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

Contents lists available at ScienceDirect

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

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

Fig. 1. Flow Chart illustrating the experimental procedure.

methods that allow a precise quantification of emulsion stability are also 2. Material and methods
of importance, since the final emulsion volume or simple visual inspection
are the most widespread characterization techniques. The effect of the 2.1. Material
different cations on emulsion formation was reported almost a century
ago by Finkle et al. [Finkle et al., 1923], and the effect of cationic The emulsions were studied with an Olympus BX41 microscope
composition on rheological properties, such as viscosity, has been re- equipped with an Olympus SC100 Digital Colour Camera. All the images
ported elsewhere [Perles et al., 2012]. The chemical nature of the salts is shown in this text were taken using an Olympus AchN 40x/0.65P
also potentially intertwined with the surfactant composition in the crude objective. The combined workflow is illustrated in Fig. 1.
oil, which is known to be extremely complex in terms of chemistry [Wen
et al., 2016]; studies using dual surfactants show how the chemical 2.2. Emulsion preparation
composition of the emulsifying mixture can abruptly influence the
properties of the emulsion [Miller et al., 1991]. The crude oil sample was used as received directly from the separator
This study aims at developing a systematic measure of emulsifica- (around 0.2% water by weight). The oil in play has a specific gravity of
tion properties with a particular focus on electrolyte composition and 0.85 g/mL and a viscosity of 5.47 mPas at 65  C which corresponds to
addition of interfacial material. The method is centered on optical reservoir conditions. No water separation was observed after centri-
microscopy. One of the main advantages that optical microscopy pre- fuging the crude at 3 000 RPM. The sample is placed in a borosilicate vial,
sents over other methods for analyzing emulsions (such as focused along with the corresponding amount of water (or aqueous solution). All
beam reflectance microscopy or rheology) is that the emulsion is the measurements herein pertain to 33% by weight water/oil mixtures;
examined in an environment that is as free of external interference as the only variable that is changed throughout the experiments is the
possible. Furthermore, visual examination allows to discern droplets salinity of the water phase. The vial is vigorously shaken manually for
from other objects, such as precipitates, that could be wrongly included 10 s, and shaken afterwards in an automatic shaker for 15 s. The mixture
as emulsion components in the analysis in other methods. Specialized is immediately introduced into the sonicator, and sonicated for 5 min.
analysts are not required to obtain or analyze the data, and a high de- After repetition of the procedure 1 mL of the emulsified mixture is diluted
gree of automatization can be achieved in this technique. in 3 mL of crude oil (to reduce droplet overlap), and homogenised under

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A.V. Mu~
noz, T.I. Sølling Journal of Petroleum Science and Engineering 159 (2017) 483–487

very soft (less than ten turns pr. Sec) magnetic stirring. The rate of the slurry was transferred to the column using a glass pipet to create a frit at
revolving magnet is carefully adjusted to avoid modifying the state of the the end of the pipet. Additional heptol (ca. 5 mL) was employed to rinse
emulsion. After approximately 30 s, a small sample is placed on a mi- the sample vial, complete the transfer of the slurry and ensure uniform
croscope slide and examined under the microscope with a 40 magni- column packing.
fication objective. Every set of data (for a given water composition)
incorporates more than 3 samples. A great deal of attention was put into 2.4.3. IM isolation
ensuring reproducibility by focusing on taking samples from the same Heptol (ca. 10 mL) was passed through the column to remove any
place in the vial and time steps involved where kept the same for each unretained compounds from the column and the eluate was collected in a
sample. The main parameter that is taken into account to evaluate sta- 40 mL glass vial (fraction 1). A 10:25 part ethanol/toluene solution (ca.
tistical significance is that the distribution follows a lognormal proba- 10 mL) was added to the column when the solvent level was around
bility distribution function. The images in the paper correspond to the 5 mm from the top of the stationary phase. The eluate was collected in the
analysis of one sample but each set of data incorporates around 250 first vial until the second eluate (which contains IM and appeared as light
droplets at least. To avoid artefacts the sample a 10 s video is recorded, brown/cream-colored droplets) reached the end of the column. The
repeating the process for several areas within the droplet. The best second eluate was collected in a 25 mL glass vial (fraction 2). Both vials
possible stills are selected from the video. were dried under N2 gas until analytes were solvent free. To reduce
interference of any residual silica that might be displaced with the second
2.3. Extraction of interfacial material solvent system, the material from fraction 2 is transferred to a new vial
and extracted with dichloromethane.
Jarvis et al. [Jarvis et al., 2015] propose a simple and effective
method to isolate interfacially active material from a crude oil sample. 2.5. Image analysis
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 The video is cut into independent frames and the individual images
chromatography column, but in this case water molecules are adsorbed at are processed by means of the software ImageJ. The image treatment is
the stationary phase surface. The stationary phase is a water-saturated subjected to the image quality, but the general approach consists of a
Silica gel formed by adding water to chromatographic silica particles contrast enhancement (0.6%) and the application of a sharpen filter. The
(60 Å), first eluted with a low polarity heptol mixture (eluting the mol- image is converted to 8-bit and a threshold is then applied (Fig. 3).
ecules not interacting or weakly interacting with the water monolayer) The automatic particle counting algorithm in ImageJ is applied by
and finally with a more polar mixture (methanol/toluene) to retrieve the setting the adjustable parameters to a minimum area of 0.45 μm and a
surface active molecules. The principle behind IM extraction is depicted maximum of 50 μm.
in Fig. 2. The change can be observed during the column chromatography
of the sample; a colour change occurs when the adsorbed material is 2.6. Data treatment
eluted (since most surface-active compounds absorb in the visible range).
The result of the droplet counting is a list of droplet areas. The areas
2.4. Detailed procedure for interfacial material extraction are then transformed into diameter using the equation for the area of a
circumference (d ¼ 2(A/π)1/2).
2.4.1. 66% Water-Saturated Silica Gel Preparation A list of diameters is then obtained, which is used to plot a histogram
Approximately 100 g of chromatographic silica gel (60 Å) was placed that will show the different droplet diameter ranges (x axis) against their
in a beaker and oven-dried overnight (110  C) to remove any residual frequency of appearance (y axis). Each bin is then plotted and fitted using
water from the silica gel. After drying, 40 g of MiliQ water previously a lognormal probability function. The more the data points follow the
filtered through a 0.22 μm filter, were slowly added to 60 g of the sil- fitting function, the higher the statistical representability of the sam-
ica gel. ple (Fig. 4).

2.4.2. Sample and Column Preparation/Loading 3. Results and discussion


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 3.1. Aqueous phase composition
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 A series of KCl solutions of different concentrations (1%, 5%, 10%,
wool was added to a 5 mL borosilicate glass pipet to create a frit at the 20% by weight) were prepared and added to crude oil in a borosilicate
end of the pipet (now a column). The ca. 5% crude oil in heptol/silica gel 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
Fig. 2. Molecular depiction of the interfacial material extraction. surfactants, with one type dominating at low salinities and the other

485
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 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
Fig. 5. Droplet Size Distribution functions at different salinities (KCl, % by weight).
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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