111Equation Chapter 1 Section 1Experimental Study on the Impact of Process

Safety Boilover Phenomena

Muhammad Ameer Zaaba1, Azizul Buang2,
1

Final Year Undergraduate Student, Chemical Engineering Department,

Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia
E-mail: amerzaaba@gmail.com
2

Final Year Project Supervisor, Lecturer of Chemical Engineering Department,

Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia
E-mail: azizul.buang@petronas.com.my
Abstract Storage of hydrocarbon materials particularly in petroleum based industry pose a fire and explosion hazard known
as boilover. The critical problems regarding boilover are to predict time and magnitude of its impact. Hence, it leads to
experiments with the objective of finding the relationship between the amount of fuel (corresponding to the thickness of the
fuel layer) and its effect on time required for occurrence of boilover and the size of area affected. To emulate the crude oil or
other hydrocarbon storage tank on a mini-scale, a used tin biscuit container in cylindrical shape with diameter of 18.5 cm was
used. It was identified that petrol and diesel alone are not possible to start boilover while combustion of mixture of petrol &
diesel and biodiesel are found to cause boilover. Increasing the fuel thickness has increased the time required for boilover for
both mixture of petrol & diesel and biodiesel. However for same thickness of fuel (2.5 cm), longer time is seen in biodiesel
(26.03 min) compared to mixture of petrol & diesel (15.18 min). The longer time could be related to higher flash point and
lower burning rate of biodiesel. As for the size of area affected (given by the distance of ejected fuel), increasing the thickness
of mixture of petrol & diesel does extends the distance of ejected fuel. For biodiesel, the trend for the distance of ejected fuel is
irregular which requires more experiments to confirm the result. Nevertheless, one thing that could be observed is mixture of
petrol & diesel resulted in longer distance (82 cm) compared to biodiesel (35 cm) for the same fuel thickness (2.0 cm). This is
probably because biodiesel have higher viscosity than mixture of petrol & diesel. Higher viscosity prevent the expanding water
beneath from easily expel the fuel layer, thereby lessen the amount of burning fuel that is ejected outward of the container.
Keywords boilover; storage tank; biodiesel; hot zone

1.0

INTRODUCTION

Daily oil and gas industry activities involve exploration

and production of various types of hydrocarbon materials.
Whether it is unrefined crude oil or processed petroleum
based product, storage of this chemical is necessary for
further transporting and processing. Storage of flammable
and volatile hydrocarbon materials such as crude oil pose a
fire and explosion hazard known as boilover. Boilover is a
violent expulsion of the hydrocarbon materials particularly
crude oil out of a burning storage tank which is caused by
vaporization and expansion of water layer inside the tank.
During its occurrence, flame from the burning tank suddenly
enlarge and would be sighted as fireball which splash hot oil
into surrounding area of the tank. Fatality, economic losses
and property damages are some of its probable effects.
Common cause of fire initiator to the crude oil or
hydrocarbon fuel storage tank is lightning [1]. While crude
oil in the tank has undergone three phase separator in the
upstream, some water from petroleum reservoir is still
entrained in the crude oil which later settle down to the
bottom of the tank [2].
A major problem with boilover is the exact mechanism
of its occurrence especially on the heat transfer mechanism
is still not fully understood by researchers who involves in
this subject matter. This factor leads to difficulties by the
firefighting and emergency response team to predict the time

of boilover occurrence. Most of the time boilover would

happen after a long period of quasi-steady burning [3].
Failure in predicting the boilover accident time affects the
success of emergency and evacuation plans. However, some
study has been conducted to identify possibility of
predicting the boilover time using micro-explosion noise
which is produced some times before the boilover [3]. Even
the premonitory period is not long, but the time will be
sufficient to evacuate people away from the burning tank.
Three criteria are essential if boilover is expected to
happen [4, 5, and 6]; presence of water in the crude oil,
downward heat transfer that is able to reach the water layer
before it is burnt out, and also the viscous nature of oil itself.
The downward heat transfer or hot zone only exists if the
hydrocarbon mixture in the storage tank is made up of wide
range of boiling points. Hot zone formation is based on
distillation process of fuel mixture in the storage tank [6].
Fuel with wide boiling point range like crude oil and fuel oil
which comprises of different components can be distillated
during the burning. During the distillation process,
components with lower boiling point vaporize and the
bubbles formed mix and homogenize the hot zone before the
vapour is burned at the fuel surface. Higher boiling point
components later sink down to the lower level while
simultaneously transfer a large quantities of heat to the
colder part of the fuel. Lighter component at the lower level
then got vaporized from in contact with the heavy

