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IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 489
STABILIZATION AND CHARACTERIZATION OF HEAVY CRUDE OIL-
IN-WATER (O/W) EMULSIONS
Liyana M.S1
, Abdurahman H. Nour2
, Rizauddin D3
, Gimbun J4
, Nurdin S5
Abstract
There has been much interest in alternative to transport viscous crude oil from reservoir which is much more abundant than
conventional oil. There are many authors hard to find the stable of oil-in-water (o/w) emulsion condition which has been considered
as critical analysis. In order to reduce the viscosity, the heavy oil is required to modify for reducing their viscosity. Applying diluent
and forming o/w emulsion are the selected as alternative for reducing viscosity. The purpose for this investigation is to study factors
that influencing stability and viscosity of o/w emulsion. From the observation, o/w emulsions reduced almost six (6) times less than
original heavy oil. However, the addition of 40% of light oil reduced oil viscosity from 478.10 mPa.sto 113.40 mPa.s. Thus, the
knowledge and understanding factors that influencing the stability and viscosity of o/w emulsion is important due to avoiding of
occurring phase inversion phenomena.
Keywords: Crude oil, Stability, Heavy oil, Viscosity, Emulsion, Shear Rate, Shear Stress.
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1. INTRODUCTION
Demanding for crude oil will be increase in the future and this
will exert pressure on oil exploration companies throughout
the whole world. Indeed, there are various companies that are
still focusing on the oil reservoir within their boundaries in the
hopes that they might develop and increase their economic
growth in the future. The important of crude oil has been
focused by developer oil and gas industry. The pipeline
transportation by using water and present of surfactant to form
oil-in-water emulsion that has been suggested by authors (Zaki
1997; Azodi and Solaimany, 2013; Ashrafizadeh and Kamran,
2010). However, the difficulty to find stability between oil and
water which is require knowledge in order to reduce the heavy
oil viscosity(Crandall and Wise, 1984; Gillies and Shook,
1992; Hardy et al., 1989; Zakin et al., 1979).Besides, adding
light oil as diluent also promotes in reducing viscosity of
heavy oil. Unfortunately, the availability of diluent reserves at
the production site indicates major difficulties to obtain.
From literature survey, the crude oil world’s which has been
discover deep in the wellhead is associated with water which
is produced as water-in-oil (w/o) emulsion (Steinhauff, 1962;
Alvarado and Marsden, 1979). This fact are also mention by
Abdurahman et al., (2007) where the hydrocarbon oils are
normally present with water or is injected as steam to
stimulate oil production. Thus, w/o emulsion is consider as
normal emulsion while o/w emulsions indicate reverse
emulsion in oil and gas industries.
Shiffert et al., (1984) reported there are three (3) requirements
to form or prepare an emulsion; 1) two immiscible liquid, 2)
enough agitation to disperse one liquid into small drops, 3) the
present of surfactant to stabilize the dispersed drops. The
applying of homogenizer forces is to break the dispersed
liquid up into many small droplets. According to Dukhin and
Goetz (2005), an emulsion are depending on the several
factors including liquid properties, surfactant content,
temperature, and mixing conditions during preparing the
emulsion. In this investigation, there are several variables that
influencing preparation of a stable heavy crude o/w emulsion
such as, mixing speed, duration time mixing, concentration
surfactant, and volume fraction of oil and water. Basically, an
emulsion can be categorized into two (2) major phases which
is classified as o/w and w/o. The term of o/w emulsion refer to
oil as discontinues phase being dispersed in continuous water
phase. While term w/o emulsion refer to water as discontinues
phase being dispersed in continuous oil phase. In other words,
the continuous phase is also referred as the dispersion
medium, while the liquid in form of droplets are called as the
dispersed phase. The stability of emulsion is an essential
valuable knowledge for both academic and industrial points of
views. The term of “stability” is defined as the combination
between two immiscible liquid which are not separated for
long period time and also reduced amount of droplet to be
coalescence. Other authors determine the stable emulsions as
water droplets are not settle out from oil phase due to their
small size and surface tension (Stewart and Arnold, 2009).
Besides, emulsions stability is verify by analysis of their drop
size, rheological properties, and other factor that effecting
stability (Mandal, et al., 2010). This factor has been explained
by Mandal et al. (2010) where the stability is dependents on
the stirring speed and time during formation. Other than that,
Murray et al. (2009) reported the stability of emulsion is effect
from small droplet size which has strong interfacial film
around oil droplets. In addition, the mixed of oil and water
will easily break and form clearly double layer because of
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 490
different density between oil and water. Besides, Stewart and
Arnold (2009) stated that the most stable emulsions often
required additional special treatment which is involved the
sufficient agitation to disperse the discontinuous phase into
continuous phase and the present of surfactant.
