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Fuel Vol. 76, No. 12, pp.

1137-1142, 1997
1997 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
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Plh S0016-2361(97)00115-4

ELSEVIER

Oxidation paths of a coking coal and


comparison of its oxidized product
with a non-caking coal
Jose E. S~nchez and Jos(~ M. Rinc6n
Departamento de Ouimica, Laboratorio de Investigaci6n en Combustibles, Universidad Nacional,
Bogota, Colombia
(Received 30 August 1996; revised 21 March 1997)
A coking coal was rendered non-caking by air oxidation at 125C. The oxidation process was followed by free
swelling index, dilatometry, FT-i.r and e.s.r. It was found that the oxidation could be divided into two steps. The
main feature observed in the first step was loss of coking properties. In addition there were increases in phenolic
hydroxyl content and e.s.r, spin concentration, and a decrease in volatiles in the dilatometric test. In the second
step, the caking properties were lost and the rate of carbonyl formation increased. The FT-i.r spectra of the
oxidized coal and a non-caking coal were very similar, indicating that the presence of oxygenated groups is
related to the absence of plastic properties. A mechanism of the oxidation process is proposed. 1997 Elsevier
Science Ltd.

(Keywords: coking coal; aerial oxidation; plastic p r o p e r t i e s )

It is well known that mild oxidation changes physical and


chemical properties of coal. The loss of plastic properties
and self-heating in piles are two of the technological
properties most frequently studied 1-8. None of the many
proposed theories explains the mechanism of the changes
produced in coking coals as a consequence of oxidation 9-11.
Mild oxidation impairs the plastic properties ~'2'6, lowers the
liquid yield from liquefaction and the volatile matter from
pyrolysis 5, and chan~es the extractability 6'12 and free
radical concentration 5 '1 3 1' 4 . The oxidation process increases
the concentration of reactive oxygen groups such as - O H ,
-COOH, - C = O and C - O - O and decreases aliphatic
hydrogen 5,6,9A2,15.
Ignasiak et al. 16.17 reported that the formation of reactive
oxygen functional groups such as hydroxyl and carboxyl
was responsible for the loss of coking properties through
oxidation. Painter et al. ~8 attributed the loss of caking
properties on oxidation to the formation of ester cross-links.
Liotta et al. 19 considered the formation of ether bonds to be
responsible for the loss of coking properties. Larsen et al. 12
detected changes in cross-linking after low-temperature
oxidation but argued that these were not responsible for the
observed decrease in free swelling index (FSI). Rhoads et
al. 15 explained this phenomenon by the loss of aliphatic
hydrogen during oxidation. All these different explanations
may arise from differences in experimental conditions, such
as oxidation time, temperature and type of coal sample.
The mechanism of coal oxidation has been the subject of
considerable study 4'5'12'18-22. It is generally accepted that
the initial stage of oxidation involves the attack of molecular
oxygen on certain aliphatic species, generally methylene
groups ~ to aromatic rings or to - O R groups, producing

peroxides and hydroperoxides which decompose to form


oxygenated groups 5,22-25.
In this work, to elucidate the structural changes during
oxidation of a bituminous coal and its influence on the
coking and caking porperties the oxidation process was
monitored by spectroscopic analysis and weight loss.
EXPERIMENTAL
Materials

Two types of coal were used: La Vega (LV) with coking


properties and Tres Bancos (TB) without caking properties.
Both coals belong to the same basin. The samples were
taken directly from the seam and kept under nitrogen during
the present study. The raw coals were ground to < 250 #m.
Oxidation

About 10 g of crushed coal LV was spread in a layer


- 5 mm thick on an aluminium plate and placed in an oven
at 125 ___ IC. Oxidation was achieved by introducing air
into the oven until the caking and coking properties were
lost as measured by standard FSI and dilatometer test
methods.
Spectroscopic analysis

FT-i.r. and e.s.r, measurements were performed to


investigate chemical changes on oxidation. The FT-i.r
spectra were taken by diffuse reflectance.
RESULTS AND DISCUSSION
The properties of the coals used are shown in Table 1. Coal

Fuel 1997 Volume 76 Number 12

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Oxidation paths of a coking coal: J. E. S~nchez and J. M. Rinc6n

Table

1 Properties of coals used

Coal

LV

Proximate analysis (wt%)


Ash (db)
Moisture
Volatile matter (daf)
Ultimate analysis (wt% daf)
C
H
N
S
O(diff.)
H/C atomic ratio
Plastic properties
FS!
Max. dilatation (%)
Max. contraction (%)
T~oft (C)
Max. fuidity (ddpm)

OLV

TB

10.8
0.9
36.0

12.1
1.4
35.2

12.0
5.2
46.2

86.9
5.6
1.8
0.6
5.1
0.77

85.4
5.0
1.7
0.5
7.3
0.70

82.2
5.6
1.8
0.9
9.5
0.82

8.5
200
30
360
1900

1.0

FT-i.r. spectroscopy

--32
380
--

-8
437
--

2ooT
o,

:o

;o

!
80

I
100

80

I00

Oxidation time ( h )

-100 1

20

40

60

Oxidation time (h)

30

2,o
I~ ~

0
0

i
40

20

,
6'0

80

of 1 was reached. The change in plastic properties with


oxidation time is shown in Figure 1. At 24 h, the dilatation
of LV was lost (Figure la) and the FSI had decreased from
8.5 to 6 (Figure lb). At 84 h of oxidation the FSI had
decreased to 1. The FSI and contraction (Figure lb,c)
showed similar profiles. The softening temperature (Figure
ld) increased during the first 24 h and then remained
constant. From the preceding observations the oxidation
process could be divided into two steps: (1) loss of coking
properties in the first 24 h; (2) destruction of caking
properties as measured by the FSI.

100

Oxidation time (h)

450

FT-i.r results for oxidized coals have been reported in


many papers 17,26,27. Figure 2 shows the FT-i.r. spectra of
LV, other Colombian coking coals CH057, CH089 and
CH107 for comparison, and the non-caking coals OLV and
TB. The four coking coals show similar spectra. The main
differences between LV and OLV are present in the regions
3600-3100, 3000-2700 and 1800-1600 cm -[ due to -OH,
C - H and C = O stretching bands respectively (Figure 3).
The oxidation path was followed by measuring the area of
the peaks related to these groups, Figure 4. During the first
step there was an increase in absorption at 3600-3100 cmdue to phenolic groups. Then the intensity of the band
decreased and finally remained constant during the second
step (Figure 4a). The carbonyl group content, as measured
by the absorption band at 1800-1600 cm -1, did not change
appreciably in the first step but increased during the second
step (Figure 4b). The aliphatic - C H groups, at 30002700 cm -1, decreased continuously in both steps (Figure
4c). From the above, it is concluded that the presence of
phenolic groups influences the loss of coking properties.
Caking properties are more related to the formation of
carbonyl groups.
Different authors4'12'15'18'21'28 suggest that oxidation of
alkyl-aromatic species in coals starts at the a position, so the
carbonyl groups found in this work probably belong to ct
groups that could be acids, esters, aldehydes or ketones.
These groups cause polarity in the aromatic rings, and as a
consequence the molar absorptivity of the aromatic rings at
1600cm -l strongly increases, as shown by the high
intensity of this band in the OLV and TB spectra (Figure
2). Therefore this high-intensity band, which has been the
subject of controversy in the literature, could be due to
highly aromatic conjugated polar groups which are of
relatively high reactivity and are cross-linking precursors 29.
[
A band at 1735 cm- is usually found as a shoulder on the
intense 1600 cm -1 broad band in the spectra of oxidized

400
350
u

300 1
0

20

40

60

80

I O0

Oxidation time ( h )

T a b l e 2 Free radical concentration and g factor as a function of


oxidation time
Time (h)

Figure 1 Effect of oxidation on plastic properties as a function of


time
LV is currently used as coking coal in industry and OLV
was obtained from LV after 84 h of oxidation. Coal TB is
normally used for combustion.

Coal oxidation
Since there is no criterion to fix the final point of
oxidation, it was decided to continue oxidation until an FSI

1138

Fuel 1997 Volume 76 Number 12

00
06
12
24
30
36
48
54
60
72
84

Spin concentration
(1019 g -I )

Increase (%)

1.65
2.96
3.06
3.10
3.16
3.29
3.37
3.34
3.47
3.66
3.29

0.0
79.7
85.7
87.8
91.3
99.6
104.1
102.7
110.2
122. I
99.7

2.0035
2.0039
2.0045
2.0038
2.0041
2.0050
2.0049
2.0047
2.0045
2.0029
2.0029

Oxidation paths of a coking coal: J. E. Sanchez and J. M. Rincon

2.00

1.00

CH057"

'

2.00
]

CH089"

LV*

1.00

,
2.00
OLV

CHI07*

.oo
4000

3000

2000

1000

cm -1

4000

3000

2000

1000

cm -1

* Coking coals

Figure 2 FT-i.r spectra of Colombian coking coals LV, CH057, CH089, CHI07 and non-caking coals TB, OLV

2.00

1.50

1.00

0.50

Y
-0.50
I

3500

3000

"

2500

2000

1500

1000 '

cm -1

Figure 3 Diffuse reflectance i.r. difference spectra of coals LV and OLV

coals. For identification it has been necesary to use the


second derivative of the spectrum. Fuller et al. 27 used this
absorption, assigned to unconjugated carbonyl groups, as an
index of the loss of coking properties during oxidation. This
peak at 1735 cm -I was also present in the TB spectrum and
as a shoulder in the OLV spectrum; after water extraction of
OLV its presence was clearly identified, and the spectrum of

OLV became very similar to that of TB (Figure 5). The


effect of water extraction has not been previously reported,
and this method may be used to quantify the intensity of the
band to measure the degree of mild oxidation. This
band seems to be very stable, since it remains after
extraction with other solvents 3. The above results
suggest that the presence of carbonyl groups, conjugated

Fuel 1997 Volume 76 Number 12

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Oxidation paths of a coking coal: J. E. S~nchez and J. M. Rinc6n

2.00
TB

20

1.00

20

40

60

80

IOO

Oxidation time (h)


3000

4000
2.00

2000

I000

cm-1

LV

14
--

13

10
1.00

/
0

i
20

i
40

n
60

80

q
100

Oxidation time (h)

4000
ZOO,

20

3000

2000

1000

cm-!