components that have just sink down, which later leave the
other part of hotter and heavier component remain at much
lower level. This process is continuously happening as the
heat zone is enlarging towards the bottom water layer [6]. In
a series of test conducted by students from University of
Science and Technology of China, they claimed gasoline
could not cause boilover while Daqing crude oil is possible
to produce boilover [7]. Viscosity of fuel is also a
contributing factor toward the occurrence boilover as lower
viscosity of water would enable the superheated water at the
bottom of tank to easily pass through the oil layer, instead of
pushing the burning fuel layer upward.
There has been many boilover studies conducted
involving experimental works and mathematical modelling.
Many of the experiments are using crude oil with variation
in the fuel thickness and diameter of the container used [5
and 6]. These parameters, when varies would affect other
parameters related to the boilover phenomena such as time
to boilover, and thermal radiation rate. Some of the studies
also use various type of fuel with different proportion during
the test [4]. However, there are lacking of studies in term of
studying the type of fuel that could boilover and its effect on
time to boilover and size of area affected. There is one study
suggesting that biodiesel is possible to produce boilover, but
more research on the matter is still needed [8]. Hence, this
paper would conduct experimental works to see the impact
of variation in the type of fuel and their thickness upon the
time required to boilover as well as size of area affected. It
should be noted that other parameters like the diameter of
container and wind velocity are not going to be studied this
project.

2.0

MATERIALS AND METHOD

2.1
MATERIALS
2.1.1
Type of fuel
Types of fuel proposed to be tested in this project are petrol,
diesel, biodiesel and mixture of petrol and diesel. Petrol and
diesel are being tested for boilover simply because they are
the two product of crude distillation unit that are more
widely used around the world compared to other fraction of
the crude oil. As the boiling point of both petrol and diesel is
different, their mixture could emulate one of the crude oil
properties which are wide boiling point. By having lighter
and heavier component, the heat zone can develop and
induce the boiling of the water layer. Biodiesel are going to
be tested in this experiment because currently there are
almost no boilover researches that identify the capabilities
of biodiesel to cause boilover. In fact, the world have started
to shift their attention towards green and sustainable energy
source and there could be a possibility that biodiesel is
going to be globally used in the future in replace of petrol
and diesel derived from petroleum.
2.1.2 Experimental site
The location suitable to conduct the experiment is at area
which is away from buildings and vehicle as the fuels are
highly flammable and the experiment involves burning. The
open area should also be away from other ignition source to

prevent unplanned fire and to have better control of the fire

in case if it is spreading away from the container.

2.1.3 Container
To emulate the open top tank of crude oil storage tank, an
open cylindrical tin biscuit container is going to be used.
The container to be used would have diameter of 18.5cm
and height of 7.0cm.
2.1.4 Video Camera
Video camera is necessary to record every runs of the
experiment. This includes the recording of micro-explosion
sound just before boilover happens. From the video camera
the flame height and its characteristic during burning can be
analysed visually. Time to boilover obtained from both of
video camera recording and on-site data recording using
stopwatch will be compared to get more accurate result.
2.1.5 Measuring tape/ruler
Measuring tape/ruler is required to measure the distance of
burning oil ejected from the container during boilover.
Horizontal distance on the ground would be measured from
wall of the container to the oil/burnt mark on the ground
after the boilover happen.
2.2