2. EXPERIMENTAL PROCEDURE
2.1 Sample Preparation
Two types of crude oil samples were used in this study which
has been obtained heavy oil from PETRONAS Refinery
Melaka and blended with forty per cent (40%) of light crude
oil from PETRONAS Kerteh. In order to investigate the most
effective surfactant, five (5) different types of emulsifiers
willused in this study, namely SDDS, Triton X-100, Span 83,
Tween 80, and Coco-Amide. The oil ratio was varied from
50%-70% by total volume. The surfactant concentration is
varied from 0.5-1% and homogenized at varied mixing speed
from 10,000-15,000 rpm. The oil as dispersed phase was
added slowly in water (continuous phase) at 5-10 min. On the
other hand, the rheological measurements for all samples were
carried out by using Brookfield Rotational Digital Viscometer
with UL adaptor and spindles 31 for measuring viscosity,
shear rate and shear stress. Figure 1 demonstrated the set-up
experiment for this investigation.
Fig 1: Overview experiment set-up
Table 1 shows the summarizing physical properties for both
types of crude oil. Meanwhile Table 2 displayed the chemical
properties according to ASTM D-2007 by applying Open
Column Chromatography method.
Table 1
Analysis Heavy
Oil
Blend
Oil
Physical Properties
Density at 25 °C (g/cm3
) a
0.9372 0.8977
API gravity (°API ) b
19.48 26.12
Apparent viscosity at 25 °C, (mPas) c
478.1 113.4
Surface tension at 25 °C (mN/m) d
33.2 25.7
Interfacial tension at 25 °C (mN/m) e
37.7 18.73
Pour Point (0
C) f
-12 15
Cloud Point (0
C) g
-8.95 20.6
a. Determined by using MicromeriticsPycnometer device in
the range 0.9–1.0 kg/m3.
b Calculated according to the relation API = (141.5/Specific
Gravity) - 131.5
c. Determined by using Brookfield Rotational Digital
Viscometer.
d.&e.Measured using SEO DST30 Tensiometer by applying
the du Nuoy ring method.
f&g. Determined by using pour point and clould point device
Table 2
Analysis Heavy
Oil
Blend
Oil
Chemical Properties (wt%)
Asphaltenes 16.54 10.32
Resin 18.31 7.58
Aromatics 18.63 49.71
Saturates 46.52 32.39
3. EXPERIMENTALRESULTS
3.1 Comparison between Influence Light Oil as
Diluent Alternative and Oil-in-Water Emulsion
Technique
This interesting idea was apply since only 10-30 % of water
used to produce emulsion compared to adding 40% light oil.
The diluent required to be recovered at the end of pipe and
need to be pumped back to the field hundreds of miles away
(Salager et al., 2001). These diluent usually demand high cost
and more valuable due to hydrocarbon fractions or light crude
oils would be sacrificed in the process (Salager et al., 2001).
O/W emulsion can be generating a much better result rather
than dilution as illustrated in Figure 2. The low cost
commodity is an advantage of this technique. The water is
used to reduce viscosity heavy oil by present of surfactant as
active agent to produce stable o/w emulsion (Langevin et al.,
2004). The o/w emulsion has been proof to reduce viscosity
and make it easier delivering oil during transportation. Hence,
it is necessary to develop further research and built knowledge
about characteristic of crude oil.
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 491
Fig 2: Viscosity as a function of temperature for a heavy crude
oil, its mixture with 40% diluent, and its emulsion with 30 %
water content.
3.2 Stability of O/W Emulsion
The stability between oil and water phase are very important
during pipeline transportation.The highest percentage of
stability is selected as the suitable surfactant to form the most
stable o/w emulsion. From Figure 3, it’s clearly shown that
Triton X-100 is the best surfactant to form o/w emulsion.
Heavy oil is stable by present of Triton X-100 where the
separation indicates less than 3 mL after 14 days. Besides that,
Table 3 also demonstrated Triton X-100 promotes highest
stability with 94%. Octyl phenol ethoxylate (Triton X-100) is
a hydrophilic group where it has a water loving portion with
13.5 value of HLB.
Fig 3: Effect of surfactant type’s on the stability heavy o/w
emulsion.
Table 3: Stability for different types of surfactant
Types Surfactant Stability
Heavy o/w
emulsion
Triton X-100 94%
Span 83 88%
Tween 80 86%
SDDS 85%
Coca-Amide 84%
The stability of emulsion is evaluated according to less
amount of water separated. In other word, the high stability of
emulsion indicates the minimum percentage of water
separation from o/w emulsion. The stability of emulsion was
calculated by using Equation 1 as below. This equation is
generated by Abdurahman et al. (2012).
Emulsion Stability= 1 −
water separated (%)
water content (%)
100 (1)
The second highest percentage of stability is Span 83 (88 %
Heavy) followed by Tween 80 (86% Heavy), Coco-Amide
(85% Heavy), and SDDS (84% Heavy). Sodium dedocyl
sulphate (SDS) from anionic group obtained the lowest
stability compared to other non-ionic group. Besides, non-
ionic surfactants can be impart the interactive particles with
the steric stabilization mechanism, while anionic surfactants
can be provide repulsive force between similarly charged
electric double layers to the particles (Chen et al., 1997). The
non-ionic surfactant was covered well the thin film droplet to
provide less time the emulsion to be coalesce. Therefore, non-
ionic surfactant is suitable to use as stabilizer for o/w
emulsion.
