Fuel 110 (2013) 310317

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Synergistic effect of alkyl-O-glucoside and -cellobioside biosurfactants

as effective emulsiers of crude oil in water. A proposal for the transport
of heavy crude oil by pipeline
Ricardo Cern-Camacho, Rafael Martnez-Palou, Benjamn Chvez-Gmez, Frisia Cullar,
Csar Bernal-Huicochea, Juan-de-la-Cruz Clavel, Jorge Aburto
Instituto Mexicano del Petrleo, Avenida Lzaro Crdenas 152, Col. San Bartolo Atepehuacan, CP 07730, Mexico City, Mexico

h i g h l i g h t s
" We synthesized two series of natural occurring molecules by an innovative approach.
" Such biomolecules present interesting surface properties for emulsication.
" We prepared O/W emulsions of crude oil to facilitate their pipeline transport.
" Such O/W emulsion characteristics vary with the formulation of biosurfactant.
" There is a synergistic effect on the emulsication process with biosurfactant mixtures.

a r t i c l e

i n f o

Article history:
Received 4 April 2012
Received in revised form 15 October 2012
Accepted 5 November 2012
Available online 3 December 2012
Keywords:
Alkyl-O-glucoside
Alkyl-O-cellobioside
Biosurfactants
Heavy crude oil
O/W emulsion

a b s t r a c t
Alkyl-O-glucoside and -cellobioside biosurfactants were synthesized with a long fatty chain (C8C18) in
order to prepare stable and low viscous oil-in-water (O/W) emulsions of a Mexican heavy crude oil.
The resulting O/W emulsions, prepared with a single alkyl-O-glucoside or alkyl-O-cellobioside, were very
unstable and broke out. Only the use of tetradecyl-O-cellobioside allowed the formation of a poor stable
complex emulsion with the broader particle size distribution and more viscous than other emulsions.
Nonetheless, we observed a synergistic effect when a biosurfactant mixture was used and the resulting
emulsions were stable for several days while water separation occurred constantly within 40 days in static conditions. The mixture of biosurfactants with a pC20 value higher than 4.0 and a CMC/C20 ratio higher
than 1.0 favored the formation of a less viscous, narrow particle size distribution and thermal stable O/W
emulsion. This feature is remarkable important when we look for the pipeline transportation of heavy
and extra-heavy crude oils as O/W emulsions. In this work, we present the characterization of biosurfactants as well as the formulation and properties of O/W emulsions of a Mexican heavy crude oil.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
According to the IEA (International Energy Agency), crude oil
production is steadily moving toward unconventional crude oils
as heavy and extra-heavy crude oils in relation to medium and
light oils [1]. Heavy crude oil is dened as petroleum with a specic gravity equal o lower than 20 API, but it is considered as an
extra-heavy crude oil when the API gravity is less than 10, meaning
that crude oil is as much or denser than water. On the other hand,
the heavy and extra-heavy crude oils represent at least one half of
the recoverable oil resources of the world in countries like Canada,
China, Mexico, Venezuela and USA [2]; and here lays the
Corresponding author. Tel.: +52 5591758204; fax: +52 5591758429.
E-mail address: jaburto@imp.mx (J. Aburto).
0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.11.023

importance for developing strategies and alternatives for its transportation using the actual infrastructure as far as possible.
The transportation of heavy and especially extra-heavy crude
oil presents many operational issues that may limit its economical
viability. The major problems for the transportation of heavy and
extra-heavy crude oils through pipeline are their low mobility
and owability due to their high viscosity and asphaltene content
[3]. These features present operational inconveniences such as
deposition of asphaltenes and/or parafns as well as pressure
drops that may cause plugging problems and stops in the pipeline
infrastructure. For this reason, the already mentioned countries are
interested on developing technologies for the transportation of
such crude oils and bitumen; for instance the bitumen-in-water
emulsion known as Orimulsion and developed by PDVSA in
Venezuela. The technological alternatives based on viscosity

