Nature and distribution of vanadium and nickel complexes in petroleum

Thesis/Dissertation · Thu Jan 01 04:00:00 EST 1976

OSTI ID:7322028

Branthaver, J F

A method was developed for isolating two of the major porphyrin fractions of Boscan crude. This method is based on the observation that 80% HF-20% H/sub 2/O demetalates petroporphyrins of the DPEP series, while other petroporphyrins require anhydrous HF to effect demetalation. NMR, mass spectral, and visible spectral studies show that the DPEP series of Boscan petroporphyrins are very similar to synthetic DPEP. The etioporphyrins in Boscan crude are different from etioporphyrins I-IV. From GPC, Boscan asphaltenes can be separated into three fractions. Evidence was obtained for the existence of non-porphyrin nickel complexes in this fraction. The porphyrins in this fraction have more of the rhodo-type porphyrins than does the rest of the crude. This fraction is very intractable, and special methods are needed to obtain significant amounts of low molecular weight materials from it. A second GPC-fraction contained porphyrin and non-porphyrin complexes in equal amounts. A third GPC-fraction had all metals accountable as porphyrin complexes. Vanadium to nickel ratios were similar in all these fractions. Boscan petrolenes were found to have relatively more etiotype porphyrins compared with DPEP-type porphyrins than did Boscan asphaltenes. These studies led to the conclusion that either the crude evolved from different progenitor capable of migration, or metal incorporation is the result of bacterial action in the reservoir. Metal content in Boscan crude was reduced by chlorine and peroxides in a radical reaction, but chlorine incorporation was also high. These reagents attack the meso-positions of metalloporphyrins at low temperatures. The adding of more than two chlorine molecules to a porphyrin molecule leads to demetalation of the porphyrin. Petroporphyrins are much more readily demetalated by chlorine than metal complexes of OEP. New metal complexes of meso-chlorinated OEP's were synthesized and spectral data reported. (DLC)

• OSTI ID: 7322028
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
023000* -- Petroleum-- Properties & Composition
ASPHALTENES
ASPHALTS
BITUMENS
CARBOXYLIC ACIDS
CHEMICAL COMPOSITION
COMPLEXES
ENERGY SOURCES
ETIOPORPHYRINS
FOSSIL FUELS
FRACTIONATION
FUELS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
MAGNETIC RESONANCE
NATURAL OCCURRENCE
NICKEL COMPLEXES
NUCLEAR MAGNETIC RESONANCE
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OTHER ORGANIC COMPOUNDS
PETROLEUM
PORPHYRINS
RESONANCE
SEPARATION PROCESSES
TAR
TRANSITION ELEMENT COMPLEXES
VANADIUM COMPLEXES