Generally, non-ionic surfactants such as Triton X-100 indicate
a good selection as emulsifiers because they are not afflicted
by the salinity of the water, low cost, and not change the oil
properties (Rivas et al., 1998). Triton X-100 is the most
soluble in water and miscible in most polar organic solvents
and aromatic hydrocarbons (Hait and Moulik, 2001). Besides,
it is suitable to form o/w emulsion and commercially available
in the industry.
3.3 Influence of Surfactant Concentration on
Stability and Viscosity of O/W Emulsion
Surfactant concentration promotes significant factors that
influence the stability and viscosity of emulsions. An effective
technique to reduce the viscosity of heavy oil is the formation
of o/w emulsions with the influence of surfactant agents
(Martinez-Palou et al. 2011). Other than that, the surfactant
concentration strongly influence emulsion stability (Ostberg et
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 492
al., 1995). As it can be observed from Figure 4 and Figure 5
the increasing of actual emulsifier’s concentration in the liquid
phase will increases emulsion stability and viscosity,
respectively
Fig 4: Effect of influence surfactant concentration on the
stability of heavy o/w emulsion.
Fig 5: Effect of influence surfactant concentration on the
viscosity ofheavy o/w emulsion.
From the graph, emulsion stability is increased as surfactant
concentration increased from 0.5% to 0.9%. This observation
is explained by Zaki (1997) where the addition of emulsifiers
demonstrated in an increase in the amount of emulsifier
molecules adsorbed at the oil/water interface. Meanwhile, the
viscosity has significantly increased when the concentration of
emulsifier increase. Eirong and Lempe (2006) found that the
addition of surfactant concentration in the emulsion will
increases along the viscosity of the emulsion. The o/w
emulsion becomes more stable by increasing the concentration
of surfactant. The high amount of surfactant promotes each
droplet was covered well to avoid the droplets from coalesce.
The adsorbed emulsifier between oil and water molecules
because of their non-ionic nature contribute a steric obstacle to
droplet oil (dispersed phase) to be coalescence (Singh, 1994;
Singh and Pandey, 1991). Furthermore, Ashrafizadeh and
Kamran, (2010) reported the increasing of emulsifiers
concentration are effect an increments of obstacle between the
two phases and promotes a good distribution of oil droplets
(dispersed phase) in the water (continuous phase).
3.4 Influence of Mixing Speed and Duration Time of
Homogenizer on Stability and Viscosity of O/W
Emulsion
The influence of mixing speed on the viscosity and stability of
o/w emulsions has been thoroughly studied. The stability of
heavy o/w emulsions have been investigated at different
mixing speeds of 10,000, 12,000 and 15,000 rpm. Results are
shown in Figure 6 and Figure 7 demonstrated relationship
speed homogenizer with stability and viscosity for heavy o/w
emulsions.
Fig 6: Influence of mixing speed on the stability of heavyand
blend o/w emulsion.
Fig 7: Influence of mixing speed on the viscosity of heavy o/w
emulsion.
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 493
From the graph illustrated the increasing mixing speed was
slightly increased the stability and viscosity. This fact is
agreed by Zaki (1997) where the increasing the mixing speed
results in an increase in the viscosity of the emulsion.
Ashrafizadeh and Kamran, (2010) also agree with the above
statement where increasing speed of mixing has a similar
effect on the emulsions quality. The stability at 70% oil
content showed 100% stable when 15,000 rpm apply during
preparing o/w emulsion. The increasing of mixing speed
promotes decreasing in the oil droplet size and increasing the
viscosity of the emulsion.However, 15,000 rpm is considered
very high speed compared to 10,000 rpm. From the
observation, the emulsion will require more than 4% of
surfactant when mixing speed below than 2,000 rpm was
applied and also need more than 20 min to agitate the
emulsion. From this condition, the o/w emulsion exhibit low
quality in term of stability. Ashrafizadeh and Kamran (2010)
has observed when applying mixing speed lower than 3,000
rpm and mixing time less than 10 min, would significantly
reduce the quality of the emulsions.
From the observation, there is no separation water or in other
word, the emulsion show 100% stable for 70% oil content.
Besides, 10K rpm is considered as high speed of mixing and
homogenizing for more than 8 min are not efficient because
the emulsion become more viscous and creamy. These
observations are explained by highly speed homogenized and
a longer mixing time will lead an o/w emulsion facing the
phase inversion. The observation has been shown that the
efficient time for high speed homogenizing at 10,000 rpm is
required maximum time at 7 min agitation for 0.9% of Triton
X-100. However, the concentration at 0.5% of Triton X-100
require less time of mixing because after 4 min agitated, the
emulsion change to w/o emulsion.
3.5 Effect of Temperature on Stability and Viscosity
of O/W Emulsion.
Temperature is another factors that is promotes strong
influence to reduce of heavy oil’s viscosity (Abdurahman et
al., 2012; Martínez-Palou et al.; 2011; Ilia and Abdurahman,
2010). Besides, the insulating of the pipeline is usually only a
solution for a small distance due to the temperature losses
reduction (Martínez-Palou et al., 2011). There are four (4)
different studied mixing temperatures, namely, 27, 60, 90, and
96°C while the other parameters are kept constant.Figure 8
shows a plot of the influence mixing speed on the viscosity of
o/w emulsions.