R. Cern-Camacho et al. / Fuel 110 (2013) 310317

reduction may be approached by temperature increasing, dilution

with lighter oil or condensates, or the formation of an oil in water
(O/W) emulsion [4,5].
The technological approach based on O/W emulsions is not new
and several studies have been undertaken in last years [6], and
many of them have assayed crude oils with an API value greater
than 22 and a chemical surfactant for emulsion formation and stabilization. We found that using biosurfactants based on glycoside
derivatives in the formulation of O/W emulsions could be an interesting and practical proposal for the pipeline transportation of
Mexican heavy oil crudes.
Sugar based surfactants like alkyl-O-glycosides are useful from
the ecological and industrial perspectives [7], which have applications in cosmetics, pharmaceuticals and detergents [8]. Many synthetic efforts have been oriented toward the development of
strategies for glycosilation such as Fisher glycosilation [9], enzymatic methods [10], protective and deprotective methods, Koenigs-Knorr reaction [11] and others. Therefore, we decided to
investigate glycoside surfactants introducing subtle variations in
both the hydrophobic and the hydrophilic part of the molecule,
i.e. glucose and cellobiose derivatives with long chain (C8C18). In
addition, we improved the synthetic procedure, and developed a
better purication procedure, permitting preparation of biosurfactants in three steps: acetylation, glycosilation and deacetylation.
We present also the formulation and characterization of O/W
emulsions with heavy oil using alkyl-O-glucosides and -cellobiosides and mixes of both. The biosurfactant mixture presents a
synergistic effect in the preparation and properties of the resulting
O/W emulsions: water segregation, particle size distribution, dynamic viscosity and thermal stability through calorimetric studies.
2. Experimental section
2.1. Materials and equipments
1-octanol, decyl alcohol, dodecyl alcohol, 1-tetradecanol, 1hexanol, 1-octadecanol, D-glucose, and cellobiose octoacetate (4)
were purchased from Aldrich Chemical Co. Zinc chloride, NaHCO3,
MgSO4 and all solvents of the highest purity available from commercial suppliers were used without previous purication. Glucose
pentaacetate (1) was prepared as reported elsewhere [12]. The
Mexican heavy crude oil was furnished by the Mexican petroleum
company (PEMEX). All NMR spectra were recorded on a JEOL
GX300 (1H at 300.53 MHz) spectrometer. Chemical shifts (d) are
in ppm and coupling constants (J) are in Hz. Internal standard
and the solvent is specied in each case at room temperature
(see Supporting information). IR Spectra were recorded on a Nicolet spectrometer Nexus 470 FT-IR with diffuse reectance mode
and KBr powder, as dispersive phase.
2.2. General synthesis of alkyl-O-glucosides and alkyl-O-cellobiosides
(Scheme 1)
2.2.1. Glycosilation
In a round-bottom ask, it was placed ZnCl2 (354 mg, 2.6 mmol)
and dried under vacuum at 100 C for 1 h before starting the reaction. Subsequently, 15 mL of toluene, 2 mmol of 1 or 4 and 2.6 mmol
of the corresponding alcohol were added. The reaction mixture was
maintained at 120 C using an oil bath and under reux conditions
by 24 h. After this time, the mixture was cooled down and 15 mL
of ethyl acetate was added to solubilize the corresponding alkylO-acetate glycoside (2 or 5). An aqueous solution of saturated
NaHCO3 (20 mL) was poured to the reaction mixture, allowed to stir
during 15 min until the bubbles disappear and then lter out the
formed salts under vacuum. The ltrate was recovered and

