CRITERIA OF INCIPIENT COMBUSTION IN COAL MINES

J. M. KUCHTA, M. HERTZBERG, R. CATO, C. D. L I T T O N , D. BURGESS AND

R. W. VAN DOLAH
P.~t~burgh ~lining and Safety Research Center, Bureau of Mines, U.S. Department of the Interior
Pittsb~urgh, Pennsylvania

The formation of carbon monoxide (CO) and other gases by various American coals was in-
vestigated to determine their relevaz~ce to spontaneous heating and to the problem of incipient
fire detection. Desorption oxperimeats under constant volume showed that ground samples of
the coals yield CO/AO~ ratios that are essentially constant for extended exposure periods in
air at 25~ and are highest for coals from mines suspected of having a self-heating hazard; the
latter coals also yield high CO/CO2 ratios. These ratios vary with particle size and surface mois-
ture content ahd con'elate best with the oxygen content of the coal, although the correlation
was not always consistent with the absolute level of CO production. Similar experiments in an
atmosphere containing the 180~ isotope revealed that the 02 reduction at ambient temperature
is most likely due to chemisorption mid the CO and CO~ formation is attributable to decarbon-
ylation, decarboxylation, or desorbed products from previous reaction of the coal in its virgin
state. Results of flow experiments at various temperatures indicated that the CO/AO2 and
CO/CO~ ratios are highly sensitive to temperathm. The temperature dependence of the rate of
CO or CO2 production between 50 ~ and 150~ was approximately comparable to that derived
frmn the adiabatic self-heating rate for each coal; apparent activation energies were between
10 and 20 keal/mole. Below 50~ the rate data were meager but supported the asstmip~,ion
that oxidation was not a significant factor at ambient temperature.
The sensitivity and reliability of combustion product sensors as mhm fire detectors were in-
vestigated with heated coal samples in flowing air. Submieron particulates appeared earlier
than measurable CO emissions, suggesting that pyrolysis is a precursor to rapid oxidation.
D a t a are presented to compare the autoignition temperature of the coal and the detection
threshold temperature as functions of particle size of the coal.

Introduction of the order of seconds or minutes. Other urine

The outbreak of a fire in a coal mine is ex-
ceptionally hazardous because of the confining
geometry of a mine with its long combustible
corridors and everpresent ventilation and because
of the explosive atmospheres t h a t can form from
extended heating of the surrounding coal. There-
fore, it is esscntial for the safety of miners to
detect such fires in some incipient stage and to
understand their causes. M o s t mine fires are
traceable to strong sources of external heating
and usually develop in combustibles that are
carried into the mine, for example, wood supports,
conveyor belting, hydraulic fluids, and electrical
insulation; here, the time scale for generation
of detectable combustion products is hkely to be
127
fires are of spontaneous origin (about 10 percent
of fires in American mines) and typically generate
oxidation and pyrolysis products for days or
weeks prior to the outbreak of fire. These prod-
ucts include carbon monoxide, smokes, and sub-
micron particulates which can be detected in the
ventilation flow or with sampling line networks.
Carbon monoxide emission as well as the ratio
of carbon monoxide to oxygen reduction ( C O /
AOe) have long been recognized as sensitive in-
dicators of the spontaneous combustion of coal. 1,2
Chamberlain, et a2., a have reported t h a t the so-
called G r a h a m indcx is between 20 and 60
(CO p p m / A O e % ) for most British coals at 50~
and can bc used to predict the temperature of a
heated coal. Howe'r such measurements can
 128 FIRE AND EXPLOSION RESEARCH

