cases, as for C

3

and akylaromatic ammoxidation, various reviews are available and

these have been referenced.

In conclusion, this overview demonstrates that the ammoxidation ﬁ eld is still a

quite attractive area from both fundamental and commercial points of view. It also

stresses that the same concepts and catalysts used for more known areas (such as

acrylonitrile synthesis) could also be successfully applied in the conversion of less -

conventional molecules.

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Metal Oxide Catalysis. Edited by S. David Jackson and Justin S. J. Hargreaves

ISBN: 978-3-527-31815-5

Base Catalysis with Metal Oxides

Khalaf AlGhamdi , Justin S. J. Hargreaves , and S. David Jackson

819

21

21.1

Introduction

With increasing recognition of the complimentarity of their behavior to that of

acid catalysts, the study of base catalysts is becoming more widespread. Whilst,

for example, both acid and base catalysts of appropriate strength can be applied

to analogous processes, there are pronounced differences in the product distribu-

tion, which is a consequence of the fundamentally different pathways involved.

An illustrative example of this behavior is the alkylaromatic side - chain alkylation

reaction, where it is observed that in the presence of a basic catalyst the side chain

of the alkyl group is alkylated rather than the aromatic ring, as would be expected

with acid catalysis [1] . In a survey of industrial processes published in 1999, Tanabe

and Holderich [2] identiﬁ ed 10 major base - catalyzed processes as compared to 103

acid - catalyzed processes and 14 solid acid – base - catalyzed processes. In this chapter

we concentrate our attention on heterogeneous base catalysts, and the examples

and discussion given are intended to be illustrative of the general ﬁ eld rather than

providing an extensive bibliography. Additional reviews detailing this topic can be

found elsewhere, for example References [3 – 8] . Within this chapter, we exclusively

direct our attention to oxide, or oxide - based, catalytic systems.

Base catalysts are extremely sensitive to the atmosphere in which they have

been stored and generally require some sort of activation procedure, usually

heating, prior to application. For materials stored in air, the formation of surface

carbonates via reaction with atmospheric carbon dioxide is problematic. Figure 21.1

illustrates the effect of pre - treatment upon base - catalyzed n - butene isomerization

[9] . It can be seen that activity increases up to a maximum of circa 650 ° C.

It is, of course, important to recognize that in general base catalysts exhibit

bifunctional behavior and are therefore, strictly, amphoteric. The same general

point can also be made concerning acid catalysts, and therefore the distinction

between acidic and basic solid catalysts is made on the basis of dominant behavior,

although in some cases, for example ZrO

2

, there may be no single dominant

behavior [10] . An illustrative example of this is the alkaline earth metal oxides,

classical base catalysts, where oxide ions behave as bases and the metal cations

820 21 Base Catalysis with Metal Oxides

can function as Lewis acids. Given the distribution of different co - ordination sites

present, as discussed elsewhere in this volume and shown schematically in Figure

21.2 [11, 12] , it can be anticipated that a range of base strengths will be exhibited,

and the stronger sites can be successively accessed by increasing severity of pre -

treatment. Furthermore, such considerations are indicative that there would be

a signiﬁ cant dependence of activity for a base - catalyzed reaction upon catalyst

Figure 21.1 The development of base - catalyzed activity at 0 ° C

over La

2

O

3

as a function of pre - treatment temperature.

(Reproduced from [9] with permission).

Figure 21.2 A schematic illustrating a variety of different

co - ordination sites on the MgO (100) surface. (Reproduced

from [12] with permission).

Jackson S.D., Hargreaves J.S.J. Metal Oxide Catalysis

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