Polycyclic aromatic hydrocarbons (PAH) are refractory structures common in heavy hydrocarbons. Thermal cracking in supercritical water (SCW) is limited but PAH can be completely oxidised if an oxidant is added. By restricting oxidant supply to substoichiometric amounts, this study aims to achieve partial oxidation as a route to useful chemicals, such as mono- and bi-aromatics. Oxidative cracking reactions of anthracene, pyrene and benzo[a]pyrene in subcritical and SCW were studied. PAH conversions well above 90 % were achieved along a fast heating ramp in a batch reactor. This quick initial oxidation took place predominantly in inner rings, weakening the aromatic structure and increasing cracking reactivity. This oxidation-cracking pathway became dominant in the SCW region, producing mostly oxygenated compounds with fewer aromatic rings. On the other hand, competing reactions leading to polymerization were favoured in the subcritical water region. PAH reactivity was found to follow the order anthracene > benzo[a]pyrene > pyrene.

多环芳烃（PAH）是重烃中常见的耐火结构。超临界水（SCW）中的热裂化受到限制，但是如果添加氧化剂，则PAH可以被完全氧化。通过将氧化剂的供应量限制在化学计量以下，本研究旨在实现部分氧化，以此作为获得有用化学物质（例如单环和双环芳烃）的途径。研究了蒽，pyr和苯并[a] py在亚临界和SCW中的氧化裂解反应。在间歇式反应器中，通过快速加热，PAH的转化率远高于90％。这种快速的初始氧化主要发生在内环上，从而削弱了芳族结构并提高了裂化反应性。这种氧化裂化途径在SCW地区占主导地位，主要生产含氧化合物，且芳环较少。另一方面，导致聚合的竞争性反应在亚临界水区域中是有利的。发现PAH反应性遵循蒽>苯并[a] py> pyr的顺序。