be misleading for coals at ambient temperature able product concentrations, ~pecially at near-
since the CO can be a result of molec~ilar ex- ambient temperatures. Most runs were made
change or other non-self-heating reactions. with 10- to 20-mesh coal, although other sizes
This paper summarizes desorption and oxida- were also used. Gas samples were taken periodi-
tion experiments that were conducted with cally and analyzed as in the static tests.
various American coals to determine the rele- Samples of several different coals wcrc also
vance of CO formation to the spontaneous submitted to the National Bureau of Standards
heating hazard. Ambient temperature desorptions to determine their self-heating rates. These
are extended to elevated temperatures using determinations were made between 70 and 175~
normal air and ~sO~ "air" to reveal the mechan- in the adiabatic ignition apparatus developed
ism of CO or C02 formation and to distinguish by Gross and Robertson; 4 about 250 grams of
between rate-controlling processes. In addition, minus 80-mesh (0.177-mm) coal was used as a
the sensitivity and reliability of CO and sub- sample in each run.
micron particulate sensors are compared.
B. Fire Delech~r Studies
Experimental Apparatus and Procedures For the comparative detector studies, the
apparatus consisted of a small oven placed in a
A. Desorption and Oxidation Studies 1-cubic-meter volume through which a ventilating
flow of 15 liters/see was maintained. Pulverized
Gas emissions by the coals were initially samples (25 g) of Pittsburgh seam coal of known
investigated under constant volume in dry air particle size were mounted in the oven pre-
at ambient temperature (25~ The general heated to 150 240~ and the sample tempera-
procedures consisted of sealing freshly ground ture was monitored by means of thermocouples
coal in a glass vessel and then sampling the gases imbedded in the sample. The ventilating flow
periodically for extended periods to determhm carried the pyrolysis and combustion products
the CO, CO~, and CH4 production and the 02 to several detectors, whose sensitivity and
reduction. The gases were analyzed by conven- specificity to different mine combustibles were
tional gas chromatographic methods which could evaluated. For coal, they were an Environment/
detect CO levels of 5 ppm and 02 changes of 1000 r One Corporation Incipient Fire Detector,* which
ppm. Most experiments were made in a 250-CC senses submicron smoke particulates as condensa-
vessel with 50-gram samples of dry coal having a tion nuclei in a Wilson cloud chamber; and an
particle size range up to 0.64 cm (88inch). Particle Energetics Science Corporation Eeolyzer, which
size, surface moisture content, vessel size, and senses carbon monoxide by electrolytic oxidation
sample size were varied in certain runs to define depolarization.
their effects.
The closed-vessel method was also used in tbe
isotope tracer experiments in which the coal Results and Discussion
samples were exposed to an atmosphere of 79
percent argon and 21 percent ~02 isotope. Here,
a coal sample of about 25 grams and 10 to 20 A. Desorption of Coals under Constant Volume
mesh (2.0 to 0.84 mm) was placed in an evacuated
cylindrical vessel ( ~ 1 1 0 ec) and then exposed to Over 35 coals were investigated in the closed-
the shnu]ated air for a predetermined period. vessel desorption experiments in air at ambient
Gas samples were analyzed by gas chromatog- temperature. Generally, CO increased and 0 :
raphy and mass spectrometry, low and high decreased linearly with time for at least a few
resolution, for x~0160, lsOlsO, C1~O, C180, da)% as long as 8 days in many cases, after wbleh
CteOt60, ClsOu~), and other possible species. they were progressively less time-dependent.
Analysis of the lsO2 reactant indicated it con- The CO2 followed somewhat the same trend as
sisted of lso1so(~93c/v) , lsol~o(~70~o), and trace CO but the rates of CO2 release were much
impurities. higher. In any case, the CO and CO~ concentra-
Flow experiments were conducted with the tions could not conceivably account for the large
coals under isothermal conditions at tempera- 02 reduction observed with each coal, regardless
tures to 150~ Ground samples (150 g) of coal of particle size and loading conditions.
were loosely packet in a 2.5-era-diameter tube,
mounted in a constant-temperature bath, and * Reference to specific equipment is made to
preheated air was passed through at 15 cc/min; facilitate understanding and does not imply en-
the low flow rate was needed to insure measur- dorsement by the Bureau of Mines.
 INCIPIENT COMBUSTION IN COAL MINES 129

TABLE I
Summary of gas analyses from ambient temperature (25~ storage tests (~24 days) in air with coals of
various compositions. Sample loading---50 g in 250-cc vessel; Particle size--<: ~ inch (0.65 cm).

