Fuel Vol. 74 No. 12, pp.

1772-1775, 1995
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Explosion risks during the confined storage

of bituminous coals
Calculation of gaseous hydrogen accumulation in ship
holds

S. L. Grossman*'t, S. Davidi* and Haim Cohen*'¢

*R. Bloch Coal Research Center, Chemistry Department, Ben-Gurion University of the
Negev, PO Box 653, Beer-Sheva 84105, Israel
?National Coal Supply Co., Ramat Gan, Israel
¢Chemistry Department, Beer-Sheva, Israel
(Received 10 February 1995; revised 19 June 1995)

Bituminous coal piles stored in the open air can undergo autocatalytic heating accompanied by the emission
of small but appreciable amounts of molecular hydrogen. When the coal is contained in a confined space and
the temperature reaches 40°C, accumulation of hydrogen is expected. This process has been observed for a
wide variety of bituminous coals. The amount of hydrogen gas expected to accumulate in the air pocket
above the coal cargo in ship holds (assuming that the coal's temperature approaches 40°C during the
voyage) has been calculated. The results clearly indicate that in most cases the hydrogen concentration will
be appreciably above the lower explosion limit in air. Hence when bituminous coals are stored in a confined
space (e.g. a ship hold), the explosive risk of hydrogen should be taken into account.
(Keywords: coal; storage; explosion hazard)

The international maritime trade in bituminous coals is O2(physically adsorbed)---+Oxycoal (chemisorbed oxygen),
growing appreciably owing to low and stable prices,
improvements in coal combustion techniques and Q] = 377kJmol-1 (ref. 6) (2)
increased energy demand. One of the operational require-
ments is the storage of large quantities of coal for long Oxycoal ~ CO2 + H 2 0 (major reaction), Q2 (3)
periods. The stored coal is in contact with atmospheric Oxycoal ~ CO, Cl~4 hydrocarbons (side reactions)
oxygen and undergoes low-temperature oxidation which
(4)
can result in autocatalytic self-heating of a pile 1. This
process can be sustained only if the heat produced by the
The oxidation-induced autogenous heating (QI + Q2 =
exothermic oxidation-related reactions cannot be suffi-
ciently dissipated by heat transfer within the stockpiles 2'3. 3 3 . 4 - 35.1 M J k g -I coal) of coal not only poses safety
and handling problems but causes a loss in calorific value
If the stockpile temperature rises above 30°C, the
of the reacted coal 6'7. However, in the low-temperature
result will be vaporization of the moisture content of the
range only a small proportion ( < 25%) of the oxygen
coal as well as the emission of low-molecular-weight hydro-
consumed is emitted as gases, mainly carbon dioxide and
carbons and carbon monoxide. The rates of vaporization
some carbon monoxide. This percentage is inversely
and emission of gases increase with temperature. The
dependent on temperature. To assess the oxidation
presence of these products appreciably lowers the self-
resistance of the various coals stored in Israel, extensive
ignition point of the coal in question, and in extreme
simulation experiments were performed in the authors'
cases spontaneous combustion can occur 4. Storage of
laboratory. Surprisingly, it was observed that the
coal in confined spaces such as ship holds, silos, bunkers
and rail wagons is of course much more susceptible oxidation of small quantities (1-20g) of coal samples
at relatively low temperatures (45-150°C) in batch glass
to self-ignition, if the storage period is more than a
reactors was accompanied by the release of molecular
month. The autogenous heating of stockpiled coal is
hydrogen in small but appreciable amounts 8. This process
generally restricted to small distinct areas commonly
was for observed bituminous coals of a wide geographi-
referred to as 'hot spots', characterized by good oxygen
diffusion and insufficient heat transfer 4,5. Thus coal cal and geological variety. An exhaustive literature
search provided only two citations 9'1° in which the low-
stockpiles can be envisaged as large chemical reactors
temperature emission of molecular hydrogen as a result
in which the reactions that take place can be generalized
as follows: of coal oxidation was mentioned. It must be stressed that
these papers dealt with oxidation at considerably higher
Coal(s) + O 2 ( g ) ---+ O2(physically adsorbed) (1) temperatures, ~240°C and so the low-temperature (45-

1772 Fuel 1995 Volume 74 Number 12

 Explosion risks during the confined storage of bituminous coals." S. L. Grossman et al.