Fig 8: Influence of temperature on the viscosity of heavy and
blend o/w emulsion
It is clear from this plot that the viscosity of the emulsion is
increased as the temperature is raised (Zaki, 1997; Sanchez
and Zakin, 1994; Abdurahman et al., 2012). The increasing of
temperature promotes increasing the interfacial tension
between oil and water. Consequently, the increase of internal
energy of the molecules may increase the pressure required to
induce the interfacial film thinning, and eventually reduces the
coalescence time (Isaaka et al., 2010). As viscosity decrease
with high temperature, the o/w emulsions are available to
transport via pipeline.As been discussed previously, the
present of surface active agent promotes an increasing of
stability and viscosity of the emulsions. However, the
solubility of the surfactant normally invert when temperature
changes, the stability of emulsion also change. The increasing
of temperature cause the flow molecules through the interfaces
also increased resulting in a decrease in emulsion stability (Ilia
and Abdurahman, 2010). These flow molecules correlated
with viscosity where the increasing temperature results in
decreasing the viscosity. AccordingStoke’s Law theory, the
velocity is increase as viscosity decreased. Furthermore, Ilia
and Abdurahman (2010) found that the viscosity is very
sensitive to temperature due to the high temperature promotes
to reduce emulsion stability.
3.7 Oil Droplet Measurement
The droplet size of an emulsion is important variables which
are affecting the colloidal stability and rheological properties
such as the flow and deformations of the emulsion (Han et al.,
2011). The droplet size distribution for the emulsions was
determined as a function of different mixing speeds and
concentration of surfactant using Carl Zeiss research
microscope equipped with the digital camera and AxioVission
AC image analysis software. The average of droplet size
distribution of emulsion is measured by taking randomly,
approximately eight to ten different droplet size images. The
influence of average droplet size emulsions on the mixing
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 494
speed and emulsifier concentration are illustrated in Figure 9
and Figure 10. From both figure, it is clear shown that the
average droplet size distribution of the emulsions decreases as
the speed of homogenizer and concentration emulsifier is
increased.
Fig 9: Influence of mixing speed on the average droplet size
of heavy o/w emulsion
Fig 10: Influence of concentration on the average droplet size
of heavy o/w emulsion
This observation has been explained by increasing mixing
speed and surfactant concentration will be reducing to droplet
oil size. The increasing the surfactant concentration will
increase an amount of obstacle between two phases to be
separate and improved the distribution of dispersed droplets in
the continuous phase (Ashrafizadeh and Kamran, 2010). This
findings are also agreed with some authors where the adsorbed
molecules of surfactant provide a strong barrier of oil droplet
to be the coalescence (Singh and Pandey, 1991; Singh, 1994).
Besides, the high surfactant concentration provide well
protection to each droplet surface, thus the uncovered droplet
surface area with water (continuous phase) is
thermodynamically unfavourable (Huda, 2011). The increment
of volume surfactant in the emulsion would reduce the
interfacial tension which promotes the breakage of droplets
into smaller ones and the interaction between particles is
increases. Consequently, the droplet between oil and water
become more tight relation and hard to break due to high
mixing speed and present of high amount of surfactant. At the
same time, the increasing mixing speed and mixing time also
could cause small droplet size which is finally increase the
stability of the emulsion (Ashrafizadeh and Kamran, 2010).
Parkinson et al. (1970) considered the influence of droplet size
distribution on the stability and viscosity of the emulsion. This
fact are already discussed by Azodiand Solaimany(2013) and
Abdurahman et al., (2012) where the increasing of surfactant
concentration and mixing speed will reduces average oil
droplets size leading to an increase of the viscosity of o/w
emulsion. The other author also agree by the decreasing of oil
droplets size (dispersed phase) results in a slight increase in
the viscosity of the emulsions (Stachurski and MichaŁek,
1996; Zaki, 1997; Pal et al, 1992). This observation is
explained by an increase in the mixing speed produced the
smaller size of oil droplets, thus influence the increasing of
viscosity (Pal et al., 1992; Briceno et al. 2001; Zaki, 1997).
The application of homogenizer may cause the formation of
oil droplets having a diameter less than 10 μm. According to
the droplet result, macro-emulsion and micro-emulsion (2.9 –
0.08 μm) had successfully applied by homogenizer
(10,000rpm-15,000rpm). Amorim (2007) also agree by
applying homogenizer are produced small size and stabilized
the emulsion. However, the droplet size have more than 1.2
µm are found as unstable emulsion due to coalesces process
are easy to occur (Jafari et al., 2008).
CONCLUSIONS
According to the result, it can be concluded that, o/w emulsion
influence various factor in order to find the stabilize condition.
This is due to the physical and chemical properties of type’s
crude oil which can beaffecting especially need to consider on
phase inversion phenomena. The less water separate indicate
the most stable o/w emulsion. Applying homogenizer proof
the droplet become smallest and displayed tight relation
between oil and water.
