Energy & Fuels, Vol.34, No.7, 8452-8465, 2020
Corefining of Fast Pyrolysis Bio-Oil with Vacuum Residue and Vacuum Gas Oil in a Continuous Slurry Hydrocracking Process
Integration of renewable raw materials in existing refineries is most likely the shortest way for the successful, largescale introduction of biofuels in the transport sector in the short term and medium term. One possible renewable raw material for this application is fast pyrolysis bio-oil (FPBO), which in this study has been coprocessed (at 0 and 20 wt %) with vacuum residue (VR, 50 wt %) and vacuum gas oil (VGO, balance) in a continuous, as well as a semibatch, slurry hydrocracking process. Experiments both with and without FPBO were performed at 450 degrees C and 150 bar with a continuous hydrogen flow through the reactor. Oil-soluble molybdenum hexacarbonyl and molybdenum 2-ethylhexanoate were used as catalyst precursors, to be sulfided in situ. The continuous trials resulted in reactor walls completely free of coking, and they resulted in a low overall coke yield (about 1 wt %). The hydrodeoxygenation reached almost 92%, and the total acid number was reduced by nearly 99% in the FPBO experiment. A mass balance of the renewable carbon from FPBO, based on the performed experiments, showed that the fossil CO, emissions can be lowered by 1.35 kg per kilogram of processed FPBO if all renewable carbon in gaseous and liquid hydrocarbons is used to replace its fossil counterparts, and all methane formed from FPBO is used to produce hydrogen. Semibatch experiments gave less successful results when upgrading FPBO-containing feedstock, with a high coke yield (8 wt %) as well as a high gas yield (24 wt %). The results of this study demonstrate that FPBO can be successfully coprocessed with heavy fossil oils in a continuous slurry hydrocracking process without negatively affecting the processing of the fossil components of the feed and that a continuous process is preferred over batch or semibatch processes when studying coprocessing of bio-oils.