311

transferred into a separation funnel where the organic phase is collected while the aqueous phase is washed with ethyl acetate
(2  10 mL). All organic extracts are mixed and dried with magnesium sulfate, the salts are ltered out and the solvent is evaporated
to yield a browny oil that corresponds to the respective alkyl-Oacetate glucoside (2) or -cellobioside (5).
2.2.2. Deacetylation
In a round-bottom ask is placed (2) or (5) (2 mmol), and dissolved with 5 mL of methanol. A solution of NaOH (4 mmol for glucose derivatives or 14 mmol for cellobiose derivatives) in 15 mL of
methanol was poured to the rst and stirred for 34 h at room
temperature to accomplish deacetylation. After this, the alkylO-glucoside (3) or -cellobioside (6) was recovered by solvent evaporation and washed thoroughly with ethyl acetate (3  10 mL),
diethyl ether (2  10 mL) and dried under vacuum. The detailed
spectroscopic data for (3) and (6) are listed in Supporting
information.
2.3. Critical micellar concentrations (CMCs)
The values of CMC were determined by tensiometry and uorometry methods. A set of different concentrations of every sample
was prepared and the surface tension was measured at 25 C using
a platinum ring on a Du Noy 70454 tensiometer. Every assay was
done at least ve times to assure repeatability. In regard to the
uorometric method, the CMC determination was performed on
a RF-5301PC Shimadzu Spectrouorometer equipped with a
150 W Xe lamp and a cell temperature controller using pyrene as
the uorophore probe. The emission spectra of pyrene and assays
with surfactants were recorded between 350 and 600 nm using
an excitation wavelength (kexc) of 334 nm at 25 C. Every CMC value was estimated by obtaining the second derivative of the surface
tension or the spectral center of mass (SCM) against biosurfactant
concentration. The SCM is a probe of chromophores environment,
i.e. pyrene; because it changes with solvent polarity and temperature and it is calculated from:

P
kIk
SCM P
Ik
where k is the wavelength and I(k) represents the uorescence
intensity at every k [13].
2.4. Formation of oil-in-water (O/W) emulsions
Preparation of the O/W emulsion was carried in a total volume
of 45 mL with 30% of water content. The biosurfactant was rst dissolved in 13.5 mL of synthetic sea water with pH 8 (see Supporting
information) at room temperature [14], and the solution was
poured into a jacketed glass reactor with water recirculation at
65 C. Immediately, the propeller of the mixer was placed so that
it remained submerged in the aqueous phase, and 31.5 g of preheated oil crude at 45 C in an oven was added to the glass reactor.
The reactor with an aqueous biosurfactant solution and the oil
crude was maintained at 65 C for 10 min, and the emulsication
proceeded at 13,000 rpm for 1.5 min using an IKA Labortechnik
homogenizer. Formation of O/W emulsion was corroborated by
dispersing a drop in water as well as by optical microscopy.
2.5. DSC measurements
These assays were carried out using a Shimadzu model DSC-60A
under N2. Every prepared emulsion was precisely weighed (ca.
10 mg) in an aluminum sample pan, which was tightly sealed. The
heat ow on the sample was followed during three heatingcooling

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R. Cern-Camacho et al. / Fuel 110 (2013) 310317