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Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 495
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Stabilization and characterization of heavy crude oil in-water

  • 1. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 489 STABILIZATION AND CHARACTERIZATION OF HEAVY CRUDE OIL- IN-WATER (O/W) EMULSIONS Liyana M.S1 , Abdurahman H. Nour2 , Rizauddin D3 , Gimbun J4 , Nurdin S5 Abstract There has been much interest in alternative to transport viscous crude oil from reservoir which is much more abundant than conventional oil. There are many authors hard to find the stable of oil-in-water (o/w) emulsion condition which has been considered as critical analysis. In order to reduce the viscosity, the heavy oil is required to modify for reducing their viscosity. Applying diluent and forming o/w emulsion are the selected as alternative for reducing viscosity. The purpose for this investigation is to study factors that influencing stability and viscosity of o/w emulsion. From the observation, o/w emulsions reduced almost six (6) times less than original heavy oil. However, the addition of 40% of light oil reduced oil viscosity from 478.10 mPa.sto 113.40 mPa.s. Thus, the knowledge and understanding factors that influencing the stability and viscosity of o/w emulsion is important due to avoiding of occurring phase inversion phenomena. Keywords: Crude oil, Stability, Heavy oil, Viscosity, Emulsion, Shear Rate, Shear Stress. ---------------------------------------------------------------------***--------------------------------------------------------------------- 1. INTRODUCTION Demanding for crude oil will be increase in the future and this will exert pressure on oil exploration companies throughout the whole world. Indeed, there are various companies that are still focusing on the oil reservoir within their boundaries in the hopes that they might develop and increase their economic growth in the future. The important of crude oil has been focused by developer oil and gas industry. The pipeline transportation by using water and present of surfactant to form oil-in-water emulsion that has been suggested by authors (Zaki 1997; Azodi and Solaimany, 2013; Ashrafizadeh and Kamran, 2010). However, the difficulty to find stability between oil and water which is require knowledge in order to reduce the heavy oil viscosity(Crandall and Wise, 1984; Gillies and Shook, 1992; Hardy et al., 1989; Zakin et al., 1979).Besides, adding light oil as diluent also promotes in reducing viscosity of heavy oil. Unfortunately, the availability of diluent reserves at the production site indicates major difficulties to obtain. From literature survey, the crude oil world’s which has been discover deep in the wellhead is associated with water which is produced as water-in-oil (w/o) emulsion (Steinhauff, 1962; Alvarado and Marsden, 1979). This fact are also mention by Abdurahman et al., (2007) where the hydrocarbon oils are normally present with water or is injected as steam to stimulate oil production. Thus, w/o emulsion is consider as normal emulsion while o/w emulsions indicate reverse emulsion in oil and gas industries. Shiffert et al., (1984) reported there are three (3) requirements to form or prepare an emulsion; 1) two immiscible liquid, 2) enough agitation to disperse one liquid into small drops, 3) the present of surfactant to stabilize the dispersed drops. The applying of homogenizer forces is to break the dispersed liquid up into many small droplets. According to Dukhin and Goetz (2005), an emulsion are depending on the several factors including liquid properties, surfactant content, temperature, and mixing conditions during preparing the emulsion. In this investigation, there are several variables that influencing preparation of a stable heavy crude o/w emulsion such as, mixing speed, duration time mixing, concentration surfactant, and volume fraction of oil and water. Basically, an emulsion can be categorized into two (2) major phases which is classified as o/w and w/o. The term of o/w emulsion refer to oil as discontinues phase being dispersed in continuous water phase. While term w/o emulsion refer to water as discontinues phase being dispersed in continuous oil phase. In other words, the continuous phase is also referred as the dispersion medium, while the liquid in form of droplets are called as the dispersed phase. The stability of emulsion is an essential valuable knowledge for both academic and industrial points of views. The term of “stability” is defined as the combination between two immiscible liquid which are not separated for long period time and also reduced amount of droplet to be coalescence. Other authors determine the stable emulsions as water droplets are not settle out from oil phase due to their small size and surface tension (Stewart and Arnold, 2009). Besides, emulsions stability is verify by analysis of their drop size, rheological properties, and other factor that effecting stability (Mandal, et al., 2010). This factor has been explained by Mandal et al. (2010) where the stability is dependents on the stirring speed and time during formation. Other than that, Murray et al. (2009) reported the stability of emulsion is effect from small droplet size which has strong interfacial film around oil droplets. In addition, the mixed of oil and water will easily break and form clearly double layer because of