3000

2000

1000

cm-1

1.00

20

40

60

80

|
100

Oxidation time (h)

Figure 4 Effect of oxidation on absorption area at 3600-3100,


1800-1600 and 3000-2700 cm -1 as a function of time

4000

Figure 5 FT-i.r spectra of water extraction residues of coals TB,


LV and OLV

and non-conjugated, in oxidized coals and in low-rank coals


is related to the absence of plastic properties.

40
35

E.s.r. data
Previous work z3 showed that the spin concentration
changes according to the oxidation conditions. The spin
concentrations and g factors are shown in Table 2; during
the first step the relative increase in spin concentration was
- 8 8 % and the g value also increased, suggesting that the
free radicals are stabilized over the oxygenated groups.

Weight loss during oxidation


Figure 6 shows the effect of oxidation on weight loss, as
measured in the FSI and dilatometric tests. Under the
conditions of the FSI test the weight loss remained constant,
whereas in the dilatometer it decreased from 27% for the
raw coal to 17% in the first step and then remained constant
in the second step. Similar results were obtained in a
simulated test by thermogravimetry. This means that during
pyrolysis, the oxidized OLV structure is thermally more
stable than the LV structure. This is consistent with the
higher bond dissociation energy for the C~-C~ bond when
there is a carbonyl group at the C~- position 3~. Another
possibility is that the free radicals in the volatiles may be
quenched by oxygenated free radicals to produce oxygenated chars.

1140

Fuel 1997 Volume 76 Number 12

30
--

25

FSI

DILAT

~ 20
~

1o
5
0
0

i
20

i
40

i
60

t
80

i
100

Oxidation time (h)

Figure 6 Effect of oxidation on weight loss in FSI and


dilatometer tests as a function of time

Oxidation mechanism
The mechanisms proposed4"L5'26 are supported by
knowledge of the oxidation mechanisms of model compounds in fluid phases where there are no mass transport
limitations. In solids like coal, there are such limitations, so
the mobile species are the oxygen and derivatives formed
during the process such as OH, HOO" and H" as follows:

Oxidation paths of a coking coal: J. E. Sanchez and J. M. Rinc6n


I: Oxygen reaction with native free radicals and labile
hydrogen
~ "

+ 02

,~ ( ~ 1 - O " O "

VI: Condensation and cross-linking


(16)

(1)

(0-0.
O-H

O,

C)"

+ H-O-O"

II: Hydroperoxide formation


(:~"

+ H-O-O"

<SD-O-O"

C)-O-O-H

+ H-O-O"

O-O-OH

(3)

+ 02

(4)

III: Hydroperoxide decomposition


(~)-O-O-H
~-O-O-H

(~3-O" + "OH thermal


+ Fe~

(~)-O"

>

O-o-O

(17)

(2)

(5)

+ OH- + Fe +'

where ( 8 ) and ( ~
are different entities in coal.
This mechanism is consistent with the results obtained in
this work such as the loss of hydrogen, the presence of
oxygenated free radicals, carbonyl and phenolic groups and
also the formation of H2 detected in other work 32,33.
From the above it can be concluded that the loss of coking
and caking properties in coals during mild oxidation is
related to the accumulation of free radicals, peroxides and
hydroperoxides, carbonyl groups and phenolic groups.
These species are labile at low temperatures and are crosslinking precursors.

(6)
ACKNOWLEDGEMENTS

C)-O=O=H

C)-0-H

+HaO

+ H-O-0H

(7)

IV: B-Elimination
(8)

R-C=O + <:~"

REFERENCES

I
H

H
I

C>-c-o.

The authors are grateful to CINDEC-U.N and FONIC for


financial support for this work.

(~-C=O

R"

(9)

I
R

3
(~C=O
I
R

H"

(10)

V: Carbon oxides formation

C:>c=o
(~

+ 02

6
7
8
> (~C=0
> (~"

-C= 0

+ H00"

(11)

CO

(12)

~-O-H

H
I
OC-X
I
H

13,

O-C-R
I
0-0H

O-

O"
I
C-R (13)
I
0"

9
10
11
12
13
14
15
16

O*

O"
I

-c~

,~,-C=O

R.

(14)

19
20
21

O.

22

O.

~.~,-c=o

17
18

(~.

CO~

(15)

23

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