Académique Documents
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Title of Heatings
Kiyoshi HASHIMOTO
!)
Contents
I. Preface ..............................479
II. The Apparatuses and the Method of the Experiments ........ 479
III. Resu]ts of the Experiments ..................... 480
IV. Considerations for the Ear]y Detection of Spontaneous Heating. . . . 492
V. Conclusion..........,.................. 495
Bibliography ........................ ..... 496
I. Preface
An oxidation experiment of coal at a constant temperature was carried out
for the purpose of theoreticai studies on the application of the result of gas
analysis to the early detection of spontaneous combustion of coal.
Hitherto, numerous publications on methods for the early detection of
spontaneous combustion from the results of gas analysis have been reported:
these include simp2e component such as CO, C02, CH4, C2H4 etc., and the values
of COI02, C02102, COIC02, COICO+C02 etc. A decisive method, however,
has not yet been set forth.
The oxidation experiments in this paper were carried out in parallel with
experiments conducted for the establishment of the theory of spontaneous
combustion reported previouslyi'2). Gas analysis were regularly made. Based
on the results a theoretical investigation on the early detection of spontaneous
combu,stion of coal was done.
The changes of gas components, in accordance with the advance of oxida-
ting time, were shown by gas analysis following the experiments of oxidation
under a fixed temperature, and the cause of discrepancies was studied. The
/). results show that the possibility of errors was much higher in the procedure of
early detection of spontaneouS combustion than expected,
The results of gas analysis notwithstanding the possibility of errors are
t.t./
usefui for the early detection of spontaneous combustion of coal, but may not
be usefu1 for the "diagnosis" of the progressing change during conibustion.
celhr.100g
20
l5
m.
E ×・ J5ooc .
8
Pi
th 10 L'--
tt. H----
:
oN
U
5 . I25oc
-.--L------m.---rLL-Ll9t9:L"mrLOOC "
e 750C
lo '' .5ooc l
lo 2o ]o 4o so 6o 7a so
OX]PATTO]ITJMEFROMSTART hr
Fig. 1. The relation between C02 generation rate and
oxidation time, particle size 20-28 mesh
・2
ki: coeflicient
0: oxidation hour
following relation arpong the initial CO, generation rate ( C,fllS?o )1,.r the
The
coethcient k, and the temperature t shows Figure 4. Figure 4 Ieads the follow-
ing experimental formula.
(`doner):Jo2
=o.o7s ee,o3st-e,one (2)
k =] e"4・42
.・. (dd9o)co,
=- O.O12 (3)
.. o.o7s eO.03B-O.Oi2a (4)
482 Kiyoshi HAsHiMo'ro
cc/hr.100g
20 ;'s.-
. ]5ooc
: 15
.
E
g
:t
E lo
:
: .s-
oos
U
. Ic'5oc
'-7'-LT"----N-.-.
L5
tr----Mg-mL---7 tC
L----fi.--mm t5C
"'f
50"C
O 10 20 ]O 40
a
5o
e)CIDATIDNTIMEFROMSTART hr
Fig. 2. The relation between C02 generation rate and
oxidation time from start (average)
A Study on tl]e Early Deteetion of Spontanequs Combustion of Coal 483
celln'.1oog
Thus Figtire 5 is led forth. Accord-
50
40
ing to Figure 5 the・ curves of the C02
io generation rate are in parallel, and conse-
20
quently the CO, generation rate of the
Cgye?') JSooe
Oyubari coal at a certain temperature is
co.=::23e-o-oie
10
te
equal to that of the coal oxidated for 82.5
hours at a temperature 250C higher than
125oc
the former. In other words, 25(aC) =.
(ag.i?-2
5 Co.'S"e.6e'o.e,s6fi
82.5(hr)
-
EF, 4
"
3 (ta-1-e2)co 10ooc O.303(OCIhr). The result of this experiment
g-
:2
ts
.'L`3-5eLO・oio3e
shows that CO, generation rate becomes
M-...
O.3
50oc
(esle02
take place at a certain density of C02,
co,HF"O・43e'eot
JJO
because other gases produced by oxidation
O,2
enter.)
Figure 6 shows an example of the
O,1 F E
n LtT
o OXIDATIO}・;・
lo 2o 3e 4o
TIIE hr
relation between CO generation rate (CO
quantity produced by 100 grams of coal
Fig. 3. The relation between C02 in one hour) and oxidation time from start.
generation rate and oxidation time
Table 2 shows the relation between the
from start (experimental valLie)
generation rate and the oxidation time by
the averages at every ten hours of oxidation time.
According to this table the co generation rate decreases as the oxidation
time passes, and increases as the size of grain becomes smaller and the temper-
ature rises. Figure 7 shows the relations among these by average.
According to this the CO generatlon ' rate is represented by the following
equatlon.
