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Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 89–94

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Improved Coward explosive triangle for determining


explosibility of mixture gas

Jian-wei Cheng ∗ , Sheng-qiang Yang


Faculty of Safety Engineering, China University of Mining & Technology, Xuzhou 221116, PR China

a b s t r a c t

It is very important to determine the explosibility of the mixture gas in the coal mine sealed area after a gas explosion
occurred. If the combustible mixture gas has high explosive tendency, the potential re-occurring explosion would
cause rescue workers’ death when they proceed with their rescue operations in the accident mine. Therefore, no one
is allowed to go down to the underground until the mixture gas is not explosive. Lots of methods have been developed
to determine the explosibility of the mixture gas in the sealed area for a long time. One of these methods is the Coward
explosive triangle method which was published by Coward in 1952. Because of its easiness and high efficiency to
determine the explosibility of the mixture gas, it gradually becomes a very popular tool for mining engineers and
rescue team members in the mining industry. However, although the Coward explosive triangle method has extensive
applications, there are still a few drawbacks in this model. Consequently, errors may be introduced when applying.
In this paper, a brief introduction of the Coward explosive triangle is described firstly. Then based on analyzing its
drawbacks, some improvements with different aspects to calibrate the Coward explosive triangle are proposed and
discussed. Finally, case demonstrations and comparisons with the old model are also shown. The results indicate
that the improved Coward explosive triangles have better accuracy and reliability and could make more accurate
judgments.
© 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Coward explosive triangle; Gas explosion; Explosibility of the mixture gas

1. Introduction corrected Kukuczka’s formulas and improved their model.


According to the comparison of results calculated by differ-
After a coal mine fire or explosion happens, an experienced ent methods shown in their research paper, the corrected
practice is to seal the related area, and then the inert gas model had the better safety margin when applying (Pei and
(N2 or CO2 ) is injected into the sealed area to extinguish the Ma, 1998). Li and Tong took account of the effect on flammable
fire and prevent potential explosions from occurring again. In limits of combustibles due to temperature variation when
order to protect rescue workers’ safety and lives, they are not the explosive triangle was constructed; an empirical formula
allowed to go underground to proceed with their operations was developed to revise flammable limits under the differ-
until the mixture gas in the sealed area is out of the explosive ent atmospheric temperatures (Li and Huo, 2008; Tong et al.,
range. Accordingly, it is necessary to analyze compositions of 2009). Bretislav and Jan (2007) developed a kind of graphical
the sealed mixture gas and then determine its explosibility. computer software named “Vybuchovy trojuhelnik” for the
Many different methods have been proposed for deter- assessment of explosibility of fuel–air mixture. Jacobs and
mining the explosibility of the mixture gas. Kukuczka (1982) Porter (1998) proposed their algorithms to generate the con-
analyzed the compositions of gases after a coal mine explo- trol chat which has a time axis, a percentage combustibles
sion, and created his own model to predict the explosibility axis, the upper and lower explosive limits of the current atmo-
with using the mathematical transformation method to con- sphere and a prediction option which allows the user to look at
vert complicated combustible products into a single gas. Based the potential changes in the atmosphere over a period of time.
on identifying errors in the Kukuczka’s model, Pei and Ma Zhou and Wang conducted a series of experiments to obtain


Corresponding author.
E-mail address: jchengwvu@gmail.com (J.-w. Cheng).
Received 20 July 2010; Received in revised form 29 November 2010; Accepted 1 December 2010
0957-5820/$ – see front matter © 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.psep.2010.12.001
90 Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 89–94

Table 1 – Vertices of explosive triangles (%).


