The catalytics transformation of polymer waste using modified clay catalysts.

A variety of modified minerals have been screened to determine their effectiveness as agents for the catalytic transformation of the thermally generated off gases arising from the pyrolysis of the polyolefinic plastic High Density Polyethylene (HDPE). This polymer has been shown to degrade through a series of known mechanisms to yield a hydrocarbon product mixture consisting of an homologous series of saturated and unsaturated hydrocarbons which include alk-1-enes, n-alkanes, alk-x-enes and a-w-dienes.Modification treatments have been wide ranging having included activation of the parent mineral by means of pillaring, ion exchange and acid activation. The activated products have been characterised by XRD, XRF, TGA and vibrational spectroscopy. Moreover, evolved gas analysis has been employed to perform catalytic screening runs on these modified minerals. In particular, attention has been paid to the activity of these materials in respect of the formation of potentially fuel applicable hydrocarbons, namely those exhibiting high octane ratings, including aromatics and branched aliphatics from the feedstock species present in the HDPE pyrolysate gas mixture.Pillared clays (PILC's) have proven ineffective in this role as a consequence of their poor reproducibility and lack of selectivity towards the formation of single ring aromatics.Likewise, ion exchange has been found to influence strongly the catalytic behaviour of previously acid activated clays, with autotransformed samples offering dehydrocyclisation (DHC) activity at levels significantly greater than seen with some ion exchanged samples, particularly protons.Acid activated metakaolinites have demonstrated poor selectivity in terms of aromatic formation, although total DHC activity is good. Metakaolin also gave rise to appreciable activity in respect of the formation of the single ring aromatics selected for monitoring in this work. Isomerisation activity was prevalent over these materials, but coking levels were high.Acid activated smectites represent the most suitable candidates to fulfil the role of single step fuel generation from the transformation of the gas stream resulting from HDPE pyrolysis. It has been found that careful control over the chemical and physical properties of acid activated clays can be achieved through consideration of the severity of the activation parameters chosen to induce modification. In addition, the nature of the activated product is strongly dependant on the nature of the base clay. In particular, acid activated beidellites have been shown to exhibit high levels of surface acidity as determined through the thermal desorption of cyclohexylamine. These materials consequently give rise to respectable activity and selectivity in terms of the formation of highly octane rated methyl substituted single ring aromatics, principally trimethylbenzene.In contrast, acid activated montmorillonites have been seen to offer lower levels of total surface acidity and have been shown to be active in promoting skeletal isomerisation reactions to yield branched aliphatics, again, highly octane rated.This activity variation has been attributed to the formation of highly Bronsted acidic silanol containing Surface Localised Acid Pools (SLAP's) on the exposed surfaces of the former as a consequence of the isomorphous substitution patterns observed in the tetrahedral sheets of beidellites.