A Study on Detonation Safety of
Some Hydrocarbon-air mixtures
Yang Lizhong, Fan Weicheng, Zhou Xiaodong and Wang Qingan
State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, 230026, Anhui Province, P.R.China
Hazards caused by detonation of hydrocarbon-air mixtures
have been a matter of concern for a long time. In this paper,
critical initiation energy of detonation of some hydrocarbon-
air mixtures have been measured in confined (rectangle shock
tube tests) and unconfined (plastic bag tests) condition. Based
on the concept of explosion length, a formula for estimating
the critical initiation energy of detonation under unconfined
condition is presented. Detonation safety analysis of the stud-
ied hydrocarbons is carried out using the experimental results.
INTRODUCTION
An accidental explosion can extort a dreadful toll in
human fatalities as well as damage to property. Blast
damages from unconfined vapor cloud explosions are
strongly dependent on the mode of the combustion of
the cloud itself. Should the cloud burn, the blast over-
pressures generated are usually negligible. However,
if the cloud detonates, then severe structural damage
can ensue over very large distances from the cloud. It
seems to have no danger for combustible dust or
vapor or gas-air mixtures which can possibly propa-
gate explosion even though these mixtures have the
highest potential hazards. Therefore, it is necessary to
analyze these mixtures’ hazards.
Generally speaking, hydrocarbons are easily com-
bustible and explosible. When their vapors or sprays
mix with air within the lower flammability limit, they
support combustion or explosion. Some may even
support detonation, which is a remote but significant
hazard. A loss analysis in the hydrocarbon pro c e s s
industry has concluded that explosion, not fire, is the
principal risk to be avoided and that more attention
must be paid to hazards of materials and re a c t i o n
kinetics [1].
P e rhaps the most macabre accident occurred on
June 3, 1989, near Nizhnevartovsk in Western Siberia.
Engineers noticed a sudden drop in pre s s u re at the
pumping end of LPG pipeline. Instead of investigating
the trouble, the engineers responded by incre a s i n g
the pumping rate in order to maintain the re q u i re d
pressure in the pipeline. The actual leakage point was
about 890 miles downstream between the towns of
Asma and Ufa, where the pipeline was located about
Process Safety Progress (Vol.19, No.2)
a half mile away from the Trans-Siberian Railway. The
escaping liquefied gas formed two large pockets in
the low lying areas along the railway line. The gas
cloud then drifted for a distance of 5 miles. Some
hours later, after the main leakage had started, a Train
from Nizhnevartovsk destined for the Red Sea resort
of Alder was approaching the leakage area when the
driver noticed a fog in the area that had a strong odor.
The driver of another train approaching from the
opposite direction (Alder to Nizhnevartovsk) observed
the same conditions as he approached the west-
bound train. Both trains were filled to capacity, with a
total of 1168 people on board, and as they
a p p roached the area, the turbulence caused by the
trains, mixed up LPG mist and vapor with the overly-
ing air to form a flammable cloud. One of the trains
ignited the cloud. Several explosions took place in
quick succession followed by a ball of fire approxi-
mately 1 mile wide which raced down the railway
track in both directions. Trees were flattened within a
radius of 2.5 miles of the epicentre of the explosions
and windows were broken as far away as 8 miles. The
accident resulted in 462 fatalities with 796 persons
hospitalized due to 70-80% burn injuries [2].
Detonation of hydrocarbon-air mixtures can injure
and/or kill personnel, damage property and cause
poisonous materials to be released into the atmos-
phere. The problems associated with, and the need to
control detonation of these mixtures, have long been
recognized by most scholars all over the world [3,4].
Even though much valuable information has been
incorporated into practical guidance for industry lots
of problems still remain despite these valuable works.
P e t rochemical production is on the increase. Raw
materials, intermediate and final products of the
petrochemical industry are all linked to hydrocarbons,
and accidents may occur unexpectedly.
Lots of tests having been carried out in confined
(rectangle shock tube tests) and unconfined (plastic
bag test) conditions are discussed in this paper. The
object of these experiments is to find an equation, that
can be used to describe the relationship of re s u l t s
between the shock tube tests and the plastic bag tests.