METHOD
The experimental works comprises of two parts; the
first part of the experiment is to test the type of fuel that will
boilover and the second part of the experiment involve on
finding the relationship between the initial fuel layer
thickness and time required for boilover to occur. Both part
of experiment would use a constant thickness of water
which is at 1.0 cm from the bottom of the container. Basic
procedure of the experimental works would be started by
calculating and preparing necessary fuel volume. Next,
water is going to be poured into the container prior to
pouring the fuel. Once at the experimental area, the fuel
would be ignited and simultaneously stopwatch would be
started. The burning would be observed until a micro
explosion noise is heard followed by the occurrence
boilover. As soon as the flame enlarges into a fireball
indicating boilover has started, stopwatch would be stopped
and time would be recorded.
2.2.1
Identification of type of fuel that can boilover
All of fuel type mentioned before would be prepared to
a same volume which is 400 ml except for mixture of petrol
& diesel which would have volume of 500 ml. Mixture of
petrol and diesel, would be mixed according to the ratio of
petrol:diesel; 30:70, 40:60, 50:50, 60:40, and 70:30
respectively.
2.2.2
Determination of relationship between initial
fuel thickness and time to boilover and size of area
affected
Continuation of results from previous part of the experiment
would be used. The selected fuel types are going to be
studied for its relationship between the initial thickness of

the fuel layer and time taken to boilover as well as the area
of size affected by the boilover. Fuel layer thickness would
start at 2.0 cm and will be varied every 0.5 cm until 5.0 cm.
The end range of fuel thickness is decided to be 5.0 cm to
account the volume for the 1.0 cm water layer and the height
of the container of 7.0 cm. Extending the range will cause
overspill of the fuel out from the container. Besides
investigating the effect of variation of initial fuel layer
thickness to the time required to boilover, distance of ejected
fuel from the container would also be recorded. Probable
size of area affected by boilover could be determined by
finding the circular area around the container through the
horizontal distance from the container to the point of oil
mark on the ground.

3.0

RESULTS AND DISCUSSIONS

As mentioned in previous section water thickness was fixed

at 1.0 cm from the bottom of container for all of the
experimental runs. This is equivalence to 269 ml of the
water. This is because it was proven from the experiment
that variation of water level does not influence very much
on the severity of the boilover. It should also be informed
that the container size and dimension used is constant
throughout the study.
3.1
IDENTIFICATION OF FUEL THAT COULD
BOILOVER
For the sake of this identification part, three type of fuel
of fuel used the same volume of fuel which was 400 ml
except for mixture of petrol and diesel which used 500 ml in
total for each runs. Volume of 400 ml is used to imply
significant higher ratio of fuel compared to water (269 ml).
In reality crude oil storage tank would have very large
volume of hydrocarbon mixture with lower water level at
the bottom. Other volume higher than 400 ml can be used
but it is better to reduce the amount of burning fuel for the
sake of the environment. As for mixture of petrol & diesel,
500 ml was chosen simply to ease the measuring of the fuel
according to fuel ratio stated before. Result of the first part
of experiment is the Table 1 below:
Table 1: Boilover status of different type of fuel

Type of Fuel
Petrol
Diesel
Mixture of
petrol and
diesel
Biodiesel
(Fatty Acid
Methyl Ester)

Boilover Occurrence
No. Petrol combusts but no boilover
incident was observed.
No. Diesel combusts but no boilover
incident was observed.
Yes. Different proportion of petrol and
diesel gave different boilover time and
distance of ejected fuel.
Yes. Biodiesel combusts and later
formed boilover.

Failure of producing boilover from the combustion of

petrol and diesel could be related to the absence of wide
range of boiling point in each of them. This prevented hot
zone formation in the single-boiling point fuel. During the
burning, fuel at the upper layer of the container would have

been burnt off faster before it could transfer heat to the

petrol & diesel of the same homogeneity at the lower level
of the container. When there was minimal heat transferred it
was insufficient to heat the water sub layer to its boiling
point and prevent the formation of steam to push the burning
fuel upward.
For mixture with different proportion of petrol and diesel,
the results of the experiment are shown as in the table below.
Table 2: Summary of boilover result for petrol and diesel mixture

Proportion of petrol
and diesel
Petrol
Diesel
30%
(150ml)
40%
(200ml)
50% (250
ml)
60% (300
ml)
70% (350
ml)

70%
(350ml)
60%
(300ml)
50% (250
ml)
40%
(200ml)
30% (150
ml)