  • 2. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 490 different density between oil and water. Besides, Stewart and Arnold (2009) stated that the most stable emulsions often required additional special treatment which is involved the sufficient agitation to disperse the discontinuous phase into continuous phase and the present of surfactant. 2. EXPERIMENTAL PROCEDURE 2.1 Sample Preparation Two types of crude oil samples were used in this study which has been obtained heavy oil from PETRONAS Refinery Melaka and blended with forty per cent (40%) of light crude oil from PETRONAS Kerteh. In order to investigate the most effective surfactant, five (5) different types of emulsifiers willused in this study, namely SDDS, Triton X-100, Span 83, Tween 80, and Coco-Amide. The oil ratio was varied from 50%-70% by total volume. The surfactant concentration is varied from 0.5-1% and homogenized at varied mixing speed from 10,000-15,000 rpm. The oil as dispersed phase was added slowly in water (continuous phase) at 5-10 min. On the other hand, the rheological measurements for all samples were carried out by using Brookfield Rotational Digital Viscometer with UL adaptor and spindles 31 for measuring viscosity, shear rate and shear stress. Figure 1 demonstrated the set-up experiment for this investigation. Fig 1: Overview experiment set-up Table 1 shows the summarizing physical properties for both types of crude oil. Meanwhile Table 2 displayed the chemical properties according to ASTM D-2007 by applying Open Column Chromatography method. Table 1 Analysis Heavy Oil Blend Oil Physical Properties Density at 25 °C (g/cm3 ) a 0.9372 0.8977 API gravity (°API ) b 19.48 26.12 Apparent viscosity at 25 °C, (mPas) c 478.1 113.4 Surface tension at 25 °C (mN/m) d 33.2 25.7 Interfacial tension at 25 °C (mN/m) e 37.7 18.73 Pour Point (0 C) f -12 15 Cloud Point (0 C) g -8.95 20.6 a. Determined by using MicromeriticsPycnometer device in the range 0.9–1.0 kg/m3. b Calculated according to the relation API = (141.5/Specific Gravity) - 131.5 c. Determined by using Brookfield Rotational Digital Viscometer. d.&e.Measured using SEO DST30 Tensiometer by applying the du Nuoy ring method. f&g. Determined by using pour point and clould point device Table 2 Analysis Heavy Oil Blend Oil Chemical Properties (wt%) Asphaltenes 16.54 10.32 Resin 18.31 7.58 Aromatics 18.63 49.71 Saturates 46.52 32.39 3. EXPERIMENTALRESULTS 3.1 Comparison between Influence Light Oil as Diluent Alternative and Oil-in-Water Emulsion Technique This interesting idea was apply since only 10-30 % of water used to produce emulsion compared to adding 40% light oil. The diluent required to be recovered at the end of pipe and need to be pumped back to the field hundreds of miles away (Salager et al., 2001). These diluent usually demand high cost and more valuable due to hydrocarbon fractions or light crude oils would be sacrificed in the process (Salager et al., 2001). O/W emulsion can be generating a much better result rather than dilution as illustrated in Figure 2. The low cost commodity is an advantage of this technique. The water is used to reduce viscosity heavy oil by present of surfactant as active agent to produce stable o/w emulsion (Langevin et al., 2004). The o/w emulsion has been proof to reduce viscosity and make it easier delivering oil during transportation. Hence, it is necessary to develop further research and built knowledge about characteristic of crude oil.
  • 3. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 491 Fig 2: Viscosity as a function of temperature for a heavy crude oil, its mixture with 40% diluent, and its emulsion with 30 % water content. 3.2 Stability of O/W Emulsion The stability between oil and water phase are very important during pipeline transportation.The highest percentage of stability is selected as the suitable surfactant to form the most stable o/w emulsion. From Figure 3, it’s clearly shown that Triton X-100 is the best surfactant to form o/w emulsion. Heavy oil is stable by present of Triton X-100 where the separation indicates less than 3 mL after 14 days. Besides that, Table 3 also demonstrated Triton X-100 promotes highest stability with 94%. Octyl phenol ethoxylate (Triton X-100) is a hydrophilic group where it has a water loving portion with 13.5 value of HLB. Fig 3: Effect of surfactant type’s on the stability heavy o/w emulsion. Table 3: Stability for different types of surfactant Types Surfactant Stability Heavy o/w emulsion Triton X-100 94% Span 83 88% Tween 80 86% SDDS 85% Coca-Amide 84% The stability of emulsion is evaluated according to less amount of water separated. In other word, the high stability of emulsion indicates the minimum percentage of water separation from o/w emulsion. The stability of emulsion was calculated by using Equation 1 as below. This equation is generated by Abdurahman et al. (2012). Emulsion Stability= 1 − water separated (%) water content (%) 100 (1) The second highest percentage of stability is Span 83 (88 % Heavy) followed by Tween 80 (86% Heavy), Coco-Amide (85% Heavy), and SDDS (84% Heavy). Sodium dedocyl sulphate (SDS) from anionic group obtained the lowest stability compared to other non-ionic group. Besides, non- ionic surfactants can be impart the interactive particles with the steric stabilization mechanism, while anionic surfactants can be provide repulsive force between similarly charged electric double layers to the particles (Chen et al., 1997). The non-ionic surfactant was covered well the thin film droplet to provide less time the emulsion to be coalesce. Therefore, non- ionic surfactant is suitable to use as stabilizer for o/w emulsion. Generally, non-ionic surfactants such as Triton X-100 indicate a good selection as emulsifiers because they are not afflicted by the salinity of the water, low cost, and not change the oil properties (Rivas et al., 1998). Triton X-100 is the most soluble in water and miscible in most polar organic solvents and aromatic hydrocarbons (Hait and Moulik, 2001). Besides, it is suitable to form o/w emulsion and commercially available in the industry. 3.3 Influence of Surfactant Concentration on Stability and Viscosity of O/W Emulsion Surfactant concentration promotes significant factors that influence the stability and viscosity of emulsions. An effective technique to reduce the viscosity of heavy oil is the formation of o/w emulsions with the influence of surfactant agents (Martinez-Palou et al. 2011). Other than that, the surfactant concentration strongly influence emulsion stability (Ostberg et
