Desulfurization with transition metal catalysts. [Desulfurization of 2-methyldibenzothiophene, dibenzothiophene, sulfones]

Technical Report · Fri Jul 31 04:00:00 EDT 1981

OSTI ID:6213232

Eisch, J J

During the seventh quarter of this two-year contract the following aspects of desulfurization were pursued: (1) study of the reactivity and the intermediates in the desulfurization of 2-methyldibenzothiophene and certain model sulfides and sulfones; (b) examination of the ratio of bis-1.5-cyclooctadiene-nickel; (c) exploration of the desulfurizing activity of soluble organocobalt complexes; (d) evaluation of the activity of aluminum hydride combinations with nickel(II), cobalt(II) and molybdenum(0) or molybdenum(IV) salts; and (e) planning experimental procedures for applying these techniques to coal-derived liquids. The following results have been obtained: (1) the desulfurization of 2-methyldibenzothiophene has been shown to be much slower than that of dibenzothiophene, and the product has been identified as 3-methylbiphenyl exclusively; as to sulfones, some interesting desulfurization routes have been revealed; (b) a 1:1 ratio of bis-1,5-cyclooctadiene-nickel(0) and ..cap alpha..,..cap alpha..'-dipyridyl exhibits an optimal desulfurization action; ratios of 1:2 or 2:1 are decidedly less effective; (c) the preparation os the complex, 1,5-cyclooctadiene(3-cyclooctenyl)cobalt has been completed and this complex, combined with ..cap alpha..,..cap alpha..'-bipyridyl in tetrahydrofuran solution at 65 to 70/sup 0/C, proved to be an effective desulfurizing agent toward dibenzothiophene; (d) the generation of low-valent metal desulfurizing agents in situ, namely by the treatment of metal salts with LiAlH/sub 4/ or R/sub 2/AlCl, shows considerable promise with nickel(II) and cobalt(II) salts, but not much for molybdenum carbonyls or molybdenum(IV) salts; and (e) a literature search is underway to identify suitable manipulative and analytical techniques for attempted desulfurizations of SRC=II coal liquids.

• Research Organization: State Univ. of New York, Binghamton (USA). Dept. of Chemistry
• DOE Contract Number: AC22-79ET14879
• OSTI ID: 6213232
• Report Number(s): DOE/ET/14879-T6; ON: DE81028935
• Country of Publication: United States
• Language: English

Related Subjects

01 COAL, LIGNITE, AND PEAT
010402* -- Coal
Lignite
& Peat-- Purification & Upgrading
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
ALUMINIUM COMPOUNDS
ALUMINIUM HYDRIDES
AZINES
BIPYRIDINES
CARBONYLS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
COBALT COMPOUNDS
COMPLEXES
CYCLOALKENES
DESULFURIZATION
ELEMENTS
FURANS
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
MEDIUM TEMPERATURE
METALS
MOLYBDENUM
NICKEL COMPLEXES
NICKEL COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PYRIDINES
REFRACTORY METALS
RESEARCH PROGRAMS
SALTS
SULFONES
SYNTHESIS
TETRAHYDROFURAN
THIONAPHTHENES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS