Cleavage of biphenyl moieties: An efficient new reaction pathway in catalytic hydrocracking

Journal Article · Thu Oct 01 00:00:00 EDT 1992 · Journal of Catalysis; (United States)

DOI:https://doi.org/10.1016/0021-9517(92)90177-J· OSTI ID:7257752

Klein, M T; Lapinas, A T; Gates, B C; Read, C J; Lyons, J E ^[1]; Macris, A ^[2]

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1. Univ. of Delaware, Newark (United States)
2. Sun Co., Marcus Hook, PA (United States)

The hydrocracking of the five-carbon-membered-ring-containing PNA fluoranthsene (I) is qualitatively different from the classical pattern. A major reaction pathway involves hydrogenation to give tetrahydrofluoranthene (II), center ring opening to give phenyl tetralin (III), and biphenyl cleavage to give tetralin (IV) and benzene. This mechanism includes protonation of (III) followed by an internal 1,5-hydride shift to afford the carbenium ion III{sup +}, of III, represented in the benzylic form. A 1,3-hydride shift of a resonance form of III{sup +} affords benzene and a carbenium ion IV{sup +}, the deprotonation of which leads to an intermediate, dialin, which is rapidly hydrogenated to yield tetralin. The noteworthy reaction in the sequence, which is a net 1.5-shift of the benzylic hydride to the ring bearing the positively charged carbon, evidently takes place along a molecular topology that includes a strong biphenyl linkage. This suggests an apparent structural moiety for efficient cleavage of strong biphenyl linkages, which otherwise would require prior hydrogenation. Thus, the authors have investigated the catalytic hydrocracking of molecules that either contain this structural moiety, or can react to form it. Experiments were done to determine the hydrocracking pathways and kinetics of 9-ethyl fluorene, 9-phenyl anthracene, and 2-phenyl naphthalene in the presence of an equilibrated Ni-Mo/Al{sub 2}O{sub 3}-catalyst-containing ultra-stable Y-Zeolite at 310-380 C and 153 atm.

• OSTI ID: 7257752
• Journal Information: Journal of Catalysis; (United States), Journal Name: Journal of Catalysis; (United States) Vol. 137:2; ISSN 0021-9517; ISSN JCTLA
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
020400* -- Petroleum-- Processing
ALUMINIUM COMPOUNDS
ALUMINIUM OXIDES
AROMATICS
BENZENE
CATALYSTS
CATALYTIC CRACKING
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CLEAVAGE
CONDENSED AROMATICS
CRACKING
CRYSTAL STRUCTURE
DECOMPOSITION
ELEMENTS
FLUORINATED AROMATIC HYDROCARBONS
HALOGENATED AROMATIC HYDROCARBONS
HYDROAROMATICS
HYDROCARBONS
HYDROCRACKING
HYDROGENATION
INORGANIC ION EXCHANGERS
ION EXCHANGE MATERIALS
KINETICS
MATERIALS
METALS
MICROSTRUCTURE
MINERALS
MOLYBDENUM
NICKEL
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PYROLYSIS
REACTION INTERMEDIATES
REACTION KINETICS
SILICATE MINERALS
SYNTHESIS
TETRALIN
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENTS
ZEOLITES