cycles between 50 and 60 C with a scan rate of 10 C/min. All

emulsion characterization by DSC were performed by duplicate
and the same day that emulsions were prepared.
2.6. Bottle test
We modied the well-known bottle test method [15] in order to
evaluate the stability of the emulsion and the segregation of water
through time. We used a glass tube of 1 cm internal diameter and
20 cm length instead of a bottle. We poured into the glass tube the
just prepared O/W emulsion and sealed it with gum caps and maintained at 45 C. The O/W emulsion stability was measured in terms
of water segregation against time and it is dened as the amount of
separated water with respect to the total amount of the emulsion.
2.7. Dynamic viscosity
The viscosity measurements were performed just after emulsion preparation to avoid aging issues using a Rheometer Reolag
Start Rheoplus QC and software. The emulsions were evaluated
at 30, 45 and 60 C using a water bath with temperature control.
The shear rate varied from 1 to 500 1/s and the assays were done
at least three times to assure repeatability.
2.8. Particle size distribution
The determination was performed with a freshly prepared
emulsion using a Particle Sizing System Accusizer 780.
3. Results and discussion
3.1. Biosurfactant synthesis
The sugar-based biosurfactants were prepared following a conventional procedure consisting of three steps: acetylation, glycosilation and deacetylation. Glucose biosurfactants are widely known
but their cellobiose counterparts have received less attention.
Banoub and Bundle prepared cellobiose methyl ester-based biosurfactants using SnCl4 as catalyst for the glycosilation reaction and
hydrazine hydrate as the deprotective agent [16], which is a highly
toxic reagent. More recently, Koto and co-workers reported the synthesis of alkyl-, cycloalkyl- and benzyl-cellobiosides using FeCl3 in
CH3NO2 but yield was low [17]. We have then undertaken a different
approach to prepare a series of alkyl-O-glucoside and -cellobioside
biosurfactants with good yields in according to Scheme 1.
The activation of the C1 atom in glucose was achieved by the
acetylation process [12], while we used a commercial octoacetate
cellobiose for the disaccharides in our reactions. The O-glycosilation step in C1 of the corresponding acetylated saccharide proceeds
using a previous dried ZnCl2 as catalyst. We obtained then an acetylated sugar with a new ether bond in position C1 with a long fatty
chain [18]. Thereafter, we proceeded to the deacetylation step with
a NaOHMeOH solution to yield the corresponding alkyl-O-sugar
based biosurfactants.
3.2. Biosurfactant characterization
We have qualitatively evaluated the solubility of synthesized
biosurfactants in the most common solvents and found that they
are insoluble in apolar solvents like hexane and toluene, insoluble
in ethyl acetate, slightly soluble in acetone and soluble in polar solvents as ethanol, methanol and water. For our purposes, biosurfactants solubility in water plays a very important role to promote the
formation of O/W emulsions, since the intrinsic and high viscous
nature of heavy and extra-heavy crude oils might diminish or avoid

surfactant partition to the wateroil interphase. Moreover, the

formulation of effective surfactants usually requires the use of
co-solvents as alcohols and ketones in order to reach the adequate
surface properties for a specic application. Therefore, we proceed
to determine the values of the critical micellar concentration
(CMC) for every biosurfactant. The CMC denotes the concentration
at which the monomeric surfactant molecules self associate to
form micelles. This is a rapid, dynamic and associationdissociation equilibrium and the concentration depends on analytical
methods. Thereafter, we calculated the following parameters in
order to assess their emulsifying properties: the hydrophilic
lipophilic balance (HLB) calculated using Grifns denition [19];
the surface tension at the CMC value (cCMC) and the minimum
surface tension of biosurfactants in aqueous solution (cmin); the
efciency of surfactant adsorption at the air/water interphase by
reducing the surface tension of water by 20 mN m1 (pC20), i.e.
the value of negative logarithm of C20; and the CMC/C20 ratio,
which is a measure of the effectiveness of the surfactant to form
micelles. In other words, the surfactant shows greater tendency
to adsorb at the interphase or to form micelles in aqueous solution
when its value is major or minor to 1.0, respectively [19b,c].
Surface properties and calculated parameters for alkyl-Oglucoside and -cellobioside biosurfactants are shown in Tables 1
and 2, respectively. It is important to notice that the evaluation
of the CMC values by surface tension and spectrouorometry
showed a good correlation. Every CMC value was estimated as
mentioned above in the method section (Fig. 1). Hence, we
observed that the CMC values decrease linearly with the increase
of the alkyl chain length for both series of alkyl-O-glucoside (see
Supporting information) and alkyl-O-cellobioside biosurfactants
(see insert, Fig. 1). This behavior is attributed to the increment of
the hydrophobic character and comparable with other homologue
series of sugar-based surfactants as reported elsewhere [20,21].
We have also noticed that the CMC values are lower for the
cellobioside derivatives, implying that the formation of micelles
is favored. The alkyl-O-glucoside and -cellobioside biosurfactants
decreased the surface tension (c) at the CMC value with respect
to water (c25C = 72 mN m1). But, the surface tension diminished
with the length of the alkyl chain till a minimum was reached,
being between C10C12 and C12C14 for the alkyl-O-glucoside and
-cellobioside derivatives, respectively. Hence, decyl- and dodecylO-glucosides afford a major reduction in surface tension as do also
dodecyl- and tetradecyl-O-cellobiosides than the corresponding
derivatives with higher alkyl chain. Indeed, such mentioned
glycosides distribute along the interphase till saturation is reached
and then in the bulk phase, contributing to reduction of the surface
tension. The more important hydrophobic interaction between
alkyl chains in higher alkyl-O-glycosides favors rather their
micellization or solvation in the bulk than adsorption at the
interphase with a minor decrease on the surface tension. We
attribute this to the increment on the hydrophobic character of
the molecules as seen by the pC20 and CMC/C20 values when
compare to glucoside derivatives (see below). The decaoctyl-Oglucoside (3f) and -cellobioside (6e) are practically insoluble in
water and their surface properties could not be measured. Indeed,
the increasing non-polar interactions between the higher alkyl
chains should diminish solvation, adsorption of the biosurfactant
at the interphase and favoring the formation of micelles.
Moreover, the pC20 values increased with the number of
carbon atoms in the alkyl chain both for alkyl-O-glucosides and cellobiosides, and reected the negative free energy of adsorption
of the hydrophobic tail at the interphase. Hence, the biosurfactants
3ad and 6ae showed a better efciency to adsorb at the air/
water interphase whilst 3e show a little decrement in pC20
value. For the alkyl-O-glucoside biosurfactants, the CMC/C20 ratios
did not show any tendency. However, 3c has a higher ratio

