Comparison of Liquid-Phase and Gas-Phase Pure Thermal Cracking of n-Hexadecane

Abstract

Thermal cracking of n-hexadecane in the mild temperature (330−375 °C) range has been investigated in liquid and gas phases. The kinetic data of liquid-phase cracking are shown to be very similar to those of gas-phase cracking. However, the pattern and distribution of the products are greatly phase dependent. In liquid-phase cracking, there is an equimolar distribution of n-alkane and 1-alkene products in the C3−C13 range at low conversion; when the conversion is increased, more alkanes than alkenes are produced. To the contrary, more alkenes than alkanes are always determined in products from gas-phase cracking. Liquid-phase cracking gives a low selectivity of gas products and a high selectivity of addition compounds (C18−C30), whereas gas-phase cracking produces a large amount of gas products and no addition compounds. The phase dependence of products can be interpreted in terms of a low concentration of hexadecane, under which β-scission occurs more preferentially than in liquid phase. Reaction mechanis...