Thermal conversion of bitumen by
visbreaking is an important technology
for partial upgrading of bitumen to pipeline transportable oil. The
product from visbreaking of bitumen will likely spend a long time
in storage or transport before being used, and due to cost considerations,
postprocessing should be minimal. This study investigated the changes
that take place over time during storage of visbroken bitumen (420
°C, 18–22 min) under nitrogen atmosphere in the dark.
The study did not investigate phase instability, and it focused on
chemical and physical changes taking place over a storage period of
20 weeks. With increasing storage time many properties of the visbroken
liquid product changed; notably, refractive index, density, viscosity,
microcarbon residue, and n-pentane insoluble content
increased, while free radical content and aromatic hydrogen content
decreased. The observed changes during storage are best explained
by the formation of products with higher molecular mass. Although
care was taken to limit the potential impact of oxidation, indirect
evidence of the impact of oxidation due to dissolved oxygen was found
during the initial 2 weeks of storage. Oxidation was not a prerequisite
for free radical reaction during storage because the visbroken product
already contained persistent free radicals, as is typical of high
boiling petroleum fractions. Free radical termination reactions took
place, but the extent of the changes in the properties with storage
time was not consistent with simple radical–radical termination
reactions as the only source of heavier products. Alkenes (olefins)
formed during thermal conversion were likely involved in free radical
propagation reactions by radical–alkene addition to form heavier
products. The relationship between free radical content and storage
instability, the nature of reactions taking place during storage,
and the nature of the species in visbroken bitumen leading to storage
instability were discussed. To reduce the formation of products with
higher molecular mass during the storage of visbroken material, in
addition to maintaining oxygen-free conditions, it is necessary to
decrease the amount of free radicals and the amount of alkenes in
the product.