Stability Behavior of Water-in-Diesel Fuel Emulsion: M. T. Ghannam and M. Y. E. Selim
Stability Behavior of Water-in-Diesel Fuel Emulsion: M. T. Ghannam and M. Y. E. Selim
C, kg/m
3
829.7
Dynamic viscosity at 20
C, mPas 5.61
Surface tension at 20
C, mN/m 30.5
Flash point,
C 76
Initial boiling point,
C 169.8
Final boiling point,
C 376.5
400 M. T. Ghannam and M. Y. E. Selim
80% at elapsed time equals zero, that is, when the homogenizer was ceased.
We only needed 5 minutes to separate the entire amount of introduced water.
Even higher mixing speeds of 60,000 rpm over 3 minutes of mixing did
not enhance the emulsion stability. We prepared another run for 20% W/D
emulsion using a mixing speed of 20,000 rpm, no added surfactant, and
a mixing period of 30 minutes. This test showed that almost 90% of the
introduced water was separated within the rst 10 minutes of elapsed time.
Therefore, this preliminary study showed that the presence of surfactant is
crucial for W/D emulsion stability. Figure 1 shows the effect of added water
on the emulsion stability in the presence of 0.2% surfactant concentration.
We prepared the emulsions using a mixing speed of 15,000 rpm and mixed
for 2 minutes. Figure 1 shows that the 10% W/D emulsion remained stable
for almost 4 weeks without any separated water. The 20% W/D remained
stable for 10 days before any water was separated. The stability prole
of 30%, 40%, and 50% W/D emulsions is also shown in Figure 1. The
last three emulsions remained stable for only 5 hours, and then the water
gradually separated from the emulsion. As can be seen, the percentage of
water separated gradually increased with the water concentration. In the 50%
W/D emulsion, for example, 67% of the introduced water was separated
within 3.8 days. Figure 1 shows the importance of the surfactants role on
the W/D emulsion stability.
It is important to determine the stability conditions for each W/D emul-
sion in terms of mixing speed, mixing time, and surfactant concentration.
Figure 2 shows the stability prole for 20% W/D emulsion. This emulsion
was prepared in the presence of 0.2% surfactant concentration, mixed for
2 minutes, and different mixing speeds ranging from 5,000 rpm to 15,000
Figure 1. Stability prole for different W/D emulsions.
W/D Emulsion Stability Behavior 401
Figure 2. Effect of mixing speed on the stability behavior of 20% W/D emulsion.
rpm. As can be concluded from Figure 2, the emulsion remained stable for
almost 6.5 hours without separating any water under all the reported mixing
speeds. Beyond this period, the stability enhanced strongly with mixing speed.
For example, the 20% W/D emulsion was reported stable for 10 days when
a 15,000-rpm mixing speed was applied. For a longer stable period, the 20%
W/D emulsion can be prepared in the presence of 1% surfactant concentration,
10-minute mixing time, and 15,000 rpm. These conditions provided a stable
period of 4 weeks as shown in Figure 2.
The stability investigation for the 30% W/D emulsion was carried out
using a mixing speed of 15,000 rpm, 0.2% surfactant concentration, and a
mixing time of 2 minutes. The 30% emulsion was only stable for 5 hours.
The water was gradually separated until 32% of the water separated within
1 week. As higher mixing times of 10 and 20 minutes were examined, the
stability prole was slightly enhanced. For 20 minutes of mixing time, the
emulsion was stable for 8.5 hours, and 11% of the water was separated within
1 week as shown in Figure 3a. In order to enhance the stability behavior of
30% W/D emulsion signicantly, we added several surfactant concentrations
over the range of 0.2 to 1.75% for a mixing speed of 20,000 rpm and a
mixing time of 30 minutes (Figure 3b). The presence of surfactant shows a
strong effect on the emulsion stability enhancement. As can be concluded
from Figure 3b, the amount of water separated from the emulsion strongly
decreased with the increase of surfactant concentration. For example, at the
surfactant concentration of 1.75%, the 30% W/D emulsion remained stable
for almost 1 week.
We prepared the 40% W/D emulsion under similar previous conditions of
20,000 rpm mixing speed, 30 minutes of mixing time, and several surfactant
402 M. T. Ghannam and M. Y. E. Selim
(a)
Figure 3a. Stability prole of 30% W/D emulsion for different mixing time.
(b)
Figure 3b. Stability prole of 30% W/D emulsion for different surfactant concentra-
tion.
W/D Emulsion Stability Behavior 403
concentrations ranging from 0.25 to 5%. In the presence of 0.25% surfactant,
the emulsion was only stable for 1 hour, and then the percentage of water
separated increased gradually until 45% of the water was separated within
1 week. As mentioned previously, the addition of up to 2% surfactant con-
centration signicantly enhanced the stability performance. In the presence
of 2% surfactant, the 40% emulsion was stable for 4 hours and only 10% of
the water separated within 1 week. Adding more surfactant will change its
behavior and negatively affect the emulsion stability due to the polydispersity
effect of surfactant micelles formed at the water-diesel interface as noted in
Figure 4 for the 3% and 5% surfactant behaviors (Wasa, Nikolou, and Ainetti,
2004). This means that there is an optimum concentration of added surfactant
to enhance the stability behavior for W/D emulsions.
