In this study, we
focus on a quantitative characterization of aromatic
cluster evolution in vitrinite-rich coal during coalification processes.
By employing high-resolution transmission electron microscopy (HRTEM)
and Fourier transform infrared spectroscopy (FT-IR), a detailed structural
evolution of the aromatic clusters has been characterized and analyzed.
Based on the results, a stepwise aromatic structure evolution was
observed and can be divided into four stages: 0.5 to ∼1.4%,
∼1.4 to ∼2.0%, ∼2.0 to 3.7%, and 3.7 to 4.2%.
In the first stage (R
o,ran =0.5% to ∼1.4%),
naphthalene and 2 × 2 aromatic rings are tailored down from the
main coal structure due to a cleavage of ether bonds and aliphatic
bridge bonds. For R
o,ran from ∼1.4%
to ∼2.0%, new naphthalene and 2 × 2 aromatic rings are
formed in the second stage through the aromatization of aliphatic
structures. When R
o,ran is from ∼2.0
to 3.7%, much more 3 × 3 and 4 × 4 aromatic rings are formed
through the condensation of small aromatic rings. In the last stage
for anthracite coals (R
o,ran > 3.7%),
larger-sized aromatic rings are formed mainly by the condensation
of 3 × 3 aromatic rings. During the coalification process, 3
× 3 aromatic rings play important roles in the evolution of aromatic
clusters. Small aromatic rings are first enlarged to 3 × 3 aromatic
rings, and then these 3 × 3 aromatic rings would form large-scale
aromatic clusters. HRTEM can also provide quantitative information
of the spatial alignment of aromatic clusters in coal. In anthracite
coals with R
o,ran >3.7%, most of these
fringes are highly aligned and share the same angle.