Fuel Vol. 76, No. 4, pp.

359 -362, 1997

© 1997 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
ELSEVIER
PII: S0016-2361(96)00220-7 0016-2361/97 $17.00+0.00

Particle size dependence of coal volatile matter: is there

a non-maceral-related effect?

J o n a t h a n P. M a t h e w s *t, P a t r i c k G. H a t c h e r *t and A l a n W . S c a r o n i *t
* The Combustion Laboratory, .t Energy & Fuels Research Center and Fuel Science Program, 211 CUL,
The Pennsylvania State University, University Park, PA 16802, USA
(Received 7 June 1996," revised 2 October 1996)

Proximate analyses were conducted on different size fractions of pure vitrinite from two bituminous coals
and demineralized vitrinite from one of the coals. CO2 surface areas were also determined, to aid in assessing
the possible influence of pore diffusion of volatiles in particles of different sizes. The results implied that for
comminuted coals, the particle size dependence of the measured volatile matter, after correction for effects
of mineral matter, is due almost entirely to differences in maceral composition. © 1997 Elsevier Science Ltd.
All rights reserved.

(Keywords: coal; volatile matter; particle size effects)

For many coals, the volatile matter as
measured by the ASTM standard 1
depends on particle size2-4. This is
often because of inorganic and organic
compositional effects due to the differ-
ences in friability among the minerals
and maceral groups and/or chemical
heterogeneity within maceral groups 2-8.
Thus, within the size range of pulverized
coal particles (70-80wt% <75#m),
particle size cuts can have significantly
different volatile matter. Unfortunately,
direct observation of the maceral dis-
tribution in particles of this size range is
difficult8. Thus, the existence of non-
maceral effects on volatile matter, i.e. by
changing the particle size while main-
taining the sample mass and composi-
tion, has not been established. It has also
been implied in the literature that, with
decreasing particle size, the path length
for pore diffusion of the volatiles is
reduced, thereby reducing the occurrence
of secondary reactions within the pores 9
and increasing the volatile matter. The
influence of particle size, in the pulver-
ized coal size range, on the volatile
matter of two bituminous coal vitrinites
is reported here. Both samples were pure
telocollinites from obvious tree remains
and so were not subject to maceral
differences among the particle size cuts.
The objective was to eliminate maceral-
based particle size effects (by using pure
macerals) and establish the existence or
not of a non-maceral-based effect.
EXPERIMENTAL
The vitrinite samples were collected from
Sigillaria (a type of lycopod) tree remains
in the roofs of coal mines from the Upper
Freeport (UF) and Lewiston-Stockton
(LS) coal seams. The samples were
comminuted in a commercial pulverizer.
Particle size separation was achieved by
wet sieving (dry sieving did not produce
sharp size cuts). The particle size
distributions were determined with a
malvern laser light instrument. The
samples were stored under a nitrogen
atmosphere in sealed bags to prevent
oxidation. A subset of the LS vitrinite
size cuts and the 3 8 - 7 5 # m cut of the
U F vitrinite were demineralized using a
I0% HC1 (weight basis) treatment over-
night followed by a concentrated H F
acid (52% weight basis) treatment for
,-~100h with occasional stirring. Any
remaining fine clays were removed by
utilizing a dispersant, which suspended
them while allowing coal particles to
settle during centrifugation. The sam-
ples were washed thoroughly with dis-
tilled water and allowed to air-dry. The
mean maximum vitrinite reflectance
was calculated in accordance with
ASTM procedures 1°.
Proximate analysis was obtained using
a thermogravimetric analyser (t.g.a.) and
a commercial instrument (Leco Mac-
400). The t.g.a, uses milligram quantities
of material as opposed to the 1 g required
for the ASTM test 11. Briefly, 5 :E 0.2mg
of sample was placed in a platinum pan
and held at 30°C in flowing nitrogen for
1 h to remove oxygen from the sample
chamber. The temperature was ramped
at 5 0 K m i n -1 to ll0°C and held at that
temperature for 10 rain, with the weight
loss reported as moisture. The tempera-
ture was then ramped to 950°C at
5 0 K m i n -1 and maintained for 7min.
The weight loss at the end of this period
was reported as volatile matter. The
temperature was reduced to 750°C at
200 K rain -1, the atmosphere changed to
flowing air and the temperature held
constant for 25min. The remaining
material was reported as ash. The Mac-
400 uses a modified ASTM procedure
for proximate analysis (not the tradi-
tional rapid heating method) I. Because
of 'popping', caused by the high ther-
mal expansion of the bituminous coal
vitrinite, the sample mass was reduced
to 0 . 5 ± 0 . 0 1 g instead of the ASTM
specified 1 g.
Surface area measurements were per-
formed on ,-~0.2g of sample, outgassed
for a minimum of 24h at ll0°C and a
pressure of 0.7mPa. The CO2 surface
areas were calculated using the Dubinin-
Radushkevich analysis of the adsorption
isotherms. The saturated pressure of CO2
at 0°C was taken to be 3.4847MPa,
while the cross-sectional area of a single
CO2 molecule was taken to be 25.3 ,~2 at
0°C. The isotherms were determined at
0°C, with the temperature maintained by
a water-antifreeze constant-temperature
bath.
RESULTS A N D DISCUSSION
The mean maximum vitrinite reflectance
values were 0.97% (s.d. 0.04%) and
0.93% (s.d. 0.08%) for the U F and LS
vitrinites respectively. Both samples were
determined to be monomaceral in com-
position, using polished briquettes with
reflected white and blue light. Particle
size distributions of the size fractions are
shown in Table 1. The 'expected' mean is
the mean of the upper and lower mesh
screen apertures.
From Tables 2 and 3 it can be seen that
the most obvious difference among size
cuts was the mineral matter content, the
larger particle sizes having high ash. The
ash decreased and then increased with
decreasing vitrinite particle size. The U F
vitrinite size cuts had similar volatile
matter (daf), although the quantity of
ash was very different (Table 2). It is
expected that the composition of the ash
would also be significantly different
among the particle size cuts, due to the

