Molecular recognition of atmospheric residues was attempted with GC-AED and GPC-ICP/MS analyses by detecting separately S, N, V and Ni elements. GC-AED could identify some molecular species on the broad distribution peak while the fraction of highest boiling range may not be eluted. In contrast, GPC-ICP/MS was expected to provide distribution of whole species while molecular recognition was basically difficult. ESR is power tool to measure the molecular states of V4+. Some petroporphyrins of V and Ni complexs were identified in sharp peaks on the broad peaks of their volatile complexs. ESR indicated that the V complex was frozen in its molecular mobility at room temperature, suggesting their trapping chemically and physically in the asphalthene moiety. GPC-ICP/MS indicated their presence in VGO and asphalthene fractions. A major part of petroporphyrin may be released thermally to be isolated from their surrounding moiety to single porphyrin molecules. Isolated molecular species of S and N were not detected, broad peak being distributed in GC-AED and GPC-ICP/MS. ARs from different crudes were recognized by the present analyses.HDM/HDS of ARs were performed in a flow reactor to find the reactivities which can be correlated to the molecular recognitions. It is found that HDM of ARs followed similar kinetic equilibrium regardless of crudes, suggesting that the total amount of metals in the crude governs the extent of HDM achievement under the same reaction conditions. Higher reactivity of V complex than that of nickel was not detected, more amount of V complex being removed more and deposited more. Such reactivity well fit to the GC-AED analyses. In contrast, kinetics of HDS were strongly influenced by crudes. Reactivity difference was definite particularly at the HDS stage where the refractory sulfur species were mainly desulfurized. Molecular moiety in the asphaltene and inhibiting species may cause the difference since aromatic sulfurs in the refractory species should be common regardless of the crude.

Recognition of molecular distribution in atmospheric residues and the correlation to their reactivities

244th National Meeting (2012)

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