Time to
boilover
12 min 20
sec
13 min 15
sec
11 min 32
sec
11 min 08
sec
10 min 16
sec

Farthest
distance of
fuel ejected
from container
71 cm
275 cm
153 cm
117 cm
193 cm

All of the proportions tested did result in boilover formation

although not all formed a proper flame enlargement. This
inferred that hot zone was formed within the container
during the combustion and the hot zone enlarged toward
water layer at the bottom. However, time required to
boilover is different for different proportion of petrol and
diesel used. Variation in the amount of light composition of
fuel (petrol) and heavier composition of fuel (diesel)
influence the burning rate and rate of hot zone enlargement.
From the table, mixture with composition of 70% petrol and
30% diesel has the shortest time for boilover to happen. One
probable reason is that the petrol and diesel are evenly
mixed at the fuel layer above the water layer and as petrol
have the lower boiling point it gets quickly heated,
vaporized and burnt off at the surface of the container. While
this was happening, heat from petrol was transferred to the
diesel components that were evenly scattered around the
petrol component. Basically the boiling point of diesel is
higher than the boiling point of petrol and it is less
flammable compared to petrol. Thus, it would require a lot
of heat energy from the heated petrol and this convective
heat transfer process to diesel could quickly happen due to
higher amount of petrol in the container. As the heating and
burning of diesel took times, heat was transferred to the
portion of the fuel mixture at the lower level of the container
and this process occurred until it reaches the water sub layer.
This proportion of 70% petrol and 30% diesel have
resulted a horizontal distance of fuel ejection up to 193 cm
from the container wall. Although it is not the farthest
distance as compared to distance made by mixture with 40%
petrol and 60% diesel, it is the second farthest distance
among all the five experiments conducted.
As for biodiesel, it did produced boilover as what has
been predicted by [8] with boilover time of 11 minute 54
second and distance of fuel ejected of 30 cm. Some of the

observation with regards to the biodiesel combustion was it

took a longer time to cause boilover compared to the
mixture of petrol and diesel of the same volume. Secondly,
the flame is relatively stable, less vigorous and slightly
smaller during the quasi-steady period, unlike flame from
the burning of petrol and diesel which is irregular in size.
The amount of soot generated was also less than soot
formed in the petrol and diesel combustion. However,
during the boilover the flame expanded and increased
greatly in height as the fire is thrusting upward (Fig. 1)
while most of the flame during boilover of petrol and diesel
mixture rather enlarging in horizontal direction.

Figure 1: Biodiesel boilover

This could be related to the difference in viscosity of the
biodiesel which have higher kinematic viscosity than diesel
which is about 6.5 7.0 centistokes at 20 C [9]. Diesel is
being compared here instead of petrol because burning
mixture petrol & diesel could be considered as distillation
process. During the premonitory period, much of the petrol
has been burnt off which leave some quantity of diesel
(heavy component) in the container. Diesel used in this
study can be considered as No. 2-D diesel fuel as this type
of diesel is the standard grade used in heavy duty trucks and
diesel cars. Their kinematic viscosity at 40 C is about 2.5
3.2 centistokes [10]. In the case of biodiesel boilover, at the
moment when the water layer got superheated and expand
explosively, the hot water could not easily pass through the
viscous biodiesel layer. Thus, when it vaporized and
expanded upward, together with the compressed force from
the fuel viscosity the superheated water pushes together the
burning biodiesel layer in vertical direction at a certain
height. This ejected but hardly impenetrable layer of fuel got
burnt and contributed to the high rise of the flame during the
boilover process.
Biodiesel is possible to produce boilover because it is a
mixture made up of many components with varied boiling
points. 97.8% of the biodiesel is made up of unknown ester
content. According to [11], fatty acid chains in the raw oils
and fats from which biodiesel is produced are mainly
comprised of straight chain hydrocarbons with 16 to 18
carbons that have quite similar boiling temperatures. The
atmospheric boiling point of biodiesel generally ranges from
330 to 357C. Still, [11] conducted standard test method for
boiling range distribution of fatty acid methyl esters
(FAME) in the boiling point range from 100 to 615C by
using gas chromatography method. In fact, the palm methyl
ester is also made up from the palm kernel oil which is rich
in C12 and C14 fatty acid [12]. Nonetheless, for future
works, the exact component of the biodiesel should be

referred to its manufacturer. Due to wide range of boiling

point, the heat wave or hot zone was able to be formed and
enlarged toward the water layer. Among the components of
the biodiesel are shown in the Table 3 below [9].
Table 3: Biodiesel composition

Property

Unit

Biodiesel Specs.