Coal analyses Gas analyses

Mois- Voia- Fixed CO/~O, CO/CO~

ture tile carbon Ash O2 CH, CO2 CO ppm/ ppm/
Coal Wt.% Wt.% Wt.% Wt.% Vol.% Vet.% Vet.% ppm Vo[.% Vol.%

Bituminous

Sunnyside No. 4.7 37.4 53.2 4.7 16.4 0.06 0.35 800 178 2285
1, Utah
Inland No. 6, 6.2 30.5 55.4 7.9 10.9 0.07 0.71 1500 150 2110
Ill.
Somerset, Colo. 2.7 37.6 53.7 6.0 2.6 1.60 0.70 2200 120 3145
Sahara No. 4.5 32.7 54.2 8.6 1.4 1.50 0.70 1400 72 2000
21, Ill.
Sunnyhill No. 7.6 41.7 44.8 5.9 3.1 0.36 0.60 1100 62 1835
9, Ohio*
Napoleon, 6.2 43.3 45.5 5.0 3.9 0.02 1.30 980 58 755
Ohio*
Vail, Ohio* 4.1 41.2 50.3 4.4 3.0 8.10 1.00 800 45 800
Bruceton, Pa.* 2.2 40.7 53.9 3.2 6.0 0.02 1.12 700 47 625
Powhatan No. 2.7 42.0 49.8 5.5 8.6 2.80 1.70 600 49 350
3, Ohio*
Allison, Ohio* 2.5 43.5 46.3 7.7 10~:6:.. 4.90 i. 00 350 34 350
Pocahontas 2.7 16.3 75.9 5.1 4.7 9.0 0.52 400 25 770
No. 3, W.
Va.

Anthracite

Forge Slope, 1.8 4.3 88.9 5.1 7.7 10.0 0.60 730 55 1215
Pa,

* Pittsburgh seam coals

Ground dry samples of the coals yielded
CO/AOs ratios that were roughly constant after
the second day for extended exposure periods,
e.g., 20 to 30 days. Table I summarizes results'
obtained for a number of representative bitumin-
ous or anthracite coals after an exposure of about
24 days; particle size was < ~ inch. All coals were
of high volatility (~, 32%) except the Pocahontas
and Forge Slope which had volatile contents
of 16.7 and 4.3 percent, respectively. Of practical
interest is the fact that the CO/A02 ratios are
highest for bituminous coals from mines sus-
pected of having a self-heating hazard, such as
the Sunnysidc (Utah), Inland (Ill.), and Somer-
set (Colo.) mines. Their CO/A02 ratios were in
the I00 to 200 range (ppm/vol %) and their
CO/COs ratios were also among the highest
values. In comparison, Pittsburgh seam coals,
which included low- and high-CH4-producing
coals, had C0/A02 ratios in the 30 to 65 range;
the one anthracite sample (Forge Slope) also fell
in this range, while the least volatile bituminous
sample (Pocahontas) gave the lowest CO/AOs
(25).
The CO/AO2 ratios of the bituminous coals
correlated best with their oxygen content, as
shown in Fig. 1, where the apparent oxygen
content is on a moisture-free basis. Since oxygen
content is even greater for lignite (~>20% O)
and subbituminous (10-20% 0) coals,a their CO
emission and CO/AO~ index am naturally ex-
pected to be greater than for bituminous coals.
 130 FIRE AND EXPLOSION RESEARCH
18C
-----T-- I I
~6C
14C
12r
o c
oo ~ o~
o o o~
2 4 6 8
CKYGEN, w t p e t
Fro. 1. CO/~O~ ratios vs oxygen COlLtentof dry
crushed coals (_<0.65 cm) in closed vessel tests at
25~ (Courtesy U.S. Bureau of Mines.)
However, rankings of all the present coals by
this index were not necessarily consistent with
their lcvcl~ of ahsolute CO production (Table I),
hldieating a single criterion of incipient com-
bustion can be misleading; Guney ~ has made the
same observation in tests with British hard coals.
Laboratory-determined CO/AO~ ratios tend
to be higher than those derived from mine air
samplings because of a combination of factors.
The ratio is higher for freshly crushed samples
than for "as received" samples and tends to be
maximum for samples consisting largely of fines.
Also, the ratio can be much greater for dry coals
than for wet coals, whereas the intrinsic moisture
content (Table I) is of little consequence. Figure 2
shows the drastic reduction of CO formation and
CO/AO~ index that occurred in closed-vessel
experiments with a thoroughly wet "as received"
sample and freshly crushed dry sample of Bruce-
ton coal at 25~ The disappearance of CO for
highly wet coals was confirmed in large-scale
experiments with 205 kilograms of wet Bruceton
coal (5.4% moisture) in a 5.fi5-ma chamber and
is consistent with Chakraborty's7 findings for
Indian coals. These results are not surprising
since the adsorption or desorption of gases by
bituminous coals is greatly reduced by adsorbed
moisture as a result of blockage in the coal pores,s
At elevated temperatures, tlie adsorbed moisture
may very well promote oxidation or self-heating
of some coals, as shown by Guney. ~
4oo
lOO I0
9 wel
TIME, cloys
FIG. 2. Variation of CO and CO/AO2 with time
for dry and wet Bruceton coal ( _<0.65 cm) in closed
I0 12 vessel tests at 25~ (Courtesy U.S. Bureau o~
Mines.)
B. Mechanism o] CO and COs Formation
The closed-vessel tests in which air was replaced
with argon and the ~O2 isotope were limited to
the Somerset coal. Table II summarizes the
mass spectrometric analyses of gas samples from
runs made at 25~ 50~ 75~ and 100~ separate
samples were taken for the high and low-resolu-
tion analyses. At 25~ and an exposure time o{
168 hours, it is seen ttmt C~60 and C~601~0 were
evolved, but no significant amounts of CI~Oj
C180tsO, or C~OX60 were detected, even though
most of the available oxygen had "reacted."
Essentially the same behavior occurred when the
exposure time was only 34 hours and appreciable
oxygen still remained; the observed trace con-
centrations of C~:), CtSOmO, or C~s0160 are not
significant considering instrument limitations
and possible test mixture impurities. These sur-
prising restflts support the assumption that the
0~ reduction at 25~ is attributable to chemi-
sorptiorl by the exposed coal and that CO and
C02 emissions represent decarbonylation, de-
carboxylation, or desorbed oxidation products
from previous reaction of the coal in its virgin
state. The formation of these products could
extend back to the coalification stage of the coal
bed.
If the above hypothesis is valid, a change in
the reaction mechanism should occur at some
slightly elevated temperature where oxidation
becomes a factor in the CO production. This
appeared to be the case here as shown by the
data in Table II. At 50~ the increase in C~0
 INCIPIENT COMBUSTION IN COAL MINES 131

