Journal of Petroleum Science and Engineering 159 (2017) 483–487

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Journal of Petroleum Science and Engineering

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

Imaging emulsions: The effect of salinity on North Sea oils

~as Mun
Alberto Vin ~oz, Theis I. Sølling *
Chemistry Department, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark

A B S T R A C T

A workflow to quantify emulsification in water-in-oil (W/O) systems by means of optical microscopy has been applied to study the effect of salinity on emulsification
with addition of KCl solutions with increasing concentration to a crude oil sample. A second order relation between droplet size and salinity has been observed for KCl.
The effect of the addition of a different salt (NaCl) has also been studied, thereby monitoring the relation between droplet size and the size of the cation. For KCl the
droplet size increases up until 5 w% after which it decrease; for NaCl the behaviour is opposite. The effect of interfacially active material isolated from the crude
sample has been tested, and the droplet size is substantially affected, with the formation of droplets of considerably smaller diameter. We propose that this observation
is due to the presence of two regimes: one where the droplet motive is strongly impacted by cation intercalation in the micellar structure (large droplets) and one
where the anions determines the outcome by binding to the surfactants (small droplets).

1. Introduction
The ability of chemical flooding agents to form emulsions has proven
to affect the mobility of oil relative to water through various mechanisms
[Pei et al., 2013], and thus the development of efficient
microemulsion-based EOR technologies offers a promising venue of
exploration. The very low interfacial tensions reached in microemulsion
systems allow them to flow more easily in porous media and could if
induced in a reservoir lead to reduced residual oil saturations and thus to
enhancing oil recovery [Austad and Strand, 1996]. A better under-
standing of emulsification in North Sea oils is key to enable the prepa-
ration of stable microemulsions and eventually utilize micro
emulsification as an EOR strategy in tight carbonate rocks. Studies that
focus on quantifying on effect of various perturbations to an emulsion are
limited which seems to indicate that it is a difficult and rather unex-
plored task.
An emulsion can be defined as a state of matter in which two
immiscible liquids are mixed by the dispersion of one of the liquids
(dispersed phase) in the other (continuous phase) in the form of micro-
scopic droplets [Tadros, 2013]. Emulsions are optically isotropic from a
macroscopic standpoint, thus hiding their complex microscopic structure
to the naked eye.
As a general case, emulsions do not form spontaneously, meaning that
they are thermodynamically unstable systems. The driving force in
emulsion formation can be mathematically by eq. (1) [Tadros and Vin-
cent, 1980]:
Δ Gf ¼ Δ Aγ12 TΔ Sconf
or m
Where ΔA is the change in interfacial area (4πr2 per droplet of radius
r) and γ 12 is the interfacial tension between phases 1 and 2 (oil and water
for the present case). The entropy contribution is described by the term
ΔSconf, which is the configurational entropy [Overbeek, 1978]:
ΔSconf ¼ nKB[lnΦ þ {(1Φ)/Φ}ln(1 Φ)] (2)
Where n is the number of droplets in the dispersed phase, KB is the
Boltzmann constant and φ is the dispersed phase volume. Thermody-
namically favourable processes are characterised by negative free energy
variations which, in the case of emulsion formation, require extremely
low interfacial tension contributions that reduce the contribution of the
first term in eq. (1). Thermodynamic instability results in the eventual loss
of the colloidal structure of the emulsion system, with the subsequent
phase separation. The transient character of this state is due to the nature
of the interactions that bring about emulsion formation. Understanding
the interactions that drive emulsification is therefore key in facilitating
the design of fluids with desirable rheological and physical properties.
This has already been achieved for simple systems [L opez-Montilla et al.,
2002], but remains a challenge for complex systems such as crude oil/-
water mixtures. Specific ion effects have long been known to be present in
colloidal systems [Kunz and Ninham, 2004]. However, a complete un-
derstanding of how different cations affect emulsification has not been
achieved. The effect of salinity on emulsion formation has been object of
study for decades [Tambe and Sharma, 1992], but even though a good
understanding of the effect of salinity on emulsion formation has been
reached, the impact of the salt composition (especially in terms of cationic
(1) composition) lacks understanding [Perles et al., 2012]. The use of

* Corresponding author.
E-mail address: theis@kiku.dk (T.I. Sølling).