Fuel 1997 Volume 76 Number 4 359

Particle size dependence of coal volatile matter: J. P. Mathews et al.

Table 1 Particle size distribution and CO 2 surface areas for the vitrinite size fractions
Coal Size ~action C O 2 surface Expected size Expected D[0.5] a D[0.9] a D[0.1] a
(US mesh) area (m 2 g-I dan range (#m) mean size (#m) (#m) (pro) (#m)
UF > 60 102 < 250 n.a. b 368 519 215
60-100 160 250-150 200 226 409 177
100-200 177 150-75 112.5 131 175 84
200-400 158 75-38 56.5 65 ll0 44
200-400 c - 75-38 56.5 63 95 42
< 400 157 < 38 n.a. 26 55 9
LS 60-100 - 250-150 200 210 343 158
100-200 - 150-75 112.5 102 135 73
200-400 - 75-38 56.5 61 92 39
< 400 - < 38 n.a. 20 41 6
a Analysis is based on volume; D[0.5] is the volumetric weighted average size, D[0.9] and D[0.1] the particle diameters such that 90%
and 10% respectively of the total volume is in particles of smaller diameter. Vitrinite particles were assumed to be spherical. These
data were collected in the model-independent mode
b Not applicable
c Demineralized sample

Table 2 Proximate analyses (wt%) of the U F vitrinite size fractions a

Method US mesh Volatile matter (db) Fixed carbon (db) Ash (db) Volatile matter (daf)
T.g.a. > 60 33.0 (0.82) 46.4 (2.30) 20.6 (3.12) 41.6
60-100 36.5 (0.72) 52.8 (1.00) 11.0 (0.65) 41.1
100-200 37.9 (0.49) 56.7 (0.36) 5.4 (0.68) 40.1
200-400 38.2 )0.40) 53.6 (0.31) 8.3 (0.68) 41.6
< 400 36.5 (0.47) 48.4 (0.83) 15.5 (0.53) 42.8
Mac-400 > 60 29.6 (0.08) 51.6 (0.63) 18.8 (0.62) 36.5
60-100 33.3 (0.09) 56.6 (0.37) 11.1 (0.29) 36.4
100-200 32.7 (0.32) 61.81 (0.53) 5.5 (0.31) 34.6
200-400 33.0 (0.18) 57.6 (0.15) 9.3 (0.04) 36.4
< 400 31.5 (0.14) 52.5 (0.16) 16.0 (0.05) 37.7
a Values in brackets are standard deviations based on three sample analyses for t.g.a, and duplicate analyses for Mac-400