Gas Flammable limits Nose limits

Lower Upper Gas Oxygen

Methane (CH4 ) 5.0 14.0 5.9 12.2


Carbon monoxide (CO) 12.5 74.2 13.8 6.1
Hydrogen (H2 ) 4.0 74.2 4.3 5.1

the laws of gas flammable limits under various influence fac- sive zone COD, thus the explosion may be triggered. Below the
tors, such as temperature, pressure, oxygen concentration, line AE is the non-explosive zone, also known as the absolute
other combustible gases and the inert gas. Based on exper- safety zone. This diagram just provides the explosive trian-
imental results, they proposed a new method to plot the gle with only one individual single combustible gas existing.
explosive triangle for determining the explosibility of the mix- If the mixture gas consists of two or three combustible gases,
ture gas in the mine fire area (Zhou and Wang, 2008). Ray and the procedure of generating the resultant Coward triangle can
Singh introduced the USBM explosive triangle which is widely be described as follows (McPherson, 1993):
used in the U.S. mining industry. The explosibility diagram uti-
lizes the concept of converting the methane, hydrogen, and
1. Determine the total combustibles percentage.
carbon monoxide in the atmosphere into an effective com-
Using subscripts 1, 2 and 3 for the three combustible gases
bustible content and the carbon dioxide and nitrogen into an
and their volume percentage are P1 , P2 and P3 , respectively.
effective inert content (Ray et al., 2004). Therefore, it is a sim-
The total combustibles’ percentage is:
ple method to determine the explosibility of the mixture gas
but not a precise model.
PT = P1 + P2 + P3 (1)

2. The Coward explosive triangle


2. Determine the flammable limits of the mixture gas.
Using Le Chatelier’s Principle to determine the upper, lower
The Coward explosive triangle which was published by Coward
and nose flammable limits of the mixed gas, the equation
and Jones in 1952 has been considered as a fast and easy way to
is as follows:
determine the explosibility of the mixture gas. However, only
three combustible gases (methane (CH4 ), carbon monoxide PT P1 P2 P3
= + + (2)
(CO) and hydrogen (H2 )) are taken into account in the original Lmix L1 L2 L3
model. The explosive triangle for each individual gas could be
easily defined through three characteristic points which are where L1 , L2 and L3 can stand for the upper, lower or nose
the lower flammable limit, the upper flammable limit and the flammable limit for each individual gas, accordingly, Lmix
nose limit. The values of these points gas are given in Table 1. is the corresponding mixed gas flammability.
Taking carbon monoxide (CO) for an example, Fig. 1 shows 3. Determine the required excess nitrogen.
its explosive triangle. This diagram is divided into four zones.
The white zone over the line AB is the impossible mixture Ln +
Nex = {N P1 + N2+ P2 + N3+ P3 } (3)
zone which means the mixture gas has no possibility to com- PT 1
pose in this area. The red zone COD is the explosive zone. (For
interpretation of the references to color in this sentence, the where Ln is the nose limit of mixed gases, N+ is the volumes
reader is referred to the web version of this article.) If the gas of excess nitrogen to be added in order to make flammable
point is in this area, the explosion would occur once the explo- gases extinctive (also called inert ratio). Table 2 gives out
sive conditions are met in such environment. The blue zone the excess nitrogen needed when only one combustible gas
AOC and ODBE are not explosive zones. However, they are still exists.
dangerous areas. If more CO or fresh air is interfused into the 4. Determine the oxygen percentage.
sealed area, the gas point will move gradually into the explo-
Oxygen (nose limit) = 0.2093(100 − Nex − Ln ) (4)

So far the resultant explosive triangle could be completely


constructed based on the above data, and the actual mixture
point can also be plotted on the same diagram. Therefore,
based on the relative position between the triangle and the
actual mixture point, the explosibility of the mixture gas can
be easily determined.

Table 2 – Volumes of excess nitrogen to be added.


Combustible gas Inert ration (N+ m3 of nitrogen per
m3 of combustible gas)

Methane (CH4 ) 6.07


Carbon monoxide (CO) 4.13
Fig. 1 – Coward explosive triangle for carbon monoxide. Hydrogen (H2 ) 16.59
Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 89–94 91

3. Improving the Coward explosive triangle

Oxygen (calibrated)
3.1. Redefining the shape of the Coward explosive
triangle

3.1.1. Common combustible gases in the mine fire area

12.64
8.47
8.00
9.47
11.53
9.69
9.75
8.52
Nose limits (CO2 as inert gas)