TABLE II
Mass spectrometric analyses from argonJB02 closed-vessel experiments with Somerset coal (10 r 20-mesh)
at various temperatures. Sample loading--~29 g in 110-cc vessel

Initial Exposure Analyses Vol.%

Temperature ~s02 time
~ Vol.~ hr. Sample* 180tsO J++O+-+O CmO C~+O CmOmO C~O~eO C~8OteO

25 15.1 168 H None 2.24 None 0.31 None 1.97 0.025

25 15.1 168 L <0.02 0.20 <0.02 <0.13 None 0.48 <0. 015
25 21.3 34 H 4.99 2.84 0.025 - - 0.002 0.28 --
25 21.3 34 L 5.07 -- 0.02 <0.04 0.006 0.14 0.01
59 21.7 22.5 IT 0.62 1.15 0.04 0.27 -- 0.85 0.03
50 21.7 22.5 L 0.78 0.16 0.04 0.20 -- 0.64 0.02
75 20.7 23 H None -- -- I. 40 -- 3.82 0. I0
75 20.7 23 L None <0.04 0.04 0.11 -- 2+30 0.08
100 20.7 23 H None -- 0. 055 0.88 -- 4.73 0.15
100 20.7 23 L <0.04 <:0.04 0.04 0.36 -- 4.35 0.16