https://doi.org/10.1016/j.petrol.2017.09.061
Received 11 June 2017; Received in revised form 20 September 2017; Accepted 24 September 2017
Available online 27 September 2017
0920-4105/© 2017 Elsevier B.V. All rights reserved.
A.V. Mu~
noz, T.I. Sølling
Fig. 1. Flow Chart illustrating the experimental procedure.
methods that allow a precise quantification of emulsion stability are also
of importance, since the final emulsion volume or simple visual inspection
are the most widespread characterization techniques. The effect of the
different cations on emulsion formation was reported almost a century
ago by Finkle et al. [Finkle et al., 1923], and the effect of cationic
composition on rheological properties, such as viscosity, has been re-
ported elsewhere [Perles et al., 2012]. The chemical nature of the salts is
also potentially intertwined with the surfactant composition in the crude
oil, which is known to be extremely complex in terms of chemistry [Wen
et al., 2016]; studies using dual surfactants show how the chemical
composition of the emulsifying mixture can abruptly influence the
properties of the emulsion [Miller et al., 1991].
This study aims at developing a systematic measure of emulsifica-
tion properties with a particular focus on electrolyte composition and
addition of interfacial material. The method is centered on optical
microscopy. One of the main advantages that optical microscopy pre-
sents over other methods for analyzing emulsions (such as focused
beam reflectance microscopy or rheology) is that the emulsion is
examined in an environment that is as free of external interference as
possible. Furthermore, visual examination allows to discern droplets
from other objects, such as precipitates, that could be wrongly included
as emulsion components in the analysis in other methods. Specialized
analysts are not required to obtain or analyze the data, and a high de-
gree of automatization can be achieved in this technique.
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Journal of Petroleum Science and Engineering 159 (2017) 483–487
2. Material and methods
2.1. Material
The emulsions were studied with an Olympus BX41 microscope
equipped with an Olympus SC100 Digital Colour Camera. All the images
shown in this text were taken using an Olympus AchN 40x/0.65P
objective. The combined workflow is illustrated in Fig. 1.
2.2. Emulsion preparation
The crude oil sample was used as received directly from the separator
(around 0.2% water by weight). The oil in play has a specific gravity of
0.85 g/mL and a viscosity of 5.47 mPas at 65  C which corresponds to
reservoir conditions. No water separation was observed after centri-
fuging the crude at 3 000 RPM. The sample is placed in a borosilicate vial,
along with the corresponding amount of water (or aqueous solution). All
the measurements herein pertain to 33% by weight water/oil mixtures;
the only variable that is changed throughout the experiments is the
salinity of the water phase. The vial is vigorously shaken manually for
10 s, and shaken afterwards in an automatic shaker for 15 s. The mixture
is immediately introduced into the sonicator, and sonicated for 5 min.
After repetition of the procedure 1 mL of the emulsified mixture is diluted
in 3 mL of crude oil (to reduce droplet overlap), and homogenised under
A.V. Mu~
noz, T.I. Sølling
very soft (less than ten turns pr. Sec) magnetic stirring. The rate of the
revolving magnet is carefully adjusted to avoid modifying the state of the
emulsion. After approximately 30 s, a small sample is placed on a mi-
croscope slide and examined under the microscope with a 40 magni-
fication objective. Every set of data (for a given water composition)
incorporates more than 3 samples. A great deal of attention was put into
ensuring reproducibility by focusing on taking samples from the same
place in the vial and time steps involved where kept the same for each
sample. The main parameter that is taken into account to evaluate sta-
tistical significance is that the distribution follows a lognormal proba-
bility distribution function. The images in the paper correspond to the
analysis of one sample but each set of data incorporates around 250
droplets at least. To avoid artefacts the sample a 10 s video is recorded,
repeating the process for several areas within the droplet. The best
possible stills are selected from the video.
2.3. Extraction of interfacial material
Jarvis et al. [Jarvis et al., 2015] propose a simple and effective
method to isolate interfacially active material from a crude oil sample.
We have employed such material to test the effect of its addition to an
emulsification mixture. The procedure is analogous to that of a standard
chromatography column, but in this case water molecules are adsorbed at
the stationary phase surface. The stationary phase is a water-saturated
Silica gel formed by adding water to chromatographic silica particles
(60 Å), first eluted with a low polarity heptol mixture (eluting the mol-
ecules not interacting or weakly interacting with the water monolayer)
and finally with a more polar mixture (methanol/toluene) to retrieve the