Based on these results, the explosion hazard of stud-
ied hydrocarbons is analyzed.
Summer 2000 103

EXPERIMENTAL DETAILS
1. Shock Tube Test
The shock tube consists of four parts: the detona-
tion tube, temperature control system, testing system
and gas supply system. The tube is described simply
in this paper. A more extensive and complete descrip-
tion of the device is given by Yang Lizhong, Wa n g
Qingan and Fan Weicheng et al [5].
The length of the shock tube is 3.68m, with a cross-
section 0.082m x 0.082m. The entire length of the
shock tube is insulated and can be heated electrically
with temperature control. The tube’s outer surf a c e
temperature is monitored by several surface-mounted
t h e rmocouples. Four piezoelectric transducers,
mounted flush with the tube wall, sense the arrival of
a detonation front. Signals from the transducers are
amplified and captured on digital oscilloscopes and
transient recorders at a sampling rate of 0.5 MHz per
channel. The computer samples the signals from the
transient recorder.
The distances of the four piezoelectric transducers
f rom the initiation end are: 2.2, 2.5, 3.1, and 3.4m.
Detonation was initiated directly by an explosive
charge. The experimental method is the Bruceton or
up-and-down method [5]. The test begins with the pri-
mary initiation energy. If a detonation is established,
the initiation energy is dropped at a finite interval. If
t h e re is no detonation, it is increased by the same
interval. Many tests (at least 20) are carried out for the
same equivalence ratio mixture. Finally, the results are
expressed by:
E = c + d ( A / N ±1 / 2) (1)
( )
S =1.620d ( NB − A ) / N + 0.029
2 2
(2)
where
k k k
N = ∑ ni , A = ∑ ini , B = ∑ i 2 ni
i −1 i=1 i =1
c = primary initiation energy (MJ/m2)
d = interval of energy level (MJ/m2)
S = standard variation (MJ/m2)
E = critical initiation energy of 50% detonation
ratio (MJ/m2 )
ni = detonation (or non-detonation) number
for a given initiation energy
k = the number of uniform increment above
the basic point.
In a group of tests, there are two possibilities: deto-
nation, indicated by n(+) and non-detonation, indicat-
ed by n(-). When conducting calculation using the
above equation, the smaller of n(+) and n(-) should
be chosen. When n(+)>n(-), - is chosen, vice versa.
The test is started by heating the tube to 60oC. It is
evacuated to a few torr and the fuel is injected, followed
104 Summer 2000
by heated, dry, compressed air and these are allowed to
mix. After mixing for about half an hour, the mixture is
sampled and analyzed using gas chromatography.
Whether or not a detonation is produced is
deduced from the pattern of the pressure wave history
and the absolute values of pressure and velocity. If a
sudden change appears in the initial form of the pres-
sure wave and the values of pressure and velocity are
high enough, detonation is assumed to have been
established.
2. Plastic Bag Test
Field tests are carried out in plastic bag, which it is
a p p roximately assumed to carry out in unconfined
condition.
The length of the plastic bag is 2m, 4m, 8m, respec-
tively, with a diameter 0.68m. At the beginning of the
experiment, the plastic bag is evacuated to a few torr
using a vacuum pump, then fuel and compressed air
filled, till the pressure of plastic bag equals the atmos-
phere pressure. Finally, the detonator is installed at
the endpoint. Test manner includes high-speed pho-
tography, high-speed video re c o r d e r, and transient
pressure and velocity measure system.
RESULTS AND ANALYSIS
1. Experimental Results in the Shock Tube
The critical initiation energy is the minimum ener-
gy, which can ignite mixtures and propagate detona-
tion. The parameter reflects the sensitivity of the
hydrocarbon-air mixtures.
For the same mixture, the critical initiation energy
depends on the equivalence ratio of mixtures. The
tested results are shown in Table 1.