Ester content

% (m/m)

97.8

Linolenic acid
methylester

% (m/m)

0.3

Polyunsaturated
methylester

% (m/m)

<1

Methanol content

% (m/m)

< 0.1

Monoglyceride
content

% (m/m)

< 0.1

Diglyceride content

% (m/m)

< 0.1

Triglyceride content

% (m/m)

< 0.1

3.2
DETERMINATION OF RELATIONSHIP
BETWEEN FUEL THICKNESS TOWARD BOILOVER
TIME
AND
SIZE
OF AREA AFFECTED
From the first part of the experiment it has been identified
that mixture of petrol and diesel and biodiesel were possible
to form boilover.
3.2.1
Mixture of 70% petrol and 30% diesel
This mixture was selected for the second part of the
experiment because of its shortest boilover time and second
largest size of area affected, thereby putting it to be the most
unsafe boilover scenario compared to the other four fuel
composition. Summary of the detail of the experiment are
presented in the table and figures below.
Table 4: Summary of fuel thickness variation on the boilover (petrol &
diesel mixture)

Fuel
Thickness
(cm)
Fuel volume
(ml)
Boilover
time (min)
Distance of
ejected fuel
(cm)

2.0

2.5

3.0

3.5

Petrol:
377
Diesel:
161
14.03

Petrol:
470
Diesel:
202
15.18

Petrol:
564
Diesel:
242
15.33

Petrol:
659
Diesel:
282
17.07

82

113

115

129

Fuel
volume
(ml)
Boilover
time (min)
Distance of
ejected fuel
(cm)

Graph of time for the first boilover vs. initial fuel thickness
20.00

Time for the first boilover (min)

15.00
f(x)
= 1.85x + 10.3
R10.00
= 0.91
5.00

538

672

806

941

1075

1210

20.23

26.03

32.05

33.22

37.05

43.16

35

45

38

65

42

55

0.00
1.00 3.00 5.00

Graph of time to first boilover vs initial fuel layer thickness

Initial Fuel Layer Thickness (cm)

60.00
Figure 2: Graph of time to boilover against thickness of mixture of
petrol and diesel

Graph of distance of ejected fuel vs initial fuel layer thickness

40.00
f(x) = 8.51x + 4.31
R = 0.97
Time to the first boilover (min) 20.00
0.00

150.00
Initial Fuel Layer Thickness (cm)

f(x)
= 28.6x + 31.1
100.00
R = 0.87
Distance of ejected fuel (cm) 50.00
0.00
1.00

Figure 4: Graph of time to boilover against initial fuel (biodiesel) layer

thickness

3.00
5.00

Initial Fuel Layer Thickness (cm)

Graph of distance of ejected fuel vs initial fuel layer thickness

Figure 3: Graph of distance of ejected fuel against initial fuel layer
thickness

Figure 2 and Figure 3 shows the trending of time

required for boilover and distance of ejected fuel from the
container wall with regards to variation of the initial fuel
layer thickness respectively. In Figure 1, the general trend is
that the thicker the layer of mixture of petrol and diesel, the
longer the time required for the first occurrence of boilover.
This is because the thicker the fuel layer, more time is
required for the heat wave or hot zone from the burning
surface of the container to travel down to reach the fuelwater interface.
Graph in Figure 3 also shows increase in the distance of
ejected fuel from the wall of the container with the increase
of fuel (mixture of petrol & diesel) thickness. Increment in
the fuel volume increase the level of fuel near the open
surface of the container, allowing for the frothing fuel to be
ejected out easily rather than hindered by the inside
container wall. Besides, once the first boilover has ejected
most of the fuel layer near by the container, the water layer
at the bottom container is still boiling, expand, and eject the
thinner and lighter fuel layer that is left from the first
boilover. This enables the superheated water to exert a
higher force to the lighter fuel surface causing it to be
ejected farther from the container.
3.2.2