surface active molecules. The principle behind IM extraction is depicted
in Fig. 2. The change can be observed during the column chromatography
of the sample; a colour change occurs when the adsorbed material is
eluted (since most surface-active compounds absorb in the visible range).
2.4. Detailed procedure for interfacial material extraction
2.4.1. 66% Water-Saturated Silica Gel Preparation
Approximately 100 g of chromatographic silica gel (60 Å) was placed
in a beaker and oven-dried overnight (110  C) to remove any residual
water from the silica gel. After drying, 40 g of MiliQ water previously
filtered through a 0.22 μm filter, were slowly added to 60 g of the sil-
ica gel.
2.4.2. Sample and Column Preparation/Loading
A total of 20 mL of heptol [50:50 (v/v) heptane/toluene] was added
to 1 g of crude oil to create an approximately 5% solution. A total of 1 g of
hydrated silica gel (ca. 66% water) was added to the 5% crude oil in the
heptol solution, and the mixture was shaken to generate a slurry. Glass
wool was added to a 5 mL borosilicate glass pipet to create a frit at the
end of the pipet (now a column). The ca. 5% crude oil in heptol/silica gel
Fig. 2. Molecular depiction of the interfacial material extraction.
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Journal of Petroleum Science and Engineering 159 (2017) 483–487
slurry was transferred to the column using a glass pipet to create a frit at
the end of the pipet. Additional heptol (ca. 5 mL) was employed to rinse
the sample vial, complete the transfer of the slurry and ensure uniform
column packing.
2.4.3. IM isolation
Heptol (ca. 10 mL) was passed through the column to remove any
unretained compounds from the column and the eluate was collected in a
40 mL glass vial (fraction 1). A 10:25 part ethanol/toluene solution (ca.
10 mL) was added to the column when the solvent level was around
5 mm from the top of the stationary phase. The eluate was collected in the
first vial until the second eluate (which contains IM and appeared as light
brown/cream-colored droplets) reached the end of the column. The
second eluate was collected in a 25 mL glass vial (fraction 2). Both vials
were dried under N2 gas until analytes were solvent free. To reduce
interference of any residual silica that might be displaced with the second
solvent system, the material from fraction 2 is transferred to a new vial
and extracted with dichloromethane.
2.5. Image analysis
The video is cut into independent frames and the individual images
are processed by means of the software ImageJ. The image treatment is
subjected to the image quality, but the general approach consists of a
contrast enhancement (0.6%) and the application of a sharpen filter. The
image is converted to 8-bit and a threshold is then applied (Fig. 3).
The automatic particle counting algorithm in ImageJ is applied by
setting the adjustable parameters to a minimum area of 0.45 μm and a
maximum of 50 μm.
2.6. Data treatment
The result of the droplet counting is a list of droplet areas. The areas
are then transformed into diameter using the equation for the area of a
circumference (d ¼ 2(A/π)1/2).
A list of diameters is then obtained, which is used to plot a histogram
that will show the different droplet diameter ranges (x axis) against their
frequency of appearance (y axis). Each bin is then plotted and fitted using
a lognormal probability function. The more the data points follow the
fitting function, the higher the statistical representability of the sam-
ple (Fig. 4).
3. Results and discussion
3.1. Aqueous phase composition
A series of KCl solutions of different concentrations (1%, 5%, 10%,
20% by weight) were prepared and added to crude oil in a borosilicate
glass vial. The experimental procedure for emulsification previously
exposed was followed and the lognormal probability function describing
the Droplet Size Distribution (DSD) for each of the mixtures plotted.
Fig. 5 shows how the DSD varies with salinity. It can be seen that the
diameter at which the highest droplet count is registered varies with
salinity, although not linearly. A plot of the highest count diameter vs.
salinity (Fig. 5) reveals a second order dependence, with a maximum at
5% salinity. The complex chemistry of crude oils leads us to propose that
a bit of caution is exercised with regard to general interpretation of the
results since there may still be variables that we have not considered and
which may be beyond our control. A number of different molecules that
act as surfactants can be found in crude oil, including both the ionic and
non-ionic types. This could explain the sudden change in trend when
increasing the salinity of the aqueous phase. Up to 5% salinity, an in-
crease in the highest count diameter is observed, with a later drop in
stability when further increasing the salinity of the aqueous phase. This
could be explained by a competitive effect between ionic and non-ionic
surfactants, with one type dominating at low salinities and the other
A.V. Mu~
noz, T.I. Sølling Journal of Petroleum Science and Engineering 159 (2017) 483–487