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R. Cern-Camacho et al. / Fuel 110 (2013) 310317

Scheme 1. Synthetic steps for preparation of alkyl-O-glucoside and -cellobioside biosurfactants used in this work.

Table 1
Surface parameters for alkyl-O-glucoside biosurfactants.
Biosurfactant

HLB

CMC (ppm) uorometry

CMC (ppm) tensiometry

cCMC (mN m1)

cmn (mN m1)

pC20

CMC/C20

GC8 (3a)
GC10 (3b)
GC12 (3c)
GC14 (3d)
GC16 (3e)

12.25
11.18
10.28
9.52
8.86

800.0
202.0
61.9
20.0
9.96

778.0
303.6
78.4
18.0
5.9

44.6
45.4
40.6
45.1
68.7

40.3
27.4
29.8
35.1
55.6

2.88
3.20
4.22
4.62
3.62

2.00
1.50
3.71
2.00
0.06

Table 2
Surface parameters for alkyl-O-cellobioside biosurfactants.
Biosurfactant

HLB

CMC (ppm) Fluorometry

CMC (ppm) Tensiometry

cCMC (mN m1)

cmn (mN m1)

pC20

CMC/C20

G2C8 (6a)
G2C10 (6b)
G2C12 (6c)
G2C14 (6d)
G2C16 (6e)

15.02
14.14
13.37
12.67
12.04

401.1
80.1
20.0
10.1
3.5

405.1
75.8
30.4
11.8
2.6

56.7
55.8
50.9
44.3
62.3

39.1
39.1
29.1
32.1
49.1

2.87
3.38
3.93
4.54
4.58

0.67
0.38
0.50
0.75
0.17

denoting a better adsorption at the airwater interphase before

micellization occurs. In the case of alkyl-O-cellobioside biosurfactants, in particular C10C16, the CMC/C20 values augmented with
the increase of the alkyl chain, meaning that adsorption at the
interphase is favored instead of micellization [22]. It should be
noted that the biosurfactant 3b and 6d shown a CMC/C20 ratio near
to one and high pC20, implying that adsorption at the interphase
and micellization are almost balanced.
In regard to the HLB values, these were higher than seven for
both alkyl-O-glucoside and -cellobioside biosurfactant series,
meaning that these compounds are water-soluble and should favor
the formation of O/W emulsions [19c]. The presence of an
additional glucose anhydride moiety in the alkyl-O-cellobiosides
signicantly increases the HLB and diminishes the CMC values.
Hence, such biosurfactants should form micelles at lower concentration, as suggested by the CMC values, and are more soluble in
water than the alkyl-O-glucosides, one of the desirable characteristics for the preparation of O/W emulsions with heavy and
extra-heavy crude oils.

