Co-Hydroprocessing of Fossil Middle Distillate and Bio-Derived Durene-Rich Heavy Ends under Hydrotreating Conditions

Abstract

Methanol-to-gasoline (MTG) and dimethyl ether-to-gasoline (DTG), as industrially approved processes for producing greenhouse gas-neutral gasoline, yield byproducts rich in heavy mono-ring aromatics such as 1,2,4,5-tetramethylbenzene (durene). Due to its tendency to crystallize and the overall poor fuel performance, the heavy fuel fraction is usually further processed using after-treatment units designed for this purpose. This research article discusses the co-hydroprocessing (HP) of bio-derived heavy gasoline (HG) with fossil middle distillate (MD), drawing on available refinery hydrotreaters. Co-HP experiments were conducted in a laboratory-scale fixed bed reactor using an industrial CoMo/γ-Al2O3 catalyst, varying the space-time between 0.7 and 4.0 cmCat3 h cmFeed−3 and the reaction temperature between 340 and 390 °C. In addition to the durene conversion, special attention was paid to the octane and cetane numbers (CN) of gasoline and MD, respectively. A six-lump model with ten parameters was developed to predict relevant fuel yields dependent on the process conditions. Under stable catalyst conditions, C10 aromatic conversions of more than 60% were obtained, while the CN remained close to that of pure MD. Harsh process conditions increased the gasoline yield up to 20% at the cost of MD, while the kerosene yield remained almost constant. With an optimized lumping model, fuel yields could be predicted with an R2 of 0.998. In this study, co-HP heavy aromatic-rich MTG/DTG fuels with fossil MD were proven to be a promising process strategy compared to a stand-alone after-treatment.