Table 3 Proximate analyses (wt%) of the LS vitrinite size fractions ~

Method US mesh Volatile matter (db) Fixed carbon (db) Ash (db) Volatile matter (daf)
T.g.a. 60-100 25.9 (0.65) 41.5 (1.41) 32.6 (2.04) 38.5 (0.27)
100-200 30.8 (0.43) 52.7 (0.39) 16.5 (0.82) 36.9 (0.16)
200-400 30.5 (0.27) 51.4 (1.56) 18.1 (1.42) 37.3 (0.84)
< 400 23.4 (0.41) 31.9 (0.44) 44.8 (0.07) 42.4 (0.77)
Mac-400 60-100 24.1 (0.13) 43.9 (0.60) 32.0 (0.44) 35.5 (0.42)
100-200 27.5 (0.13) 54.1 (0.19) 18.4 (0.06) 33.6 (0.33)
200-400 26.7 (0.13) 54.8 (0.95) 18.5 (1.07) 33.8 (0.28)
< 400 19.7 (0.35) 34.0 (0.23) 46.5 (0.12) 36.5 (0.59)

As in Table 2

different friabilities of the minerals 6. This
has an influence on the volatile matter,
due to the weight loss associated with
clays releasing water from their
lattices, iron sulfides oxidizing and
releasing sulfur dioxide, and carbonates
decomposing and releasing carbon
dioxide 12. Thus both the quantity and
composition of the mineral matter may
influence the volatile matter of the size
cuts. The situation is exacerbated in the
higher-ash, LS vitrinite samples (Table 3),
where the volatile matter (daf) varied
significantly with particle size. The use of
daf values in this situation can be
misleading, if only the contribution of
the organic structure to the volatile
matter is desired, as demonstrated by
the difference in the volatile matter (daf)
for LS raw and demineralized vitrinite
size cuts given in Tables 3 and 4,
respectively. The use of dmmf values is
preferable, but this calculation assumes
a certain mineral matter composition
and thus is likely to be biased for
samples of different mean particle
size. Demineralization reduces the effect
of the mineral matter on the volatile
matter (daD, and values for the deminer-
alized LS vitrinite (Table 4) were not

