Single-core PAHs in petroleum- and coal-derived asphaltenes: size and distribution from solid-state NMR spectroscopy and optical absorption measurements
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Date
2016
Authors
Majumdar, R. Dutta
Bake, K. D.
Ratna, Y.
Pomerantz, A. E.
Mullins, O. C.
Gerken, Michael
Hazendonk, Paul
Journal Title
Journal ISSN
Volume Title
Publisher
American Chemical Society
Abstract
Using solid-state 13C NMR spectroscopy of two different asphaltenes, one derived from petroleum and the other from coal liquids, it was shown that the asphaltene molecular architecture consists of a spectrum of sizes, ranging from smaller polyaromatic hydrocarbons (PAHs; <5 condensed rings) to much larger ones (>9 condensed rings), but their distribution varies between the two. It is shown that smaller PAHs are likely more abundant in the coal-derived asphaltenes, while the largest PAH cores of the two different asphaltenes are similar in size. These observations are reinforced by optical absorption. The coal-derived asphaltenes were found to contain a small fraction of archipelago-type structures, where a small PAH is tethered to the larger PAH core via an aryl linkage, which are less evident, and likely less abundant, in the petroleum asphaltenes. An important difference between the two asphaltenes lies in their alkyl fraction, with the petroleum asphaltenes possessing significantly longer and more mobile alkyl side chains, on average ∼7 carbons long, as opposed to an average chain length of ∼3–4 in the coal asphaltenes. The petroleum asphaltenes also possess a larger fraction of alicyclics. The longer length increases the propensity of the petroleum asphaltene alkyl side chains to intercalate between the aromatic rings of adjacent asphaltene aggregates, which is not observed in coal-derived asphaltenes. This work demonstrates the utility of combining cross-polarization dynamics and directly polarized 13C solid-state NMR spectroscopy in studying asphaltenes, while adding to the body of evidence supporting the single-core model of asphaltenes, which appears to be the dominant structural motif for this fraction of petroleum.
Description
Accepted author manuscript
Keywords
Asphaltenes , PAHs
Citation
Majumdar, R. D., Bake, K. D., Ratna, Y., Pomerantz, A. E., Mullins, O. C., Gerken, M., & Hazendon, P. (2016). Single-core PAHs in petroleum- and coal-derived asphaltenes: Size and distribution from solid-state NMR spectroscopy and optical absorption measurements, 30(9), 6892-6906. https://doi.org/10.1021/acs.energyfuels.5b02815