9 Sample H analyzed by high-resolution and sample L by low-resolution technique.

is just discernible but sufficient to indicate some
reaction of the coal with the ~02 isotope. With
a further increase to 75~ or 100~ there appeared
to be little change in the C~O, but the CmO~60
increased markedly. Nevertheless, 5 percent
of the total C02 was found as CmOZ~O,indicating
most of the C02 was probably derived from
deeaxboxylation or previous oxidation of the
coal; the fact that C~O~O was not detected was
somewhat unexpected. I t was also found that
the H2 formation increased from 0.4 to 0.6 per-
cent when the temperature was increased from
~0~ to 100~ In any event, the self-heating of
this coal should display a marked change in its
reaction mechanism at about 50~ or higher.
C. Desorptlon or Oxidation Under Flow Condi-
tions
The CO and C02 emissions in the flow tes~
were particularly sensitive to temperature and
exposure time of the coal. Typical CO results
for three coals (10 to 20 mesh) of low, high, and
intermediate reactivity are compared in Fig. 3,
where the CO levels at 50~ 100~ and 145~
peaked within about 1 hour, after which they
tended to level off or decrease slightly. However,
the CO formation at 25~ appeared to require
over 2 hours to achieve a nearly constant rate,
whereas this rate was practically constant from
the start in the static tests. Thus, the initial stage
a t elevated temperatures conceivably corre-
sponds largely to desorption or decarbonylation
and the subsequent stage to steady-state oxida-
?,ion.
Corresponding CO/AO~ or CO/C02 ratios
also increased greatly with temperature, but
the variations with coal composition diminished
(Fig. 4). At 50~ the CO/A02 was between 100
and 200 for the three coals in Fig. 4, indicating
a greater reactivity than observed with British
coals,a These ratios represent equilibrium values
( ~ 2 4 hr) and are consistent with large-scale
test results. In comparison, H~, C2H4, or C8H6
were barely detectable below 100~
For most coals, the equilibrium CO rates per
mlit mass (coal) displayed an Arrheuius-type
temperature dependence between 50~ and 145~
Such plots are shown in Fig. 5 for seven coals;
the rates were linearly normalized to 20,9 percent
0~ since 0~ consumption varied with time and
temperature. Here, coal composition effects
were more evident at 145~ than at 50~ Apparent
activation energies derived from the CO rate data
were generally between 10 and 20 kcal/mole
for all the coals investigated (Table III), al-
though two of the most reactive coals, hfland and
Sunnyhill, displayed a greater temperature
dependence above 100~ These low activation
energies can be expected in sudace oxidations
controlled by physical processes and are also
comparable to those associated with the formation
and decomposition of oarboxyl or carbonyl
complexes in coal. 9 However, the CO formation
below 50~ appears to be less temperature
dependent, as shown in Fig. 5 for the Bruceton
coal, and the apparent activation energy is less
than 10 kcal/mole. Therefore, based on these
and the 180~ data, it is concluded that the CO
emission and O~ reduction at near-ambient
 132 FIRE AND EXPLOSION RESEARCH
T,~
I~ I 1 9 = h
+ I,~0 125 leO 75 50 ~5
IO 4 I I I I
(~ Inland
9 Sunnyhill
/p-o ~- o ~---o. ~. ~omerset
v Powhatan
9 Sruceton
IO 3 ~',-,_~ I00 ~ C ~ : O Pocahontas
$0] ~ o Forse slope

F
Z
KEY
vBruoeton E. i0 z
I0 2 Opor
I ~0~C
G

I0 i
101 I I IL
2 4 6 8 ' 24
F L O W D U R A T I O N . hours

Fzn. 3. Effect of temperature on CO formation

in flow tests (15 cc/min) with 3 different coals of
10 to 20 mesh (0.2 to 0.085 cm). (Courtesy U.S. '~162 ~!+ ~'.s :e ~'o s'.~ s.,
Bureau of Mines.) I000/1", ~ *1

FIO. 5. Temperature dependence of rate of CO

104 formation in flow tests (15 ec/min) with 7 different
I I r I I coals of 10 to 20 mesh. (Courtesy U.S. Bureau of
Mines.)

at 70* to 100~ (Table III). Even the corre-

E sponding CO~ rates gave a similar correlation,
i 0 ~.
8 Slope) was capable of self-heating when initially
~102
=c J I
2s 5o 7s
TEMPERATURE,~
FI(+. 4. Variation of CO/AOS and CO/COs ratios
with temperature in flow tests (15 ce/min) with 3
different coals of 10 to 20 mesh. (Courtesy U.S.
Bureau of Mines.)
temperatures are primarily attributable to
desorption and sorption processes, respectively.
Apparent activation energies derived from the
CO rate data compared favorably with values
obtained from adiabatic self-heating experiments
as indicated for the Bruceton coal in Fig. 6. Thus,
the process controlling CO or CO~ emissions over
this temperature range seems to be the same as
that governing the self-heating of the coal. It is
interesting that even the anthracite coal (Forge
heated to 100~ Calculations based on the Frank-
Kamenetskiil~ thermal theory and kinetic con-
KEY
x Somerset stants from the adiabatic heating tests revealed
o Pocohontes that the critical diame2er for self-ignition at 250C
v Bruceton would be about 500 cm for the anthracite coal
and between 100 and 200 cm for the bituminous
coal. The level of this ignition hazard will neces-
I L L sarily depend upon coal composition, particle size,
~oo ~25 ~5o =Ts
air ventilation rate, and geometric factors.
D. Detector St~dles
Products-of-combustion sensors offer a rea-
sonable compromise of sensitivity and wide area
coverage. Air ventilation is required in mines,
and the ventilation current provides an extensive
sampling network within the active areas. Such
sensors arc adequate for slowly developing or
incipient combustion in large, unattended regions;
however, the strength and structure of the flow
 / N C I P ! E N T COM~BUSTION IN COAL MINES 133