360 Fuel 1997 Volume 76 Number 4


Table 4 Proximate analyses of the demineralized LS vitrinite size fractions using t.g.a, a
US mesh Volatile matter (db)
60-100 29.9 (1.12)
100-200 29.0 (0.62)
200-400 30.0 (1.38)
< 400 30.1 (1.04)
a Values in brackets are standard deviations based on duplicate analyses
significantly different for the various size
cuts.
Over most of the rank range, mac-
erals differ considerably in organic
and physical structure. As a general
trend, the volatile matter and H/C
atomic ratio increase in the order
inertinite < vitrinite < liptinite s'13-22.
Thus, significant variations in the vola-
tile matter (dmmf) are often explained
by maceral concentration differences in
the various size fractions. The rationale
for non-maceral particle size effects is
that an increase in the bed depth or
surface area (either external or internal)
available for volatiles to reattach to the
coal matrix decreases the volatile
matter. This 'capture effect' has been
illustrated by reducing the bed depth
(sample mass) in the proximate analysis
test, with an accompanying increase in
the yield of volatiles 23. This effect is
also used to explain the greater yield of
volatiles in the t.g.a, than in the Mac-
400 (Tables 2 and 3), the bed depth
being significantly greater in the latter.
However, decreasing the particle size
over the range studied here, while
maintaining the same sample mass,
changed the bed depth by only 14%
(calculated by the number of particles
present, based on D[0.5] diameters,
compared with the number of particles
necessary to equal the surface area of
the bottom of the pan, assuming a
density of 1.32gcm-~). This reduction
in bed depth was not sufficient to cause
an increase in volatile matter (a 14%
reduction in bed depth for the UF 60-
100 US mesh size cut yielded a Mac-400
daf volatile matter of 34.8wt% (sd
0.3 wt%), in comparison with 34.5wt%
(sd 0.3wt%) for the 0.5g (100% bed
depth) sample). However, the number of
particle layers, determined from the
ratio of the total number of particles
present to the number of particles
necessary to equal the surface area of
the bottom of the pan, increased from 1
to 8 for the 5 mg sample in the t.g.a, and
from 4 to 63 for the 0.5g sample in the
Mac-400 for the UF vitrinite particle
size cuts. Whether this increase in the
number of layers is significant depends
on the mechanism of volatiles release.
At slow heating rates, such as in the
modified ASTM test 11, the quantity of
volatiles will depend on their diffusion
rate out of the particle and through the
bed. Under these circumstances, the
Particle size dependence of coal volatile matter: J, P. Mathews et al.
Fixed carbon (db)
69.0 (1.00)
69.5 (0.71)
68.9 (1.17)
68.5 (1.05)
particle size and the number of layers
are important, as these affect the resi-
dence time and the surface area avail-
able for volatiles to recombine with the
coal matrix.
It has been proposed that with decreas-
ing particle size, the pore diffusion path
length is reduced, possibly reducing the
extent of secondary interactions of the
volatiles 9, thus increasing the volatile
matter. However, in the rank range of
these vitrinites, most of the surface area
exists in micropores24. For the UF particle
cuts (other than the > 60 mesh) there was
little difference among the CO2 surface
areas (Table 1). Furthermore, it is unlikely
that the extent of secondary reactions will
increase with an increase in the number
of particle layers, as the external surface
area is negligible compared with the
micropore area (N 2 surface areas were
< l m 2 g - l ) . The postulate that with
decreasing particle size the pore
diffusion path length decreases is also
questionable for microporous coals. If
the pores are assumed to be cylindrical
and randomly oriented, then a random
walk of pores of 12A diameter
(assuming 25 an aspect ratio of 10:1)
yields a ratio of 12:1 for the total
distance travelled to the straight-line
distance travelled, e.g. for every 120A
travelled the distance from the starting
point is 10A for these pores. Thus,
micropores will dominate the pore path
length, with little contribution from
the macropores. During comminution,
the cleavage plane will be through the
macropores; thus, changing the particle
size would not greatly reduce the pore
diffusion path length. Furthermore, the
similar CO2 surface areas (Table 1) are
also consistent with a uniform pore
diffusion path length, as the extent of
'secondary reactions' should be similar
for the size cuts and hence the composi-
tion and quantity of the volatiles should
not change (in the size range considered
here) if the organic composition does not
change. The data presented here are
consistent with the hypothesis that chan-
ging the particle size of a microporous
material does not greatly influence the
pore diffusion path length.
Since the chemical structure of the
vitrinite was uniform over the particle
size range considered here, these results
indicate that increasing the number of
layers (while maintaining a constant
bed height) or reducing the volatiles
Fuel 1997 Volume 76 Number 4
Ash (db) Volatile matter (daf)
1.5 (0.14) 29.9 (1.12)
1.5 (0.60) 29.5 (0.64)
1.2 (0.28) 30.3 (1.32)
1.5 (0.01) 30.8 (0.63)
residence time within the particle (under
these conditions) did not influence
the extent of reattachment of the vola-
tiles to the coal matrix. Furthermore,
for the demineralized LS monomaceral
particle size cuts, no significant differ-
ences in volatile matter were found.
CONCLUSIONS
Non-maceral particle size effects on
volatile matter (daf) were not significant
for a demineralized bituminous vitrinite
in the pulverized coal particle size range.
This implies that for comminuted coals,
the particle size dependence of the volatile
matter (after correcting for mineral
matter influences) is due almost entirely
to maceral effects. This is consistent with
the postulate that for microporous bitu-
minous coal particles, the pore diffusion
path length for volatiles does not depend
significantly on particle size.
ACKNOWLEDGEMENTS
The authors thank the Kanawha Division
of Cyprus-Amax and the Rochester and
Pittsburgh Coal Company for access to
their mines for sample collection.
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