We carried out the emulsication process at room temperature using
a homogenizing unit to prepare a stable W/D emulsion to produce a low
cost and stable emulsion for at least 1 week. The formation of the W/D
emulsion is signicantly affected by the method used to mix the emulsion
components together. We recommend from experience that the water phase
should be added gradually into the mixing material of the diesel phase with an
emulsier. The surfactants role is complicated but crucial. For the surfactant
to be effective, it must be transported to the W/D interface where it is
absorbed and forms a surface layer. This migration is accelerated by intense
mixing. This mechanism produces a stable emulsion of the water droplet
phase within the continuous diesel phase (i.e., W/D emulsion). The stability
of water droplets within the emulsion depends on two competitive factors:
(a) the presence of the emulsier material around all the droplets surfaces to
stabilize the W/D emulsion and (b) the droplets coalescence mechanism
Figure 4. Effect of surfactant concentration on 40% W/D emulsion.
404 M. T. Ghannam and M. Y. E. Selim
to destabilize the emulsion. For the destabilization of W/D emulsion to
occur, the water droplet phase goes through several steps before the complete
separation of the water phase from the W/D emulsion. If the repulsive forces
between droplets are too weak, droplets move to each other. The single
droplets are replaced by multiple droplets separated by a thin lm (i.e.,
occulation process). The thin-lm thickness is reduced by the Van der Waals
attraction forces. Once the lm thickness reduces to a critical value, the lm
breaks suddenly to form a larger droplet (i.e., coalescence process). Once the
coalescence process has started, the water droplets will settle to the bottom
due to the density difference (i.e., sedimentation process). Both occulation
and coalescence processes lead to larger droplets until the complete phase of
separation occurs (Sherman, 1983).
Water Droplet Distribution
Using the computer image analyzer system, we investigated several W/D
emulsions with different water concentrations. Among numerous tested sam-
ples in terms of stability behavior, we decided to investigate the best stable
samples for each water concentration and tested six samples of W/D emul-
sions over the water concentration range of 10 to 50%. Table 2 shows the
preparation conditions and stability period for each sample.
For the 10/90 W/D emulsion sample, Table 2 shows that the preparation
conditions of 30,000 revolutions and 0.2 wt% surfactant were enough to
produce stable emulsion for 4 weeks. For a higher concentration of wa-
ter content, the total number of revolutions and/or surfactant concentration
should be increased signicantly to obtain a stable emulsion. Stability can
be improved even more through the conditions that avoid the coalescence
mechanism of small water droplets, whereas coalescence will produce larger
water droplets and eventually lead to an unstable W/D emulsion. The smaller
the droplets are, the more intense the agitation should be to disrupt them.
The water droplet distribution analysis for each investigated emulsion is
Table 2. Preparing conditions for stable W/D emulsions
W/D
Emulsion
Speed
rpm
Mixing time
minutes
Surfactant
%
Stable
period
10/90 15,000 2 0.2 4 weeks
20/80 15,000 10 0.2 10 days
20/80 15,000 10 1.0 4 weeks
30/70 20,000 30 1.7 1 week
40/60 20,000 30 2.0 4 hours
50/50 20,000 30 2.0 1 hour
W/D Emulsion Stability Behavior 405
Figure 5. Droplet diameter distribution for different emulsions.
displayed in Figure 5. It shows that the water droplet distribution decreased
gradually over the water concentration range of 10 to 30% because of the
signicant increase in the total number of mixing revolutions and therefore
produced smaller diameters of water droplets. Figure 5 shows that if there is
any further addition of water concentration beyond 30%, the water droplets
distribution slightly increases, producing larger diameters of water droplets.
This change can be attributed to the use of the same total number of mixing
revolutions for the 30%, 40% and 50% water concentrations as listed in
Table 2. The Sautor mean droplet diameter (D
sv
; equation 2) was used
to measure the average diameter of the water droplets for each emulsion
(Sherman, 1983; Table 3). The size distribution of water droplets within
the W/D emulsion samples listed in Table 2 was observed by the com-
puter image analyzer system. Figure 6 shows typical examples of water
droplet distribution within different W/D emulsions for different water con-
centrations.
D
sv
D
X
N
i
D
3
i
.
X
N
i
D
2
i
(2)
in which N
i
is the number of water droplets and D
i
is the droplet diameter.
Table 3. Average diameter of water droplets
W/D Emulsion 10/90 20/80 30/70 40/60 50/50
D
sv
, m 4.24 3.71 1.70 2.25 2.62
406 M. T. Ghannam and M. Y. E. Selim
Figure 6. Photomicrographs of 10/90, 30/70, and 50/50 emulsions.