( dd9o )..= ( dd9e )g.e-k2o
(5)
k2: coefllcient
e: oxidation hour
484 Kiyoshi HAsHIMoTO
eclhr.loog
50 o.
40
30
z・o
10 o. 1
"L
t.
"}
.ty
:
Es 9sKS
g
o,es
o,
g/ 4 e<Ng<r,"v"'
'U-
di 3 :
re
[i 2 HU
:-
le,;e-a':?--ooi2o g
g u
:1
a'
O.Ol
o.
=-H
H
o,5i, o,oos
o,
O.4
O.5
e.2
O.1 o'coi
isO
o,
25 so 7T5EMpERATuREIcooc l?5
2
Figure 8 shows the relationship between the generation rate of CO which
is logarithm, and oxidation time from start. This suggests the possibility of
the calculation of the generation rate of CO produced by oxidation at the lower
temperature.
Moreover the fol!owing relation between the coecacient ki of the CO,
generation rate and the coeMcient k2 of the CO within the scope of the ex-
per!ment under 1500C is:
k, < k,
and the lower the temperature becomes, the greater its difference is.
As a matter of fact the density of CO and C02 can be acquired as a result
of the analysis of gases in the underground, but the quantity of air leakage
cannot be calculated. Consequently, it is impossible to know the generation
rate of CO and C02・
Under a certain condition the high density of CO and CO, indicates a
higher tempera' ture, if the air leakage is assumed to be almost constant. In
A Study on the Early Detectfon of Spontaneous Combustion of Coal 485
celbr.1oog
50
40
30
20
'(,)iCixei?'?:o,"" t50oc
L) J'
e'Oo,.,o '
IO '
'
(,sv'?,,,li.-l'
li'5oc
5
"ei
k' bi
E t}'
{ti'f]tli?et)
4
g]
: loooc
E (W.J'2'
:2
8 s
Oo?Xjde'oot.L
oo
oN
7soc
v 1
('
ag,Q )to,'
"= tJe'Oo,.io
e
o.5
5ooc
O.4
Cxti'e'?-2
O.5 co,,li"='
05e'Vcheoe
o.?
'
O.1
o 10 2-O ]o 40 5o
OXIDA?ION TIME ltr
cclhr,Ioog
'10.0
7.5
--
p]
- -
E
g 5.0
.
.
: .
E 15ooc
y.
8・i i'
.-.
Ob ?.5 .
J?sac
.
.
100C,c
! 1
f E t
o
o 10 20
Jo ao 50 60
hr
70 80
'OXIDATIOII Tl'L{E
'
486 Kiyoshi.HAsmMoTo
cclhr.)OOg
le
a
a
g J5ooe
¥t 5
,z
g
LX--"----gL-ii
100oc
oo iioE2[o[Jt 4o so OXIDATIo}1TIvE, hr
Fig. 7. The relation between CO generation rate and oxidation time (average>
(
general, however, the higher the temperature rises, the more the leakage of air
increases, which is particularly remarkable in the cases of steep pitching seams
and the thick seams. Therefore, the rise of temperature,gives the dilution of
the density of gases, from the point of view of air leakage, The increase of
density of CO suggests a greater danger than it is assumed to be, for the
generation rate of CO has a tendency to decyease as the time elapses in the
experiments of oxidation at a constant temperature.
i
A Study on the Early Detection 6f Spontaneous Combustion of Coal 487
(E,IJ22 J5oec
5
values, due to the diluted gases by other 4 coSX e.oe'-aot
doe
oxidation gas or air after oxidation. This d
xx
)
1?sec
tendency is feasible in actual coal mines ge 2 (g,o.]
a
sites. The rate of dilution by air cannot coXS F.3e'Ootosa
CO,. g・
c e"2
Consequently, in order to detect the
aYa
% 2S
o
di
2sJlh
fi 20
oN ge
st.
>8 e
ac e
15 4B-65
o" 7o2B
e 2eh5 e
8
10
g
A
ff
1 1
s 10 15CO(IDATION
20 25 ]O }5 40 45
5
o
TINE hr
Fig. 9., The relation between C02!02 value and the oxidation time
temperature ・1500C, o mark -is the mean value
488 KiyoshiHAsHIMOTO -
9o LO-.
r
-;
/
di
Do
20 isooe..f-t `7' '
t' "
-- 'J-t3--/ ・
ov
R.i
-.- .-t.J"
- r.;-
R l5
A t2- vsec ..t.-rs-"t-J.:..:tt-'"
nn "-rt'=;?-'-o't-;"F'
.r.
U F---'t/' ...=t....tpt'S'
.. t.: .-- -----J" "- - - T.=-X
8 !o "' pdec .-}:tX;'" lioill"tft- ;' JJ-"'--7'f-'"'
="
8
3 -- ,...t.....s-tt.-
5 --
if"' soec
--- --
-m..J--"r-"-"`='pt-
ptpt"
o
10 15 OXIDATIQNTIME
20 25 }O hr55 40 qs
Fig .