3.3. Preparation of O/W emulsions

All biosurfactants were tested for the preparation of the O/W
emulsions. The alkyl-O-glucoside biosurfactants could form the
emulsions but they remained stable 1 h or less. Although, the tetradecyl-O-cellobioside (6d) could form a stable emulsion during
10 days. So, we decide to use a mixture of biosurfactants that
may form a more stable emulsion since synergism is a well-known
property of surfactant mixtures [22].
For this purpose, we used then the alkyl-O-glucoside series (3)
that may form the emulsion and tetradecyl-O-cellobioside (6d) as
stabilizer in 1:1 weight ratio. The tested mixtures of alkyl-O-glucosides and -cellobiosides that could form stable O/W emulsions
were 3a/6d, 3b/6d, 3c/6d and 3d/6d; and their creaming and/or
breaking stability studied.
The modied bottle test was carried out at 45 C to evaluate the
stability of O/W emulsions against creaming (segregation of water
and oil phases without emulsion breaking) and/or oil droplet
coalescence (emulsion breaking with or without phase separation)

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R. Cern-Camacho et al. / Fuel 110 (2013) 310317

70

3.0
65

2.5
Log10CMC G2Cn

CMC

60

(mN/m)

55
50

2.0
1.5
1.0
0.5

45

0.0
8

40

10

12

14

16

Number of carbons
35
30
25
0

100

200

300

400

500

600

emulsion did not break out and it is attributed to an appropriate

packing of polar headgroups belonging to the glycosides and strong
enough non-polar interactions of the alkyl chains that synergize,
form and stabilize the O/W emulsion [24a].
The CMC was calculated for the mixture of surfactants 3b/6d
using the equation of Sierra and Svensson model [24b]. In this case,
we calculated a CMC value of 22.7 ppm whilst the experimental
value was 21.6 ppm. The CMC/C20 and pC20 values of the biosurfactant mixture show a similar trend to each separated biosurfactant,
but where adsorption at the interphase is favored with respect to
micellization, which resulted in a more stable emulsion. These
results are evidence of synergism in the surface properties of the
mixture because promoting adsorption at the oilwater interphase, lowering of the surface tension and more stable against
creaming and oil droplets coalescence and emulsion breaking
(see Fig. 3 and Table 3).

Concentration (ppm)

3.4. O/W emulsion characterization

Fig. 1. Prole of surface tension (c) as a function of dodecyl-O-cellobioside (6c)
concentration (closed squares). In this case, the second derivative shows the CMC
value for this surfactant (dotted line). Insert plot: log10CMC values versus the
numbers of carbon atoms for the series of alkyl-O-cellobioside biosurfactants by
tensiometry (d; log CMC = 4.52497  0.25194n, r2 = 0.9888) and uorometry (D;
log CMC = 4.57141  0.25942n, r2 = 0.9831).

20
18

Water segregation volume [%]

16

14
12
10

8
6
4
2
0
0

10

12

14

36 38 40 42

Time [days]
Fig. 2. Water segregation (%) measured by the bottle test at 45 C. The symbol ()
indicates the breaking of emulsion. Surfactants used: 6d (j), 3a/6d (d), 3b/6d (s),
3c/6d (N) and 3d/6d (h).