Fig. 3. a) raw frame extracted from the video recording of the emulsion b) contrast enhanced image c) contrast enhanced image after application of a sharpen filter d)8-bit image to which
the particle counting algorithm Is applied.

Fig. 4. a) raw image b) image after thresholding the 8-bit image shown in Fig. 3d c) outline of the particles counted by the particle counting algorithm d) histogram of the
droplet diameters.

dominating at high. Even though this should be interpreted carefully, as have different solvation spheres and cation sizes, and any change in
stated before, the coincident turning point in salinity of both salts (5%) emulsification will be associated with the nature of the cation, since the
studied (see next section) strengthens the suggested rest of variables are kept constant. Results can be found in Fig. 6.
competing mechanism. The plot shows a trend reversal. For both systems a new effect kicks in
at 5 pct and another one takes over. We propose that this observation is
3.2. Influence of the cation due to the presence of two regimes: one where the droplet motive is
strongly impacted by cation interaction in the micellar structure (large
Experiments have been performed using two different salts, sodium droplets) and one where the anions determines the outcome by binding
chloride (NaCl) and potassium chloride (KCl), in order to study how the to the surfactants (small droplets). At small weight percentages there is a
nature of the cation affects emulsification. Two different solutions with smaller number of chloride ions for the KCl solutions compared to NaCl.
monovalent cations have been used (Naþ and Kþ). Sodium and potassium This allows a larger number of chloride ions to be solvated by hydrogen

486
A.V. Mu~
noz, T.I. Sølling
Fig. 5. Droplet Size Distribution functions at different salinities (KCl, % by weight).
Fig. 6. Highest diameter count versus salinity.
bonding to the water whereas the potassium ions are intercalated.
Thus, potassium is not necessarily more effective, there are simply
less cations in solution compared to NaCl in a similar weight percentage.
3.3. Addition of interfacial material
The addition of interfacial material to the emulsion that was formed
from with a 20% KCl brine (brine to oil 33%) has proven to decrease the
droplet diameter to the highest extend. The diameter with the highest
count is found at 1 μm, which is lower than in any of the other cases. This
observation underlines the importance of surface active material in the
stabilization of emulsions and therefore the fact that surfactants are the
driving force in emulsion formation and we speculate that the behaviour
is in line with the size dependence of the salt and ion composition In the
case of the addition of pure interfacial material there will be more
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Journal of Petroleum Science and Engineering 159 (2017) 483–487
droplets that form in there purest from i.e. without intercalation as the
presence of interfacial material surely will be the limiting factor in oil
emulsification.
4. Conclusions
Optical microscopy has proven to be a valuable tool in evaluating the
effects of the aqueous phase composition in water-crude oil emulsions,
supporting previous studies [Moradi et al., 2011]. Further development
is needed to further automate the method so that the number of analysed
droplets per sample can be increased to achieve proper statistical rep-
resentation of the sample. The results are encouraging and confirm the
validity of the method. Variation of the salinity in the aqueous phase has
shown a significant effect over the droplet size. The nature of the cation
in the aqueous phase affects the droplet size variation with salinity in a
non-linear manner; we propose that this is due to various degrees of
perturbation to the micellar structure as a function of concentration.
The interfacial material extraction method has proven to be very
convenient for further studies of surface active molecules and the addi-
tion of the extracted interfacial material has an effect on emulsification in
the sense that the emulsion droplets seem to become smaller and we take
that to indicate formation of unperturbed emulsion droplets. The incor-
poration of more effective homogenizing tools could increase the quality
of the images, making the image analysis more prone to encompass a
higher number of droplets. This, along with a more thorough control of
temperature is indeed a must before any commercial implementation.
Acknowledgements
The authors are thankful to Dr. Martin Vad Bennetzen (Maersk Oil)
for insightful discussions of emulsification. This research was funded by
the Danish Hydrocarbon Research and Technology Centre (DHRTC).
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