Heavy hydrocarbon upgrading is attracting more interest amidst growing supply of heavier crudes. These materials, often distinguished by high aromatic and asphaltene contents generate larger volumes of residue upon processing. The present study investigates the potential of partial oxidative cracking in water as an alternative to the conventional thermal cracking or hydrocracking upgrading routes. Sub and supercritical water partial oxidative cracking experiments have been carried out in a batch micro-bomb reactor using model compounds of three to five-membered ring polycyclic aromatic hydrocarbons (PAHs). The goal is twofold; to establish the optimum operating window for the PAH oxidative cracking and to evaluate the reactivity patterns between different PAH compounds. It was found that partial oxidative cracking of PAH depends strongly on reaction temperature and oxidant concentration. Using a 0.38 O/Ostoic atomic ratio (38% of the oxygen needed for complete combustion), phenanthrene and anthracene were converted at short reaction time of 0 min into mostly oxygenated intermediates (DCM solubles) at subcritical water conditions. Under the more reactive supercritical water conditions, ring cleavage products, which include phenols, aromatic acids, ketones and unsubstituted aromatics (DCM solubles) were favoured. Most of these intermediates were formed via middle ring oxygenation which could potentially contribute to higher cracking efficiency upon subsequent thermal treatment. In addition to the target compounds, polymerized materials (DCM insolubles) were also produced under both conditions. A good compromise between the two major product streams was obtained at 400 oC whereby the DCM fraction contains a balanced mixture of oxygenated and cracking compounds. PAHs exhibit higher degree of stability with increasing ring size. A higher reaction temperature of 450 oC was needed in order to convert pyrene and benzo[a]pyrene. The reactivity order with respect to PAH conversion into the desirable DCM soluble fraction was established as follows: anthracene > phenanthrene > pyrene > benzo[a]pyrene.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:555895 |
| Date | January 2011 |
| Creators | Daud, Ahmad Rafizan Mohamad |
| Contributors | Kandiyoti, Rafael : Millan-Agorio, Marcos : Hellgardt, Klaus |
| Publisher | Imperial College London |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/10044/1/9592 |
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