  • 4. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 492 al., 1995). As it can be observed from Figure 4 and Figure 5 the increasing of actual emulsifier’s concentration in the liquid phase will increases emulsion stability and viscosity, respectively Fig 4: Effect of influence surfactant concentration on the stability of heavy o/w emulsion. Fig 5: Effect of influence surfactant concentration on the viscosity ofheavy o/w emulsion. From the graph, emulsion stability is increased as surfactant concentration increased from 0.5% to 0.9%. This observation is explained by Zaki (1997) where the addition of emulsifiers demonstrated in an increase in the amount of emulsifier molecules adsorbed at the oil/water interface. Meanwhile, the viscosity has significantly increased when the concentration of emulsifier increase. Eirong and Lempe (2006) found that the addition of surfactant concentration in the emulsion will increases along the viscosity of the emulsion. The o/w emulsion becomes more stable by increasing the concentration of surfactant. The high amount of surfactant promotes each droplet was covered well to avoid the droplets from coalesce. The adsorbed emulsifier between oil and water molecules because of their non-ionic nature contribute a steric obstacle to droplet oil (dispersed phase) to be coalescence (Singh, 1994; Singh and Pandey, 1991). Furthermore, Ashrafizadeh and Kamran, (2010) reported the increasing of emulsifiers concentration are effect an increments of obstacle between the two phases and promotes a good distribution of oil droplets (dispersed phase) in the water (continuous phase). 3.4 Influence of Mixing Speed and Duration Time of Homogenizer on Stability and Viscosity of O/W Emulsion The influence of mixing speed on the viscosity and stability of o/w emulsions has been thoroughly studied. The stability of heavy o/w emulsions have been investigated at different mixing speeds of 10,000, 12,000 and 15,000 rpm. Results are shown in Figure 6 and Figure 7 demonstrated relationship speed homogenizer with stability and viscosity for heavy o/w emulsions. Fig 6: Influence of mixing speed on the stability of heavyand blend o/w emulsion. Fig 7: Influence of mixing speed on the viscosity of heavy o/w emulsion.
  • 5. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 493 From the graph illustrated the increasing mixing speed was slightly increased the stability and viscosity. This fact is agreed by Zaki (1997) where the increasing the mixing speed results in an increase in the viscosity of the emulsion. Ashrafizadeh and Kamran, (2010) also agree with the above statement where increasing speed of mixing has a similar effect on the emulsions quality. The stability at 70% oil content showed 100% stable when 15,000 rpm apply during preparing o/w emulsion. The increasing of mixing speed promotes decreasing in the oil droplet size and increasing the viscosity of the emulsion.However, 15,000 rpm is considered very high speed compared to 10,000 rpm. From the observation, the emulsion will require more than 4% of surfactant when mixing speed below than 2,000 rpm was applied and also need more than 20 min to agitate the emulsion. From this condition, the o/w emulsion exhibit low quality in term of stability. Ashrafizadeh and Kamran (2010) has observed when applying mixing speed lower than 3,000 rpm and mixing time less than 10 min, would significantly reduce the quality of the emulsions. From the observation, there is no separation water or in other word, the emulsion show 100% stable for 70% oil content. Besides, 10K rpm is considered as high speed of mixing and homogenizing for more than 8 min are not efficient because the emulsion become more viscous and creamy. These observations are explained by highly speed homogenized and a longer mixing time will lead an o/w emulsion facing the phase inversion. The observation has been shown that the efficient time for high speed homogenizing at 10,000 rpm is required maximum time at 7 min agitation for 0.9% of Triton X-100. However, the concentration at 0.5% of Triton X-100 require less time of mixing because after 4 min agitated, the emulsion change to w/o emulsion. 3.5 Effect of Temperature on Stability and Viscosity of O/W Emulsion. Temperature is another factors that is promotes strong influence to reduce of heavy oil’s viscosity (Abdurahman et al., 2012; Martínez-Palou et al.; 2011; Ilia and Abdurahman, 2010). Besides, the insulating of the pipeline is usually only a solution for a small distance due to the temperature losses reduction (Martínez-Palou et al., 2011). There are four (4) different studied mixing temperatures, namely, 27, 60, 90, and 96°C while the other parameters are kept constant.Figure 8 shows a plot of the influence mixing speed on the viscosity of o/w emulsions. Fig 8: Influence of temperature on the viscosity of heavy and blend o/w emulsion It is clear from this plot that the viscosity of the emulsion is increased as the temperature is raised (Zaki, 1997; Sanchez and Zakin, 1994; Abdurahman et al., 2012). The increasing of temperature promotes increasing the interfacial tension between oil and water. Consequently, the increase of internal energy of the molecules may increase the pressure required to induce the interfacial film thinning, and eventually reduces the coalescence time (Isaaka et al., 2010). As viscosity decrease with high temperature, the o/w emulsions are available to transport via pipeline.As been discussed previously, the present of surface active agent promotes an increasing of stability and viscosity of the emulsions. However, the solubility of the surfactant normally invert when temperature changes, the stability of emulsion also change. The increasing of temperature cause the flow molecules through the interfaces also increased resulting in a decrease in emulsion stability (Ilia and Abdurahman, 2010). These flow molecules correlated with viscosity where the increasing temperature results in decreasing the viscosity. AccordingStoke’s Law theory, the velocity is increase as viscosity decreased. Furthermore, Ilia and Abdurahman (2010) found that the viscosity is very sensitive to temperature due to the high temperature promotes to reduce emulsion stability. 