Table 1 Characteristics of the coals studied a

Australian Colombian S. African American

Proximate analysis (wt%)

Moisture (as received) 7.6 11.9 7.9 6.8
Ash (dry basis) 11.0 8.7 13.9 7.3
Volatiles (daf) 29.0 41.8 33.4 40.0
Gross calorific value (MJ kg -1) 35.35 33.61 33.64 35.03
Ultimate analysis (wt% daf)
C 84.3 81.0 84.8 84.4
H 5.0 5.6 4.9 5.5
N 2.0 1.6 2.0 1.6
S 0.6 0.8 1.0 1.5
CI <0.1 0.1 <0.1 0.1
O 8.1 9.9 7.3 6.9
HGI 60 49 50 53

"Analyses performed in accordance with A S T M except for oxygen, calculated by difference

150°C) oxidation-related emission of hydrogen 1~ can be respectively). Most of these cargoes are transported in
regarded as a novel result. In a later joint study 12 it was large Cape-size vessels (120 000-180 000 t), particularly
confirmed that the release of molecular hydrogen occurs coal that is shipped from South Africa, Australia,
also with German coal (Westerholt). The joint study was Colombia and the USA. The problem of self-heating
performed with a flow reactor and showed that this due to coal oxidation is usually considered to be the main
process occurs at temperatures as low as 40°C. Two other cause of (1) deterioration of calorific value in the ship and
observations reported recently have confirmed these (2) worse, ship fires. The risk of possible accumulation of
findings: British Coal observed]3 that in silos containing molecular hydrogen should also be considered, as it may
large amounts of bituminous coals (50-150 t), emission of occur in ship holds, as discussed later.
hydrogen and carbon monoxide occurred at relatively low
temperatures (50-150°C) and K. Vorres (personal com-
CALCULATIONS
munication, 1993) reported that during long-term labora-
tory storage (years) at room temperature of coal, molecular The calculations are based on the results obtained in the
hydrogen was found to be present. authors' laboratory. The coals studied and their proper-
Explosions in confined storage facilities are a well- ties are listed in Table 1. The amounts of hydrogen
known, undesired phenomenon and unfortunately have produced and oxidation rates (oxygen consumption) as a
been reported frequently, with loss of life, mainly in deep function of coal type at 95°C are given in Table 2. The
mines but also in large silos (where the coal is left for amount of H 2 released by an oxidation-related process is
relatively long periods). Generally two main reasons are related linearly to the amount of oxygen consumed (as
offered for such events: (1) accumulation of high con- long as the ratio of mass of 02 consumed to mass of coal
centrations of coalbed methane; (2) occurrence of large is > 0.02-0.03). Thus, in argon and nitrogen atmospheres
amounts of high-surface dust, usually in the atmosphere the concentrations of H 2 produced in 60ml reactors
of a mine. To prevent such situations from occurring, were 80 and 34 ppmv, respectively, when 5 g samples of
efficient ventilation and filtration of the dust as well as American coal were heated for 70h, whereas replace-
on-line monitors are installed in mines. In ship holds, no ment of inert gas with air or oxygen increased the
measures are taken to detect the presence of dust, though amount of H2 to much higher concentrations (350 and
organic explosive gases are monitored. Explosions do 1100 ppmv, respectively). The small emission of H 2 in an
still occur in some cases even though no indication of inert environment is the result of decomposition of some
methane or dust accumulation has been observed (in chemisorbed oxygen due to some leakage of air to the
silos). In March 1994 a mine in South Africa was shut reactors. The maximum difference in the production rate
down owing to fires and possibly explosions with the loss of hydrogen between the different coals in air is about
of 18 lives14. The new recent finding that small but threefold (232 ppmv for Australian coal and 600ppmv
appreciable concentrations of molecular hydrogen are
evolved as a consequence of low-temperature oxidation Table 2 Molecular hydrogen in the gas phase of batch reactors for
raises the question whether transient accumulation of different coal types heated for ~65 h at 95°C in air
hydrogen locally above the lower explosion limit (LEL) Particle size Oxidation rate H2
might initiate a chain reaction leading to an explosion. Coal type (#m) (mlO2 g -1 h -1) (ppmv)
The authors therefore decided to examine the possibility
Colombian ~<74 0.128 488
that such a situation might develop inside a ship's hold
Australian ~<74 0.142 232
loaded with bituminous coal. American ~<74 0.027 646
The international maritime trade in bituminous coal American 75-250 0.066 390
amounts to roughly 350 million tonnes per annum. This S. African ~<74 0.038 370
trade employs ships of different sizes; handy, pana- S. African 75-250 0.74 320
S. African />315 372
max and Cape ( < 30 000, 30 000-80 000 and > 80 000 t,

Fuel 1995 Volume 74 Number 12 1773

Explosion risks during the confined storage of bituminous coals. S. L. Grossman et al.

