468 A. Marcilla et al. / J. Anal. Appl.

Pyrolysis 68
/69 (2003) 467
/480

1. Introduction

The consumption of plastics has become a need for the developed countries. In the
middle of the seventies, the world-wide consumption of thermoplastics was around
13 million tons yr 1, but with the increase in the application of these materials in the
following years, the present demand exceeds 70 million tons yr1 [1]. For this
reason, plastic materials, mainly polyethylene (PE) and polypropylene (PP) have
became an important part of solid urban wastes mainly from containers and
packaging, in spite of the fact that a significant quantity of these plastic materials is
used in the production of long-life products. PP is used in several markets, for
instance, in food packaging, medical bags, computer components, car components,
pipes and general containers. . . This versatility of PP is due to its good chemical
resistance and its low density (good relation properties per weight). PP has a
relatively high melting point compared with other similar polymers, thus being useful
to contain hot substances. This material represents nowadays 22% of the thermo-
plastics’ market, with a strong increase since 1983 [2].
Nowadays, incineration is the more widely-used way to eliminate solid residues at
the same time as electric and calorific energy are generated. But uncontrolled
incineration can produce serious health and environment problems due to the
possible emission of dioxins, furans, acid gases and heavy metals. For this reason,
the search for different recycling alternatives is more and more necessary [3].
The pyrolysis of such materials is an alternative process which consists in the
thermal degradation of the polymer macromolecules in the absence of oxygen,
producing a mixture of hydrocarbons, operating in a temperature range of 500
/
850 8C [4
/7]. However, this degradation requires a considerable quantity of energy
due to its endothermic character and the low thermal conductivities of the plastic
materials throughout the process [8].
The use of catalysts allows the reduction of the temperature of the process to the
350
/550 K range and thus, increases the versatility of the pyrolysis as a recycling
technique at an industrial scale [9
/14]. In this way, with the right selection of the
catalyst and operating conditions, it is also possible to optimise the product
distribution in order to obtain a more profitable process. Normally, the catalysts
used in the catalytic pyrolysis of plastic materials are acid solids such as zeolites,
amorphous silica-alumina and MCM mesoporous materials [2,15
/24]. In all these
cases, the use of the catalyst reduces the energetic demand of the process and
improves, from the economic point of view, the product distribution by increasing
the yield of the more volatile products and lowering the yield of subproducts.
However all these catalysts are expensive and, at the moment, there are no useful
ways to improve their short life and difficult recycling, so their use involves a cost
increase in the operational process.
Fluid catalytic cracking (FCC) is a process used in refineries to upgrade the
heavier crude fractions in order to improve the global yields of higher added value
products, such as liquefied petroleum gases (LPG), naphthas, and medium
distillates. Furthermore, from the petrochemical point of view, FCC is of great
importance due to the high olefin yields in LPG and naphthas, which allows, for