Biodiesel
The summary of the boilover experimental runs using
biodiesel is displayed as in the table and figures below.
Table 5: Summary of fuel thickness variation on biodiesel boilover

Fuel
Thickness
(cm)

2.0

2.5

3.0

3.5

4.0

4.5

80.00
60.00
f(x)40.00
= 6.74x + 24.75
Distance of ejected fuel (cm)R 20.00
= 0.31
0.00

Initial Fuel Layer Thickness (cm)

Figure 5: Graph of distance of ejected fuel (biodiesel) against initial

fuel layer thickness

Based on graph in Figure 4, time required for boilover

increase almost linearly with the increase in the thickness of
biodiesel. As the thickness increase more time is needed for
heat to travel down to reach the fuel-water interface layer
before it could heat and vaporize the water. Noted that the
for the same fuel thickness as compared with mixture of
petrol and diesel, biodiesel takes more time to burn. This is
probably because biodiesel have higher flash point and
boiling point as compared to the flash point and boiling
point of petrol and diesel. Biodiesel used in the study have
the flash point of at least 120 C and boiling point of 347 C
[9] while petrol have flash point and boiling point of 43 C
and 200 C respectively. As for diesel the flash point and
boiling point is 60 C and 160 400 C. It could be seen that
biodiesel requires more heat energy to reach certain
temperature and later burn. The longer time of biodiesel
combustion could also be related to its lower burning rate
(1.55 mm/min) when compared to petrol (4.5 mm/min) and
diesel (2.5 3.0 mm/min) [8].
Graph in Figure 5 shows the relationship between the
thickness of biodiesel layer and distance of ejected fuel from

the container during boilover. It was observed that the

distance is not as far as the ones made by the mixture of
petrol and diesel boilover. High viscosity and density of the
biodiesel fuel might prevent the burning fuel from being
ejected farther. Assumption could not be made that
increasing the fuel thickness would increase the size of area
affected because from data obtained there is not much
distance difference between previous data and next data.
Hence, further experimental runs and researches are
required to identify whether increasing the biodiesel
thickness would affect the distance of ejected fuel.
3.3

RECOMMENDATIONS

In order to achieve more accurate readings, it is

suggested that for future experimental runs there could be
barriers be placed a certain distance around the container to
minimize the effect from wind disturbances. Secondly, a
layer of sand could be spread at the ground before placing
the container. This is to ensure the container is level and not
tilting. Placement of sand could also ease the measuring of
distance of the ejected fuel as it can be clearly seen on the
sand. Another recommendation is to combust the fuel as
quick as possible after it has been poured into the container
especially which involve petrol as it is highly volatile and
there could be some loss if it is left for a long time.

4.0

[1]
[2]
[3]

[4]

[5]

[6]
[7]

CONCLUSION

Understanding the mechanism of boilover and factors

that trigger the occurrence would be very helpful for future
prevention or prediction on the time to boilover. Even
though the accident is getting rare with the advancement in
the storage tank design and maintenance, but if it happens
the damage and loss incurred would be catastrophic. From
experiment conducted, it was concluded that only fuel with
wide range of boiling point like mixture of petrol & diesel
and biodiesel can cause boilover.
In general, mixture of petrol and diesel are faster to
boilover in comparison to biodiesel for the same amount of
fuel. It was also found out that as the thicker the fuel level,
the longer time required for boilover. As for the size of area
affected by boilover, experimental runs shows the area get
wider when the fuel thickness increase. However, this is not
the case for biodiesel which have inconsistency in the trend
of the distance of ejected fuel data. Many factors including
wind disturbance, surrounding temperature, and fuel
viscosity does affect the boilover time, area affected and
also the behavior of the flame. Nevertheless, it is concluded
that future works are essential to understand boilover better
especially on the formation of hot zone and prevention
methods.

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