Table 3 Rate of hydrogen emission as a function of temperature in an so the above assumption that hydrogen will accumulate
oxygen environmenta in the upper air pocket is reasonable. D a t a taken at
Oxidation Temperature H2 emission Hz production rate loading ports show that coal is loaded at roughly
period (h) (°C) (ppmv) (ppmvg-1 h-l) atmospheric temperature (~20-30°C). An increase of
2-10 K occurs during the course of a 3 - 4 week voyage.
12 55 25 0.090
48 55 370 0.335 However, on rare occasions cargoes bound for Israel 15
168 55 1751 0.453 have reached 50°C. International Maritime Organization
0 95 0 0 (IMO) procedures 16 as well as national regulations of
0.5 95 21 3.82 such countries as South Africa 17 and Australia clearly
2 95 223 10.1
4 95 378 8.61 dictate temperatures (generally 45°C) above which coal
12 95 1347 10.2 should not be loaded aboard a vessel. The I M O also
24 95 2707 10.3 dictates that if a cargo's temperature exceeds 55°C the
vessel should sail to the nearest port that can offer
a All oxidation experiments performed with an American coal (size
~<74#m) in 120ml glass reactors. Sample mass was 23g for suitable assistance. There have been instances of coal
experiments at 55°C, and 11 g at 95°C cargoes self-heating and reaching a serious self-ignition
stage during long-term voyages of several weeks 18. These
vessels ply the ocean for 15-32 days, and it should be
for American coal). Furthermore, no appreciable effect noted that most of the voyages are in warm waters.
of particle size is observed (Table 2, South African coal), Hence the hold of a coal-bearing vessel could be likened
meaning that the emission occurs not only on the outer to a giant batch reactor, since the ingress of fresh air is
surface of the coal particle but also inside the larger pores minimized by closing the hatch covers.
(radius > 10 nm) where diffusion of the gas molecules is The temperature chosen here for the calculation of the
not restricted. Calculation of the amount of molecular concentration of accumulated hydrogen in the hold is
hydrogen produced in the gas phase, relative to the per- 40°C. The emission rate of hydrogen can be calculated by
centage of oxygen consumed by the same mass of a given taking the reported activation energy 19 for the production
coal, shows that this value is constant: ~ 11.4 + 2 p p m v of H2, 47.7 kJ mo1-1 . If we take this analogy of a ship s hold
per 1% 02 consumed at 95°C. as a giant batch reactor to its logical conclusion, then the
The production of hydrogen is a temperature- and amount of molecular hydrogen produced in a ship's hold
time-dependent process. The effects of temperature and during a voyage can be calculated by taking into account
time were measured with American coal and are pre- some parameters of the hold and the trip.
sented in Table 3. The amount of hydrogen produced is To assess the possible accumulation of hydrogen in a
independent of the moisture content or particle size of ship's hold during extended voyages, the following
the coal and only slightly dependent on the amount of parameters have to be estimated: length of voyage,
oxidized coal. amount of coal in the hold, volume of reacting oxygen,
To examine the possibility that the hydrogen concen- rate of oxygen consumption by the coal, volume of free
tration in the space above the coal pile in a ship's hold space where hydrogen will accumulate, average tem-
could reach the LEL, the example was taken of a typical perature of the transported coal, and type of coal
Cape-size coal vessel with 150000t of cargo in nine shipped. Some of these parameters depend on the
holds, each containing ~ 17 000 t occupying a volume of importing and exporting countries. Here the values
2 0 0 0 0 m 3. The dead space or pocket of air above the existing in coal shipments to Israel have been taken to
trimmed body of coal may be up to 1 m deep directly perform the calculation. Israel imports coals from South
underneath the hatch, though it thins out towards the Africa, Australia, Colombia and the USA. In Table 4 the
edges of the hold. In this pocket the molecular hydrogen average values of the parameters are given. The coals
produced by the heated, oxidized coal is expected to studied represent a broad spectrum of those that are
accumulate. A rough estimate of the dead space would be ubiquitously traded worldwide. They originate from a
500m 3, not including of course the interparticle space wide range of geological eras, from the Carboniferous
within the coal cargo. There is always the possibility that (USA and Germany), Permian (South Africa, Australia)
hydrogen is absorbed inside the pores of the coal. How- and Tertiary (Colombia). Despite the variation in rank,
ever, experiments to measure the amount of hydrogen ash content and provenance, all the coals examined emit
adsorbed inside the pores of coal particles at the tem- significant quantities of molecular hydrogen.
perature range 25-65°C have proved that it is negligible The calculation of the amount of accumulation of
compared with the amounts emitted to the atmosphere, hydrogen in the ship's hold during transportation from