W/D Emulsion Stability Behavior 407
Table 4. Density and surface tension at 20
C
W/D
Emulsion
Density,
kg/m
3
Surface tension,
mN/m
10/90 835 44.0
20/80 846 42.5
30/70 875.2 41.0
Emulsion Physical Properties
It is important to investigate the physical properties of W/D emulsions to
assess the role of the water presence within the diesel emulsions and the
interaction between the water droplet phase and the diesel continuous phase.
These properties are density, viscosity, and surface tension. Table 4 reports
the density and surface tension for the stable tested emulsions at 20
C.
Because the emulsion preparation, storage, and transportation can be
carried out at different temperatures, it is important to study the effect of
temperature on the density and viscosity of the stable W/D emulsions. The
effect of temperature on emulsion density is displayed in Figure 7a over the
temperature range of 20
C to 60
C
to 60
C for different
stable emulsions. All the tested emulsions showed strong non-Newtonian
behavior (called yield-pseudoplastic) of shear thinning with a yield stress.
Figure 7b shows a strong viscosity reduction with a shear rate for all tested
emulsions at 20
C to 60
C.
The Herschel-Bulkley model (equation 3) can be used to model the
ow behavior (Chhabra and Richardson, 1999) in which
o
is the appar-
ent yield stress in Pa, P is the corresponding shear rate in s
1
, m is the
consistency index Pas
n
, and n is the ow behavior index that is dimen-
sionless. Modeling analysis according to equation 3 is carried out for all
the stable emulsions at different temperatures from 20
C to 60
C. Table 6
shows the yield stress values, consistency index (m), and ow behavior
index (n), respectively. It is well known that the mechanical properties of
structured liquids modify strongly over a narrow low range of stress level.
Below this stress level, the material deforms elastically with nite rigidity
to show solid-like behavior. Above this stress level, the material shows con-
tinuous deformation to observe viscous liquid-like behavior. The stress level
at this transition stage is known as apparent yield stress. The yield stress
directly inuences the initiation of an emulsion ow from a container by
pumping the emulsion into a transportation pipeline. The values of
o
, m,
and n are signicantly dependent on emulsion composition and temperature
(Table 6).
D
o
CmP
n
(3)
The modeling analysis for the yield stress .
o
), consistency index .m/; and
ow behavior index .n/ are carried out versus temperature according to equa-
tions 4, 5, and 6, respectively. The tting analysis estimates the coefcients
A and B for each stable emulsion for yield stress, consistency index, and
ow behavior index. The modeling analysis was carried out for all the stable
Table 6. Fitting parameters of equation 3
10/90 Emulsion 20/80 Emulsion 30/70 Emulsion
Temperature,
C
o
m n
o
m n
o
m n
20 15.01 10.76 0.41 13.3 5.39 0.46 3.17 1.15 0.58
30 3.42 8.42 0.40 6.32 1.48 0.52 3.44 0.65 0.63
40 3.64 4.84 0.39 5.62 1.37 0.53 3.29 0.44 0.68
50 5.19 1.06 0.55 3.02 0.28 0.72
60 5.04 0.65 0.62 2.59 0.38 0.68
410 M. T. Ghannam and M. Y. E. Selim
Table 7. Modeling analysis for
o
, m, and n
W/D
Emulsion A
1
B
1
A
2
B
2
A
3
B
3
10/90 141.9 0.113 22.60 0.036 0.483 0.055
20/80 22.1 0.031 25.83 0.081 0.221 0.243
30/70 3.9 3.17 2.51 0.041 0.348 0.176
emulsions with an average regression factor of 0.95 (Table 7).
o
D A
1
exp.B
1
T / (4)
m D A
2
exp.B
2
T / (5)
n D A
3
T
B3
(6)
CONCLUSIONS
The study of the emulsied W/D emulsion showed the following points:
1. The presence of surfactant is crucial to stabilize the W/D emulsions for a
reasonable period of time.
2. In the presence of 0.2% surfactant, 15,000 rpm, and 2 minutes of mixing
time, the 10% W/D and 20% W/D emulsions remain stable for 4 weeks
and 10 days, respectively. For higher water concentrations, however, the
stability period is limited to 5 hours.
3. To stabilize higher water concentration (i.e., >20% W/D emulsion), it is
required to increase the surfactant concentration and the total number of
mixing revolutions.
4. Due to the polydispersity effect of added surfactant, the optimum surfac-
tant concentration for 40% W/D emulsion is about 2% surfactant.
5. Water droplet distribution decreases gradually with water concentration
for 10%, 20%, and 30% W/D emulsions due to the increase of the total
number of mixing revolutions.
6. Water droplet distribution increases gradually with water concentration for
30%, 40%, and 50% W/D emulsions due to the application of the same
total number of mixing revolutions.
7. The density of W/D emulsion increases with water content. The temper-
ature has signicant inuence to lower the density of W/D emulsion.
8. All stable emulsions showed yield-pseudoplastic behavior. Strong viscosity
reduction with shear rate is reported for all stable emulsions. The Herschel-
Bulkley model can be used to simulate the ow behavior of stable W/D
emulsions.
W/D Emulsion Stability Behavior 411
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