Only three typical combustible gases (methane, carbon


monoxide and hydrogen) are considered when the Coward
triangle is constructed. However, in practices, because coal
Gas (calibrated)

oxidation or combustion is often induced by the tempera-


ture in sealed atmosphere after an explosion happens, the
mixture gas always has so complicated compositions. Gen-
erally, it consists of two general categories: atmospheric gases
5.93
5.19
15.67
3.52
3.68
2.56
2.71
3.27 and byproducts of oxidation, combustion or explosion. Atmo-
spheric gases are those typically found in an ambient gas
sample and include nitrogen, argon, oxygen, and carbon diox-
Oxygen

ide. Other byproducts, consist of carbon monoxide, hydrogen,


12.32
8.46
8.01
9.45
11.17
10.92
11.57
8.51

and the alkane (Cn H2n+2 ), alkene (Cn H2n ), and alkyne (Cn H2n−2 )
series of hydrocarbon gases, and carbon dioxide produced by
mine fires (Timko and Derick, 2006).
Under the condition of the high temperature in the sealed
5.96
5.20
15.67
3.53
3.82
2.50
2.61
3.27
Gas

area, hydrocarbon gases are often produced by coal oxidation


and combustion continually, the general chemical reaction
equation can be written as follows:
Oxygen (calibrated)

acoal + bO2 = cCO + dCO2 + eH2 O + f Cx Hy

where a, b, c, d, e and f are stoichiometric coefficients.


Some typical chemical reaction equations to produce com-
bustible gases are also listed as follows: (Deng et al., 2010;
9.86
5.11
5.15
6.09
8.40
6.28
6.34
5.07

Timko and Derick, 2006):


Nose limits (N2 as inert gas)

coal + HEAT → coke


Gas (calibrated)

limestone + HEAT → CaO

coke + CaO + 1100 ◦ C → CaC2 + H2 O + C2 H2


5.17
4.20
13.06
2.88
3.12
2.09
2.22
2.63

4CH4 + O2 + 820 ◦ C → C2 H2 + 2CO + H2

In addition, alkenes can form from alkanes through the loss


Oxygen

of hydrogen atoms by pyrolysis:


6.06
8.41
7.62
8.36
5.07
12.2
5.1
6.1

large alkanes + HEAT → smaller alkanes + alkenes + H2

In this regard, more common combustible gases found in


5.90
4.30

2.89
3.12
2.09
2.21
2.67
Gas

13.8

the coal mine fire or explosion area should be completely


integrated into the Coward triangle in order to make sure
the judgments on the explosibility of the mixture gas more
accurate. Generally, combustible gases which are typically
Flammable limits

Upper
Table 3 – Vertices of explosive triangles (%).

analyzed through gas chromatography and also recognized


14.00
74.20
74.20
28.60
12.50
20.51
20.49
80.00

as the indicator to indicate the atmospheric status in the


Data are given by Yu (1992) and Walter (1989).

mine sealed area are methane (CH4 ), ethylene (C2 H4 ), ethane


(C2 H6 ), propene (C3 H6 ), propane (C3 H8 ) and acetylene (C2 H2 ).
Although the total amount of some certain gases may be very
Lower

5.00
4.00
12.50
2.75
3.00
2.00
2.12
2.50

small, they have significant effects on the shape and position


of the explosive triangle, especially when coal spontaneous
combustion becomes so severe that lots of gases are produced.
Hence, without considering these combustible gases, some
Carbon monoxide (CO)

errors might be introduced to lead wrong judgments. Table 3


presents flammable limits for these eight combustible gases.
Acetylene (C2 H2 )
Ethylene (C2 H4 )

Propane (C3 H8 )
Propene (C3 H6 )
Methane (CH4 )
Hydrogen (H2 )

Ethane (C2 H6 )

3.1.2. Revising the nose limit of the combustible gas


The flammable limits of combustible gases are obtained by
Gas

experiments. However, due to different experimental equip-


ments or conditions in the laboratory, various experimental
92 Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 89–94

Table 4 – Inert rations.