The emulsion characterization was achieved by particle size

distribution (PSD), dynamic viscosity studies and thermal stability
through heatingcooling cycles by DSC. In the case of PSD, the O/W
emulsions showed a mean diameter in the range of 1050 lm. For
instance, the O/W emulsion with 3d/6d presented a mean diameter of 13 lm, while larger oil droplets were obtained with the biosurfactant 6d (47 lm of mean diameter; Fig. 4, left). The latter
biosurfactant allowed the formation of an O/W emulsion with
the broader particle distribution with the highest value of pC20
when compared to the pC20 values of 3b and the mixture 3b/6d,
meaning that the surface tension is reduced 20 mNm1 with the
minor quantity of such biosurfactant. Moreover, the 6d aqueous
solution presented a CMC/C20 ratio lower than for 3b or the mixture 3b/6d, meaning that the micellization of the biosurfactant
6d is favored with respect to adsorption at the O/W interphase,
which results in a broader particle distribution. The particle size
distributions showed also that the diameter of the oil drops in
the emulsion diminished with the length of the alkyl chain on
the alkyl-O-glucoside biosurfactants. Such behavior may be attributed to a better adsorption of the increasing hydrophobic tail of the
biosurfactant at the O/W interphase as seen by the pC20 values,
which allows then the formation of smaller oil drops.
All prepared emulsions showed non-Newtonian shear thinning
behavior through viscosity dynamic measurements (Fig. 4, right),

70
65
60
55

(mN/m)

as seen in Fig. 2. Whether the creaming process is faster than the

coalescence of drops, the emulsion consist in general of two zones:
(1) a creaming or sedimentation zone in which drops are far apart
from each other and (2) a densely packed zone in which the distance between adjacent drops is so small that they deform to form
thin lms of the intervening water continuous phase [23]. The
more unstable emulsions were obtained with biosurfactant 6d
and the mixture 3a/6d, where the emulsions broke at eight and
4 days, respectively. The O/W emulsions with biosurfactants 3b/
6d (GC10 + G2C14), 3c/6d (GC12 + G2G14) and 3d/6d (GC14 + G2C14)
were stable until 40 days and creaming, i.e. water segregation; of
approximately 20% occurred. This means that ca. 66% of the total
water creamed off from the original O/W emulsion. The different
stabilities are a consequence of a synergistic effect between 6d
and the different alkyl-O-glucoside biosurfactants. Creaming stability diminished with short alkyl chains as C8 but increased for alkyl chains comporting C10C14. Here, creaming occurs mainly by
the density difference between the aqueous and the oily phases,
1.0 and 0.93 gcm3 at 25 C, respectively. Nevertheless, the

50
45
40
35
30

100

200

300

400

500

600

700

800

900

1000

Concentration (ppm)
Fig. 3. Surface tension prole (c) for alkyl-O-glucoside (3b;N), alkyl-O-cellobioside
(6d; h) and the corresponding mixture (d; 1:1 w/w) at 25 C.

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R. Cern-Camacho et al. / Fuel 110 (2013) 310317

Table 3
Inuence in surface properties of mixture surfactants (GC10 + G2C14) respect to pure surfactants.
Biosurfactant

CMC (ppm)

cCMC (mN m1)

cmn (mN m1)

pC20

CMC/C20

GC10 (3b)
G2C14 (6d)
3b/6d

303.6
11.8
21.6

45.4
44.3
46.1

27.4
32.1
33.9

3.20
4.54
4.14

1.50
0.75
1.57

Fig. 4. Particle size distribution (left) and proles of dynamic viscosity at 30 C (right) for O/W emulsions in synthetic sea water. O/W emulsions with 6d (D), 3a/6d (j), 3b/6d
(h), 3c/6d (d) and 3d/6d (s). Crude oil (N).

