Aromatic Hydrocarbon Generation from a Simulated Bio-oil Fraction by Dual-stage Hydrogenation-cracking: Hydrogen Supply and Transfer Behaviors

The improvement of the hydrogen-poor composition of bio-oil is important for its cracking to produce aromatic hydrocarbons. In this work, a mild hydrogenation pre-treatment and methanol cocracking were combined to implement proper hydrogen supplementation for cracking. Acetic acid (HAc), hydroxypropanone (HPO), and cyclopentanone (CPO) were selected as model compounds and mixed to prepare a simulated distilled fraction (SDF) of bio-oil. The hydrogen supply and transfer behaviours in hydrogenation-cracking were investigated. For the conversion of individual components: HAc was difficult to be hydrogenated, and therefore in the cracking stage, the conversion and oil phase yield were low; ketones were successfully hydrogenated to alcohols, and thus high aromatic hydrocarbon yields were achieved. Hydrogenation-cracking of SDF showed that the inferior performance of HAc was improved by an internal hydrogen transfer, namely the alcohols produced from ketones supplied hydrogen for HAc conversion. However, because of the high HAc content in SDF, this hydrogen supplement was not sufficient. Therefore, methanol (MeOH) was used as the coreactant for secondary hydrogen supply. The integral efficient conversion of SDF and MeOH to aromatic hydrocarbons was achieved when the MeOH blending ratio was 30%. Finally, a reaction mechanism of hydrogenation-cocracking was proposed.