Catalytic Hydrocracking—Mechanisms and Versatility of the Process

Abstract Hydrocracking of saturated hydrocarbons can proceed by means of four distinctly different mechanisms. On bifunctional catalysts comprising hydrogenation/dehydrogenation and Brønsted acid sites alkenes and carbocations occur as intermediates. The current mechanistic views of bifunctional hydrocracking of long‐chain n ‐alkanes are discussed in detail with emphasis on the now widely accepted concept of ideal hydrocracking. Other mechanisms are hydrogenolysis and Haag–Dessau hydrocracking which proceed, respectively, on monofunctional metallic and acidic catalysts. Even without a catalyst, thermal hydrocracking occurs in chain reactions via radicals. The chemistry of hydrocracking naphthenes on bifunctional catalysts resembles that of alkanes. A peculiarity, however, is the pronounced reluctance of cyclic carbenium ions to undergo endocyclic β‐scissions. The effect manifests itself in the so‐called paring reaction, which, in turn, forms the basis for measuring the Spaciousness Index for characterizing the effective pore width of zeolitic catalysts. Hydrocracking on bifunctional catalysts is among the very important processes in modern petroleum refining. It is primarily used for converting heavy oils into diesel and jet fuel. Besides, hydrocracking is appreciated for its pronounced versatility: numerous process variants exist which help to meet specific requirements in refineries or petrochemical plants. Two recent developments are briefly discussed in this review, viz. the conversion of surplus aromatics, e.g., in pyrolysis gasoline, into a synthetic feedstock for steam crackers, and quality enhancement of diesel fuel by selective ring opening of polynuclear aromatics.