TABLE I I I T,*C
150 125 IO0 75 50 25 I02
104 I I
(]emparison of apparent activation energies for rate
data from flow tests and adiabatic self-heathlg
tests in dry air

Apparent activation energy, I0 i

io3
Coal kcal/mole

Flow tests
(d(CO)/(it)
Self-heathlg tests
(dT/dt)
{ =

.10 z 0 O _-
StmnysideNo. 1 19.7 (50~ ~ 15.9 (75~ ~ %
Inland No. 6 14.5 (50~ ~ --
Somerset 15.4 (50~ ~) 17.2 (75~ ~)
Sahara No. 21 18.4 (50~ ~
Sunnyhil] No. 9 ]3.0 (50~ ~ 17.3 (75~ ~ 0-1
I01
Napoleon 15.3 (50~ ~ --
Vail 13.2 (50~ ~ --
Bruceton 15.2 (50~ ~ 17.1 (90~ r
Powhatan No.3 14.4 (50~ ~
Allisen 15.3 (50~ ~ --
I I I i I 0~
posahont~-~ 13.3 (50~ ~ -- 22 24 26 28 ~0 32 3.4
Forge Slope 10.3 (500-150~ 9.9 (100~ ~ I , O 0 0 / T , eK "l
16.0 (140~ ~)
FIG. 6. Temperature dependence of rate data
in flow tests (dn/dt) arid adiabatic self-heating
tests [dT/dt) with Bruceton coal. (Courtesy
network has a controlling influence on their U.S. Bureau of Mines.)
effectiveness and applicability. One present
example is based on the view that the CO/AOs
index is a reliable indicator of spontaneous com- explosives. The presence of such sources sets
bustion of coal within active areas. Scaled or less practical limits on sensitivity and reliability.
active areas are less effectively sampled, and it is Extensive laboratory tests were performed
necessary to use remote in situ detectors or with a Pittsburgh seam coal, for which a typical
sampling tubes with external pumps to monitor run is shown in Fig. 7. A 25-gin sample of 2- to 7-
these locations individually. micrometel~diameter coal was exposed in an
Many products of combustion sensors are oven at 150~ and the combustion products
commercially available, and several of these sensed in an ambient ventilating flow of 15
were evaluated in terms of their relative sen- liters/see. The sample temperature is shown as a
sitivity to mine combustibles. It is important function of time and compared with that of an
to recognize that such sensors m a y respond to inert blank. The coal self-heated cxothermically
ambient background or stray sources which have and ignited at a sample temperature of about
no relation to spontaneous combustion. For 170~ after 58 minutes. Detector signals are also
example, the ventilation return of the Brueeton shown and these indicate threshold appearance
experimental coal mine was monitored daily for temperatures of 174~ for particulates and 209~
submlcren condensation nucleii and apparent for CO with delays of 64 and 75 minutes, re-
CO content. Routine mining shifts generated spectively. Generally, the sensor thresholds
ambient levels as high as 200 000 partieles/cc correlate well with the onset of autoignition or
and 13 ppm CO. The growth and decay of sub- rapid pyrolysis.
micron particles correlated with the operation The pyrolysis behavior and threshold tempera-
of an underground diesel shuttle car, whereas tures are sensitive to heating rate, air flow, and
the CO responded more slowly :mu was influenced particle size. The pa[~icle size dependence is
also by other activities. Recent measurements shown in Fig. 8. The sample ignition tempera-
from metal and non-metal mines show similar ture, at ghc slowest heating rate for which
correlations with both diesel exhausts and ex- ignition was obtainable', is seen to increase mono-
plosives blasting. Both sensors respond readily tonically with particle size. The distribution
to the controlled combustion of uiesel fuel and ranges of the particle sizes in the samples are
 FIIL~ AN]) EXPLOSION t~SEARCH