Table 4 Average coal transportation parameters for voyages to Israel and estimates of hydrogen gas accumulation in ship's hold
Coal type Australian Colombian South African USA

Voyage duration (d) 29 18 16~, 29b 15

Hold volume (m3) 15 700 21 000 21 000 14400
Mass of coal in hold (t) 13350 17800 17 800 12200
Free space (m3) 500 500 500 500
H2 accumulated during voyage (vol %) 3.1 5.3 3.1", 5.4b 4.1

Through the Suez Canal

b Via the Cape

1774 Fuel 1995 Volume 74 Number 12

 Explosion risks during the confined storage of bituminous coals. S. L. Grossman et al.
the USA is given as an example. The equation used is:
Volume H2 produced = (Rate of H 2 released) x (Voyage
duration) x (Coal amount in hold)
Typical variables used for the calculation are:
Rate o f H 2 release: 0.15 p p m v (g coal) 1 h-l (in 120ml
batch reactor in oxygen atmosphere)
Duration of voyage: 15 d
A m o u n t of coal in hold: 12200t
When the values of the different variables are used in
the equation, the amount of hydrogen produced in one
hold during a voyage from the USA to Israel (for
Pittsburgh No. 8 coal) is 15.8 m 3, assuming that the tem-
perature of the coal is kept at 40°C during the voyage.
Thus the concentration of the hydrogen in the 500m 3
pocket above the coal pile will reach 4.1 vol. %, which is
above the L E L 2° (4.0 vol %). The above calculation has
been repeated for the different coals imported into Israel
and the results are given in Table 4. As can be clearly
seen, in voyages of coal from the USA, South African
coal via the Cape and Colombian coal, the hydrogen
accumulation in the pocket above the coal pile in the
ship's hold is above the LEL, indicating possible risk of
explosion if a chain reaction is initiated (e.g, by an
electrostatic charge or a spark). In Australian coal trans-
port, the concentration of hydrogen rises to a dangerous
level, 3.1 vol %, which is close to the LEL in air. This
possibility occurs if the temperature of the coal is at least
40°C and there is no dilution of the hydrogen nor leakage
of the hydrogen out of the hold. Thus if such a scenario
actually unfolds during the marine transport of coal,
clearly the role of hydrogen should be considered whilst
evaluating safety risks.
DISCUSSION
All the risk evaluations above were based on the
assumption that the ship's hold behaves similarily to a
closed batch reactor. However, in the event that the hold
has some gas exchange with the outside atmosphere,
either as a precaution or inadvertently owing to a poorly
sealed hatch cover, two opposing processes will result:
(1) increased rate of hydrogen production due to the
continuous supply of oxygen, which is a precursor
for hydrogen emission (due to the decomposition of
surface oxides)l l;
(2) dilution of the hydrogen, preventing the build-up of
dangerous concentrations.
Without a more detailed study of the atmosphere
prevailing in ship's holds it is premature to reach a
conclusion as to the effect of ventilation on the safety
risks. The test case of ship's hold described above is only
one example; underground coal mines (especially those
at great depth where higher temperatures prevail) may
pose an even greater risk.
When explosive gases accumulate, industrial practice
recommends the ventilation of the relevant confined
space. The I M O for example dictates that a ship's hold
should be aerated under such circumstances. The results
of this study however point to different means of
reducing the risk of explosions. Hydrogen and appar-
ently other explosive gases (light hydrocarbons) are
directly correlated with the consumption of oxygen,
hence in order to retard the build-up of these explosive
gases the ingress of oxygen should be prevented.
Ventilating a troublesome confned space with an inert
gas would be ideal. Furthermore, means of alarm and
detection are not geared to hydrogen emissions, so the
risk posed by this gas is overlooked in current practice.
As it is a relatively simple experimental procedure to
sample the gas atmosphere in the free pocket above a
coal pile in a ship's hold, it is suggested that such
experiments be carried out in order to check the above
calculations.
ACKNOWLEDGEMENTS
The authors would like to thank the R. Bloch Coal
Research Center, Ben-Gurion University of the Negev
for their support of this work. S.L.G. would like to thank
the Israeli National Coal Supply Co. for assistance.
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Fuel 1995 Volume 74 Number 12 1775