Combustible gas Inert ration Inert ration
(m3 of nitrogen (m3 of carbon
per m3 of dioxide per m3
combustible of combustible
gas) gas)

Methane (CH4 ) 9.23 5.69


Hydrogen (H2 ) 16.98 10.46
Carbon monoxide (CO) 4.77 2.94
Ethylene (C2 H4 ) 23.59 14.54
Ethane (C2 H6 ) 18.18 11.20
Propene (C3 H6 ) 32.39 19.96
Propane (C3 H8 ) 30.35 18.71
Acetylene (C2 H2 ) 27.81 17.14
Fig. 2 – Redefined Coward explosive triangle.

results may be got. Muzyczuk developed a series of equa-


tions to generalize the combustible gas nose limit as follows
(Muzyczuk, 1974): Fig. 3 shows the comparison of redefined Coward explosive
triangles when different dilute gases are used. The explosive

⎪ (1 + gj )Li zone due to CO2 is smaller than that of N2 . In other words, the
⎨ Ci,j = inert ability of CO2 is much higher than that of N2 .
1 + (gj Li /Ui )
  (5)

⎩ Ki,j = hj 1 + 1
Li Ui 3.2. Correcting the position of the mixture gas point

Oi,j = 0.2093[100 − Ci,j (1 + Ki,j )] (6)


Because nitrogen is a cheap inert gas and also easy to be
obtained, it is frequently used as dilute gas injected into the
where Ki,j is the new inert ratio of inert gas “j” to combustible sealed area. Carbon dioxide (CO2 ), which is also an inert gas
gas “i”. Table 4 lists inert rations of eight combustible gases. Li but original existing in the sealed atmosphere in quantity
and Ui are the upper and lower flammable limits about com- already, has the inert effect on the flammabilities of all com-
bustible gas “i”, respectively. Ci,j and Oi,j are gas percentage bustibles (Ma et al., 2010). This problem is not taken into
and oxygen percentage to make up the new nose limit after account in the Coward explosive triangle. Accordingly, it is
revised. g and h are coefficients with respect to the specific necessary to identify how much the CO2 can affect com-
inert gas, their values are shown in Table 5. The revised nose bustibles when plotting the position of the mixture gas in
limits of each combustible gas to different inert gases are also the explosibilty diagram. A polish scientist, Kukuczka, ana-
presented in the Table 3. lyzed this problem and developed a series of mathematical
Eqs. (1)–(4) are still used to construct the explosive trian- formulas to correct the position of the mixture gas point
gle; but five more combustible gases should be added into in his explosive determination model constructed by him-
corresponding equations. self (Kukuczka, 1982). Fortunately, his formulas could also be
used here and are combined into the Coward explosive tri-
3.1.3. Example analysis angle to correct the mixture gas point position for acquiring
A sample taken from a sealed area yields the mixture compo- more precise results. The calculation procedure is described as
sition as follows: CH4 : 5.30%; H2 : 2.00%; CO: 3.00%; C2 H2 : 4.00%; follows:
C2 H4 : 0.50%; C2 H6 : 0.40%; CO2 : 17.00%; N2 : 57.80%; O2 : 10.00%.
As presented in Sections 3.1.1 and 3.1.2, the redefined Cow-
ard explosive triangles are constructed based on the above 1. Determine the explosive triangle (as discussed in the pre-
data. vious section).
Fig. 2 shows the redefined triangle with more combustibles
included. It can be seen that the redefined triangle is obviously
larger than the original one. In this case, using the original tri-
angle and the mixture point to determine the explosibilty of
the mixture gas, there is no explosive hazard since the mix-
ture point is out of the triangle. However, based on the relative
position between the redefined explosive triangle and the new
mixture gas point, the mixture gas is considered as explosive.
Therefore, the redefined triangle could obtain more accurate
results.

Table 5 – Inert gas coefficients.


Coefficient Nitrogen (N2 ) as Carbon dioxide
inert gas (CO2 ) as inert gas

g 0.054 0.321
h 71.77 44.23 Fig. 3 – Redefined triangles under different dilute gases.
Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 89–94 93

Table 6 – Values of different coefficients.


