Structural determination by XAFS spectroscopy of non-porphyrin nickel and vanadium in maya residuum, hydrocracked residuum, and toluene-insoluble solid
Jt. Miller et al., Structural determination by XAFS spectroscopy of non-porphyrin nickel and vanadium in maya residuum, hydrocracked residuum, and toluene-insoluble solid, ENERG FUEL, 13(3), 1999, pp. 719-727
The local structure of non-porphyrin Ni and V in Maya residuum, hydrocracke
d residuum, and toluene-insoluble solid were determined by XAFS spectroscop
y. In residuum, the first coordination shell of non-porphyrin V is similar
to that for vanadyl tetraphenylporphyrin with four N at a distance of 2.08
Angstrom and one O at 1.67 Angstrom. Similarly, the first coordination shel
l of Ni non-porphyrin is similar to that in nickle tetraphenylporphyrin, i.
e., four N at a distance of 1.90 ii. The Ni and V coordination geometries a
re remarkably stable toward thermal cracking, catalytic hydrogen, and H2S.
After hydrocracking to about 60% conversion of the residuum, the local coor
dination of Ni and V in the hydrocracked residuum is little changed. During
hydrocracking, approximately 1% of the residuum is converted to toluene-in
soluble solid, which contains high levels of Ni and V. Approximately 10% of
the Ni and V in the solid is still present in a porphyrin-type coordinatio
n geometry, while the remaining Ni and V has an octahedral coordination. In
the latter, the V coordination contained one O at 1.64 Angstrom, four N at
2.14 Angstrom, and one N (or O) at 1.96 Angstrom, and the Ni coordination
contained six N at 2.09 Angstrom. Ni or V sulfides are not formed in the to
luene-insoluble solid.