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1137-1142, 1997
1997 Elsevier Science Ltd. All rights reserved
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ELSEVIER
1137
Table
Coal
LV
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
30
2,o
I~ ~
0
0
i
40
20
,
6'0
80
100
450
400
350
u
300 1
0
20
40
60
80
I O0
Oxidation time ( h )
Coal oxidation
Since there is no criterion to fix the final point of
oxidation, it was decided to continue oxidation until an FSI
1138
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
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
1139
2.00
TB
20
1.00
20
40
60
80
IOO
4000
2.00
2000
I000
cm-1
LV
14
--
13
10
1.00
/
0
i
20
i
40
n
60
80
q
100
4000
ZOO,
20
3000
2000
1000
cm-!
3000
2000
1000
cm-1
1.00
20
40
60
80
|
100
4000
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.
1140
30
--
25
FSI
DILAT
~ 20
~
1o
5
0
0
i
20
i
40
i
60
t
80
i
100
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:
+ 02
,~ ( ~ 1 - O " O "
(1)
(0-0.
O-H
O,
C)"
+ H-O-O"
+ H-O-O"
<SD-O-O"
C)-O-O-H
+ H-O-O"
O-O-OH
(3)
+ 02
(4)
(~)-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.
(~-C=O
R"
(9)
I
R
3
(~C=O
I
R
H"
(10)
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
Dryden, I. G. C., in Chemistry of Coal Util&ation, Supplementary Volume, ed. H. H. Lowry. Wiley, New York, 1963,
Chapter 6.
Wender, I., Heredy, L. A., Neuworth, M. B. and Dryden, I.
G. C., in Chemistryof Coal Utilization, Second Supplementary Volume, ed. M. A. Elliott. Wiley-Interscience, New
York, 1981, Chapter 8.
Clemens, A. H., Matheson, T. W., Lynch, L. J. and
Sakurovs, R., Fuel, 1989, 68, 1162.
Clemens, A. H., Matheson, T. W. and Rogers, D. E., Fuel,
1991, 70, 215.
Khan, M. R., Usmen, R., Newton, E., Beer, S. and
Chisholm, W., Fuel, 1988, 67, 1668.
Seki, H., Ito, O. and Iino, M., Fuel, 1990, 69, 317.
Nordon, P. and Bainbridge, W., Fuel, 1983, 62, 619.
Krishnaswamy, S., Agarwal, P. K. and Gunn, R. D., Fuel,
1996, 75, 353.
Seki, H., Ito, O. and Iino, M., Fuel, 1990, 69, 1047.
Wheeler, R. V. and Clark, A. H., Journal of the Chemical
Society, 1913, 103, 1704.
Van Krevelen, D. W., van Heerden, C. and Huntjens, F. J.,
Fuel, 1951, 30, 253.
Larsen, J. W., Lee, D., Schmidt, T. and Greent, A., Fuel,
1986, 65, 595.
Yokono, T., Miyazawa, K., Sanada, Y. and Marsh, H., Fuel,
1981, 60, 598.
Ripmeester, J. A., Couture, C., MacPhee, J. A. and Nandi, B.
N., Fuel, 1984, 63, 522.
Rhoads, C. A., Senftle, J. T., Coleman, M. M., Davis, A. and
Painter, P. C., Fuel, 1983, 62, 1387.
Ignasiak, B. S., Szladow, A. J. and Montgomery, D. S., Fuel,
1974, 53, 12.
Szladow, A. J. and Ignasiak, B. S., Fuel, 1976, 55, 253.
Painter, P. C., Sayder, R. W., Pearson, D. E. and Kwong, J.,
Fuel, 1980, 59, 282.
Liotta, R., Brons, G. and Isaacs, J., Fuel, 1983, 62, 781.
Getner, L. S., Fuel, 1987, 66, 1091.
Wachowska, H. M., Nandi, B. N. and Montgomery, D. S.,
Fuel, 1974, 53, 212.
Cronauer, D. C., Ruberto, R. G., Jenkins, R. G., Davis, A.,
Painter, P. C., Hoover, D. S., Starsinic, M. E. and Schlyer,
D., Fuel, 1983, 62, 1124.
Cronauer, D. C., Ruberto, R. G., Silver, R. S., Jenkins, R. G.,
Ismail, Y. M. K. and Schlyer, D., Fuel, 1983, 62, 1116.
Fuel 1997 V o l u m e 76 N u m b e r 12
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