240 1 1 I I I
220 -- / Cool scruple

200
, igniti~
/
t80~

oO 160 ~ Inert

"" [ / t Subm'cr~ -IO0

~_Q" Izo S [ porticulotes ~ ~ E
,,i o.
P I00 ~ - 80

/i Corbon a
80 / /monoxide ~-~ - 60 O

60 . - 40 ~
! z
o
o m
4o / ~ zo ,~
/ / ~
200
t~
20 40
~ _ 1 80
60
I
I00
- o

TIME, minutes
Fro. 7. I~fition temperatlLre and detector ~nsit,ivity for 2 to 7 ~m Bruceton Cosl. (CmLrtesyU.S.
Bureau of Mines.)

shown as horizontal lines, and ~he importance of
the fine fractious is dearly seen from t.he data
for minus 74- aml minus 44-micrometer coal dusta.
The submicron particulate threshold lags ignition
slightly, and the CO threshold appears signifi-
cantly later. Thegn result,s suK~est that some
form of pyrolysLs occurs as a general precursor
to rapid oxidation.
Convective flow velocities markedly lower
the ignition temperature. For example, 170-
to 285-micrometer particles held in a wire mesh
in an Olmn oven igitited at a .'~unplc temperature
of only 100~ the particulate appearance tem-
perature was 130~ Clearly, forced convection
of initially cold air at high velocities would tend
to cool the ~rople and hence, for a given size
of c.oal and configuration, there should exist
ml optimum velocity which minimizes the igai
tion tempcrature. While it. is difficult t~) scale
these data to the )nine configuration, the rea-
soning is analogous. For low vcntilatioll velo-
eiti~ (or sealed stagnant conditions) oxygen
is ad~rhed by the coal, and the rate is limited
by ox'gen supply', for very high velocities,
convective (x>oling may limit i3m heating rate.
Conclusions
Coal (le~rption studies ~ o w that the O2
reduction in air at ambient temperatures is
attributable to ehemisorption and that the CO
and COs formation reprt.'.~ent deearbouylation,
decarboxylatkm, or desorbed products from pre-
 INCIPIENT COMBUSTION IN COAL MINES 135

O
220 , ,i
C3 J /.,
.I
0 210
W
J
p- J
200
Z
o
0
190
k--dk---I 9 Iqnition

0
180
// ..... Porticutote threshold
Z CO threshold -
0
I,-
r~
170 A I
W
/'/
160

A I
I,-
~501
I0 I00
PARTICLE DIAMETER, p.m
1~o. 8. Ignition temperature and threshold appearance temperature vs particle size of coal (Brueeten).
(Courtesy U.S. Bureau of Minss.)

vlous reaction of the coal. The C0/A02 and
(X)/CO~ ratios vary with particle size, 02
content, and surface moisture content and axe
greatest for coals from mines suspected of having
a ~lf-heating hazard. These ratios are highly
aensitive to temperature, but coal composition
effects tend to diminish as rapid oxidation
occurs. Apparent activation energies derived
from CO rate data were comparable to those
calculated from adiabatic self-heating rates and
sUpport the assumption that CO emissions of the
coals at ambient temperature are not a result
of immediate oxidation.
The appearance of combustion products
correlates well with the onset of autoignition
or rapid pyrolysis and is strongly sensitive
to particle size and air velocity. Submicron
particulates appear earlier than significant CO
PrOduction, which suggests some form of pyroly-
as a precursor to rapid oxidation. The presence
of background sources from diesel exhausts or
explosives blasting complicates the evaluation
of fire detectors for use in mines.
Acknowledgment
The authors wish to express their appreciation
to Robert F. Chaiken and Robert W. DaD,ell for
their helpful consultation and to Richard G. Left,
George Martindill, Joan C. Biordi, and Helen W.
Lang for their assistance in various experimental
phases of this work. Acknowledgment is also made
of the assistance of Alex F. Robertson from the
National Bureau of Standard~ who provided the
self-heating test data.
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136 FIRE AND EXPLOSION RESEARCH

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