3.7 Oil Droplet Measurement The droplet size of an emulsion is important variables which are affecting the colloidal stability and rheological properties such as the flow and deformations of the emulsion (Han et al., 2011). The droplet size distribution for the emulsions was determined as a function of different mixing speeds and concentration of surfactant using Carl Zeiss research microscope equipped with the digital camera and AxioVission AC image analysis software. The average of droplet size distribution of emulsion is measured by taking randomly, approximately eight to ten different droplet size images. The influence of average droplet size emulsions on the mixing
  • 6. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 494 speed and emulsifier concentration are illustrated in Figure 9 and Figure 10. From both figure, it is clear shown that the average droplet size distribution of the emulsions decreases as the speed of homogenizer and concentration emulsifier is increased. Fig 9: Influence of mixing speed on the average droplet size of heavy o/w emulsion Fig 10: Influence of concentration on the average droplet size of heavy o/w emulsion This observation has been explained by increasing mixing speed and surfactant concentration will be reducing to droplet oil size. The increasing the surfactant concentration will increase an amount of obstacle between two phases to be separate and improved the distribution of dispersed droplets in the continuous phase (Ashrafizadeh and Kamran, 2010). This findings are also agreed with some authors where the adsorbed molecules of surfactant provide a strong barrier of oil droplet to be the coalescence (Singh and Pandey, 1991; Singh, 1994). Besides, the high surfactant concentration provide well protection to each droplet surface, thus the uncovered droplet surface area with water (continuous phase) is thermodynamically unfavourable (Huda, 2011). The increment of volume surfactant in the emulsion would reduce the interfacial tension which promotes the breakage of droplets into smaller ones and the interaction between particles is increases. Consequently, the droplet between oil and water become more tight relation and hard to break due to high mixing speed and present of high amount of surfactant. At the same time, the increasing mixing speed and mixing time also could cause small droplet size which is finally increase the stability of the emulsion (Ashrafizadeh and Kamran, 2010). Parkinson et al. (1970) considered the influence of droplet size distribution on the stability and viscosity of the emulsion. This fact are already discussed by Azodiand Solaimany(2013) and Abdurahman et al., (2012) where the increasing of surfactant concentration and mixing speed will reduces average oil droplets size leading to an increase of the viscosity of o/w emulsion. The other author also agree by the decreasing of oil droplets size (dispersed phase) results in a slight increase in the viscosity of the emulsions (Stachurski and MichaŁek, 1996; Zaki, 1997; Pal et al, 1992). This observation is explained by an increase in the mixing speed produced the smaller size of oil droplets, thus influence the increasing of viscosity (Pal et al., 1992; Briceno et al. 2001; Zaki, 1997). The application of homogenizer may cause the formation of oil droplets having a diameter less than 10 μm. According to the droplet result, macro-emulsion and micro-emulsion (2.9 – 0.08 μm) had successfully applied by homogenizer (10,000rpm-15,000rpm). Amorim (2007) also agree by applying homogenizer are produced small size and stabilized the emulsion. However, the droplet size have more than 1.2 µm are found as unstable emulsion due to coalesces process are easy to occur (Jafari et al., 2008). CONCLUSIONS According to the result, it can be concluded that, o/w emulsion influence various factor in order to find the stabilize condition. This is due to the physical and chemical properties of type’s crude oil which can beaffecting especially need to consider on phase inversion phenomena. The less water separate indicate the most stable o/w emulsion. Applying homogenizer proof the droplet become smallest and displayed tight relation between oil and water. REFFERENCES [1]. Abdurahman, H. N., Yunus, R. M., Jemaat, Z. 2007. Chemical demulsification of water-in-crude oil emulsions. Journal of Applied Sciences, 7(2): 196-201. [2]. Abdurahman, N.H., Rosli, Y.M., Azhari, N.H. Hayder,B.A. 2012. Pipeline transportation of viscous crudes as concentrated oil-in-water emulsions. Journal of Petroleum Science and Engineering, 90–91: 139-144.
  • 7. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 03 Issue: 02 | Feb-2014, Available @ http://www.ijret.org 495 [3] Alvarado, D., and Marsden, S.S. 1979. Flow of oil-in- water emulsions through tubes and porous media. Old SPE Journal, 19(6): 369-377. [4]. Amorim, F.A., Welz, B., Costa, A., Lepri, F. G., Vale, M. G. R., Ferreira, S.L. 2007. Determination of vanadium in petroleum and petroleum products using atomic spectrometric techniques.Talanta, 72(2): 349-359. [5]. Ashrafizadeh, S.N. and Kamran, M. 2010. Emulsification of heavy crude oil in water for pipeline transportation. Journal of Petroleum Science and Engineering, 71(3–4): 205-211. [6]. Azodi, M., and Solaimany, N.A.R. 2013. An experimental study on factors affecting the heavy crude oil in water emulsions viscosity. 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