Gas Coefficients

ai bi ci di ei fi c i d i e i fi

Methane (CH4 ) 10.376 3.016 0 1 0 −0.78 0 0 1 −2.852


Hydrogen (H2 ) 14.918 3.533 4.643 0.140 −0.010 −0.107 5.401 0.116 0.698 −2.435
Carbon monoxide (CO) 13.039 3.396 3.117 0.161 −0.007 −0.400 3.622 0.133 0.797 −2.619
Ethylene (C2 H4 ) 14.269 3.526 4.121 0.385 −0.009 −0.216 4.849 0.072 0.729 −2.519
Ethane (C2 H6 ) 11.872 2.909 1.937 1.052 −0.005 −0.724 2.233 −0.037 0.875 −2.391
Propene (C3 H6 ) 12.869 3.383 2.934 1.098 −0.006 −0.429 3.442 −0.061 0.808 −2.637
Propane (C3 H8 ) 12.105 3.294 2.164 1.382 −0.005 −0.538 2.537 −0.110 0.858 −2.710
Acetylene (C2 H2 ) 15.308 3.577 4.901 0.127 −0.011 −0.045 5.719 0.115 0.680 −2.415

2. Determine the influence factor “˛” for the flammable limit


due to the existing carbon dioxide

PCO2 − 0.03
˛= (7)
PCO2 + PN2 − 3.778 × PO2

3. Determine the total combustibles percentage

PT = PCH4 + PCO + PH2 + PC2 H2 + PC2 H4 + PC2 H6 + PC3 H6 + PC3 H8 (8)

4. Determine the influence factor “ˇ” for each combustible gas


due to the existing carbon dioxide

20.93 − (PO + 0.2093PT )


ˇi = (9)
ai − bi ˛
Fig. 4 – Corrected position of mixture gas point.
Note: if the value of “ˇ” is over “1”, it must be reset as “1”.
5. Determine the position of the actual mixed gas point
(a) Eq. (10) can be used to compute the “X” coordinates larger. Consequently, a proper early warning index should be
(combustible gas percentage) established to track the movement of the mixture point and
provides an advance warning to remind people to take pre-

n
Pi
vention measures.
X= (ci + di PT + ei PO2 + ˛ˇi fi ) × (10) Supposing the actual point is at point “P” in Fig. 5. Accord-
PT
i=1 ing to properties of the explosive triangle, if more fresh air
is mixed into the sealed atmosphere, the point “P” will move
(b) Eq. (11) can be used to compute the “Y” coordinates to the point “A” along with the line AB. Therefore, the line
(Oxygen percentage) AB is called “dilution line”. In addition, if more combustible
gas is mixed into the sealed atmosphere, the point “P” will

n
Pi move away from the original point along with the line OE.
Y= (ci + di PT + ei PO2 + ˛ˇi fi ) × (11)
PT The early warning index (EW) could be built based on these
i=1
principles.
where Pi is the volumetric percentage of a certain com- Generally, the line AB has two intersection points with the
bustible gas, ai , bi , ci , di , ei , fi , c i , d i , e i , and f i , are explosive triangle, one is called the upper flammability limit
corresponding coefficients for different combustibles (UFL), the other one is called the lower flammability limit (LFL).
and their values are listed in Table 6. Supposing the gas point is like in Fig. 5 and it is over UFL. The
closer the point approaches to UFL, the more dangerous the

Using sample data in the Section 3.1.3 to plot the position of


the original mixture gas point and the corrected one, respec-
tively, Fig. 4 shows that the new gas point has moved since the
effect of carbon dioxide on all combustible gases is considered.

4. Early warning index to forecast


explosion hazard

The Coward explosive triangle just tells us whether the sam-


ple gas is explosive or not, but as each new sample analysis
becomes available, the mixture point on the explosibility
diagram moves while the explosive triangle also changes
its shape. Assuming the mixture point moves continually
toward to the explosive triangle, although it is not explosive
under this circumstance, the potential risk becomes larger and Fig. 5 – Determining EW index.
94 Process Safety and Environmental Protection 8 9 ( 2 0 1 1 ) 89–94

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