10. The relation between C02102 value and the oxidation time (average)
(CoO ,2
) ==' a, + b, e
(6)
ai: a coeflicient
bi:. a coefficient
e: the oxidation hour
%5
x
4
u;
e
di
R
] tE"1 q's-6s 65-100 e
n
v
20-28
8
2s-55
ts
?
35-a8
hl
B
gl
o
a 5
10 l5OXIDAailOI"TaaE
20 25 JOhr15 4Q 45
Fig. 11. The relation between the COI02 value and oxidation time
(The oxidation temperature: 1000C)
490・ Kiyoshi HASHIMOTO
TABLB 4. The relation between the CO!O, value and oxidation time
Oxidation time ±rom start
Temperature Particle size Caverage at every 10 hours of oxi dation)
N
%6
.
5 1500C 1
.
di
a4
opt
125eC . .
>g ,
a
g s .
looec -
.
ts
g2
s
l 7
o
o 5 10
15axIDATTONTIME
20 25 ]Ohr}5 40 45
According to the subsequent results, the value of CO/02, during the oxi-
dation at a constant ternperature, tends to increase more or less as time goes
on, but the rate of increase is not so high.
The following relation is seen between the value of CO!O, and the oxi-
AStudyontheEarloDetectionofSpontaneousCombustionofCoal 491
(CoO,)=a,+b,e-c,o2 (7)
where (CoO,):thevalueofCO!02
a2: a coeMcient
,,..,, " L'- bi': a coefficient
L・ ' "=" '' ttE-:"-a' 'coeracient
'F
O.1
o 2o 25 JO.55 40'
1
5 10
45
o 15
CO[IDATIONTIHE 11r
between the value of 601C02 and
Fig. 13. 'The relation
the oxidation time and temperature.
492 Kiyoshi HAsHIMOTO
6.s
O.4
ofXs
? O.5
----- 1250L
ou
bU - --. "-
R 02 -"-h'- :50eg
eE apooq
O.l
OO s lo ls 2o 2s so Js 40 45
OXIIIKTIONTIHE hr
Fig. 14. The relation between the value 'of COICO+C02
and the oxidation time and temperature.
these values do not have any importance in the early detection of spontaneous
combustion of coal.
Next, the effects of mixing of the gases produced by oxidation must be
considered as the result of diffusion of gases. Mixing gases produced by oxida-
tion is not reasonably considered to cause changes under temperatures of 5000C.
Figure 15 shows an example of the changes of the values of CO!O, and
C02!02 when these gases are mixed at a rate of 50 and 50 after values have
been ealcu!ated at a temperatures of 1500C, 1000C, 750C and 500C respectively.
(a) shows the oxidation at the beginning, (b) shows that of ten hours later and
(c) thirty hours later. Though the highest temperature of the gas is 1500C, the
values of CO/O, apd CO,/O, are shown approximate}y at 1250C. The values
of these are shown at the lower temperature-about 1000C-in Figure 16.
This means that these values show the lower states instead of the higher
ones when these gases are mixed with other low temperature oxidation gases,
though there is no change in the value when these gases are diluted by pure
air. This reveals a crucial defect of the value of CO/O, and C02102 and so
on for the detection of spontaneous heatings in the underground.
oou %
x.. 20 M
U
X--
U
m5
.olO '---- '
5・ colo2.
go
25 50
A 75-------
1oo 125 150
O]EMPERATURE eC
%
oN 20
x ou
oo
oj 15 e
N C02/02
R8 !o
.
g 5 , CO!02
:
.
,
g o
25 50 75 1oo 125 150
TEMPERATURE oC
cu
%
o 20
×pa
oo
15
di
co21o2 .
98
ou
10
CO/02
,
ts
5
s '
'
g o
25 50 75 IOO l25. I50
TEMPERATURII OC
FIg. IS. The changes of the values of COI02 and C02/02
(a) The oxidation at the beginning (b) The oxidation at 10 hours
later (c) The oxidation at 30 hours later, particle size 20-28mesh,
and mixture ratio 1500C 1 125eC 1 1000C 1 750C 1 50eC 1.
)) 7)
494- Kiyoshi HAsHIMoTo
CV' l"
-El 20
."N,
uaj l5 C02/02
oou Lmm-.-
'li io '
,
CO/02
ts 5
,
S .
go
25 50 75 1oo 125 L50
TEMPERATURE OC
Fig. 16. The changes of the values of COI02 and COI02
mixture ratio 1500C 1, 125eC 2, 1000C 3, 750C 4, 500C 5.
24 5.0
50
96 7.0
24 6.0
70 11.0 18
96 2.0
100
48 16.5 2.8 17
96 15.4 2.6 17
24 16.0 4.0 25
120
96 23.0 5.0 22
24 20.0 6,O 30
140
96 36.0 7.0 20