Table 1. The Critical Initiation Energy of Hydrocarbon
Air Mixtures
Hydrocarbon Equivalence Concentration Critical Energy
Ratio (vol.%) (MJ/M2)
0.89 3.0 1.081
Butane 1.19 4.0 0.971
1.80 6.0 1.330
0.95 2.5 0.693
Hexane 1.12 3.0 0.689
2.01 5.4 1.10
It can be deduced that the critical energy decreases
with the equivalence ratio first, then increases with
the ratio. There must exist the minimum ratio in
which the critical initiation energy is the smallest. The
minimum ratio is slightly higher than 1[5]. Mixture of
the minimum ratio may easily ignite and cause a
major accident. For butane and hexene, the tested
minimum ratio is 1.19 and 1.12 respectively.
2. Experimental Results in Plastic Bag
F i g u re 1 is a typical detonation of plastic bag
test. The detonation front can be identified from the
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FIGURE 1. Typical detonation of plastic bag test.
Table 2. Experimental Results of Critical
Initiation Energy in the Field
Mixture Equivalence Critical Energy
Ratio
Butane+air 0.89
Butane+air 1.19
Butane+air 1.80 >10.22
graph. Table 2 gives experiment results of the critical
initiation energy in the field.
3. Analysis
Zeldovich pointed out that the critical initiation ener-
gy is proportional to chemical reaction time (or chemi-
cal reaction zone length) [6]. According to this concept,
Lee, J.H. and Ramamurthi proposed an explosion length
related to energy of explosion source [7, 8].
1
Ro = ( Eo / po ) j +1
w h e re j=0,1,2 for planar, cylindrical, spherical,
respectively.
p0 = initial pressure of mixture.
E0= energy of explosion source. Its unit is J/m2, J/m
and J for planar, cylindrical, spherical, respectively.
Lee, J.H, had concluded that the explosion length
for the same mixture should be equal for diff e re n t
geometric conditions [9]. Thus, the following equation
can be obtained:
Es Ec
= = Ro
Ec E p
Because the ratio of the length to the diameter of
the shock tube is very large, the wave produced by
the point explosion is assumed to be a planar wave.
T h e re f o re, the explosion length can be deduced
according to the results in the shock tube.
Ep
Ro =
1.013 × 10
5
By the substitution of equation (5) into equation
(4), the following relationship is obtained:
Es = 0.974 × 10 −10 E 3p
Process Safety Progress (Vol.19, No.2)
Table 3. Calculation of Critical Initiation Energy
Mixture Equivalence Critical Energy
Ratio (MJ)
Butane+air 0.89 4.03
Butane+air 1.19 2.79
Butane+air 1.80 11.1
Equation (6) gives the relationship between critical
initiation energy of shock tube test and that of field
test. Table 3 is the value calculated using formula (6).
(MJ) As can be seen from Tables 2 and 3, the values cal-
culated using formula (6) are found to be a good
3.58 a g reement with experiment results. Thus, it’s very
convenient to assess the critical initiation energy of
2.81 hydrocarbon-air mixture in unconfined condition. So
do for safety analysis of these mixtures.
CONCLUSIONS
In this paper, experimental investigations of the
detonability of some hydrocarbon-air mixtures have
been presented in confined and unconfined condi-
tions. A simple formula is presented for estimating the
critical initiation energy of detonation under uncon-
fined conditions. This approach has proven to be sim-
ple, practical, and as accurate as other complicated
numerical models. This method which measures the
detonation property of hydrocarbon-air mixtures in
(3)
the shock tube provides a way for evaluating conve-
niently the hazard of these mixtures.
Applying the results of this paper, we can easily
assess the hazards associated with the hydrocarbons
that are used in the transportation, storage and chemi-
cal process industries under accident conditions.
Thus, appropriate precautions are taken against fire,
and explosion and detonation.
ACKNOWLEDGMENTS
The authors wish to thank the workers of the Insti-
tute of Chemical Engineering, Nanjing University of
Science and Technology for their help during experi-
(4) ments. The Project supported by National Natural Sci-
ence Foundation of China (Grant No: 59936140).
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Summer 2000 105
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106 Summer 2000
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