i.e. the viscosity diminishes as shear rate increases; as conrmed

by the plot of shear stress versus shear rate of all emulsions and
the heavy crude oil (see Supporting information). Initial viscosity
at low shear rate is rather similar between the heavy crude oil
and the O/W emulsions, but the viscosity gap grows importantly
at high shear rates. For the crude oil, such behavior has been attributed to disentanglement, stretching and parallel orientation of
crude oil molecules to the driving force that reduces its viscosity.
For the O/W emulsions, viscosity is affected by volume fraction,
droplet size distribution as well as chemical composition of every
phase [25]. We observed also that emulsion viscosity diminished
with the mean diameter size of oil droplets dispersed in the water
continuous phase. Here, the prepared emulsions are comported by
micro-sized oil droplets dispersed in water that should be not so
tight together, allowing enough free water volume around them
and allowing enough oil droplet movement and then viscosity
reduction. In the case of nano-emulsions, i.e. nano-sized oil droplets, the free water volume should be quite reduced when compare
to micro-emulsions where the oil droplets tight together, and
increasing viscosity emulsion. At such conditions, all O/W emulsions prepared with the biosurfactant mixture presented a viscosity diminution with respect to the original crude oil (ca. 260 mPas
at 250 s1), except for the O/W emulsion prepared with 6d that
reached a minimal viscosity around 140 mPas. The lowest oil drop
size distribution and viscosity was obtained with the O/W emulsion prepared with the biosurfactant mixture comporting the tetradecanoyl-O-glucoside and -cellobioside (1:1, blend 3d/6d).
Here, the biosurfactant mixture allowed both a drop size and
viscosity reduction of the O/W emulsion, meaning that there are
enough free volume in the continuous water phase to allow better
displacement of oil drops that reects on a lower viscosity. Moreover, viscosity of O/W emulsions reduced further at 45 and 60 C,
but there are still lower and distinctive than for the crude oil
(see Supporting information). This is important because the

viscosity is low enough and near to ambient temperature to allow

emulsied crude oil mobility by pipeline.
The behavior of an O/W emulsion through heatingcooling cycles may give some insights about emulsion thermal stability.
The test consists in regularly cooling down and heating up a
non-diluted emulsion sample, to obtain information about freezing
temperature of the continuous phase of water, micro-droplets of
water, emulsion type and stability [26]. The shown results correspond to the cooling cycle, since the heating ramp shows only
the thermodynamic fusion of all water near 0 C.
In the rst cooling cycle from 50 to 60 C, it is possible to observe different signals corresponding to water freezing at three and
one temperature values for the biosurfactants 6d and the mixture
3b/6d, respectively. Such water freezing signals correspond to free
water in a continuous phase around 24 to 26 C and water crystallization contained in micro-droplets surrounded by oil around
39 to 50 C as discussed elsewhere [27]. The cooling thermogram of a freshly O/W emulsion prepared with 6d shows three signals, one attributed to free water in continuous phase (26 C) and
two signals attributed to water micro-droplets inside an oil phase
(39 and 50 C). The presence of several water phases identied
by DSC in the emulsion (Fig. 5A and B), i.e. O/W, W/O, O/W/O, W/O/
W, and the broader particle size distribution (see Fig. 4 left) are
also responsible of a higher viscosity when compared with the
emulsion prepared with the biosurfactants mixture (Fig. 4 right).
This can be explained in terms of a reduced free volume of the
aqueous continuous phase, i.e. the oil droplets can tight together;
as well as a higher intrinsic viscosity of the oil phase. Such emulsion is complex since water is presented as continuous and dispersed phase simultaneously. Despite its viscosity is lower than
original crude oil, this kind of emulsions must be avoided during
preparation and pipelining since pressure drops during transport
as well as a more difcult dehydration process that may be present
before crude oil rening.

316

R. Cern-Camacho et al. / Fuel 110 (2013) 310317

2mW

2mW

B
1st cycle

1st cycle

2nd cycle
2nd cycle

3rd cycle
3rd cycle

-60

-55

-50

-45

-40

-35

-30

-25

-20

-15

-10

-60

-55

-50

-45

Temperature [C]

-40

-35

-30

-25

-20

-15

-10

Temperature [C]

5mW

2 mW

D
1st cycle

1st cycle

2nd cycle
2nd cycle

3rd cycle
3rd cycle

-60

-55

-50

-45

-40

-35

-30

-25

-20

-15

-10

-60

-55

-50

-45

Temperature [C]

-40

-35

-30

-25

-20

-15

-10

Temperature [C]

Fig. 5. DSC thermograms showing the cooling cycles for O/W emulsions freshly prepared (A), and after 4 days (B) with the biosurfactant 6d and freshly O/W emulsion (C), and
after 4 weeks (D) prepared with biosurfactant 3c/6d.

On the other hand, the O/W emulsion prepared with 3b/6d possessed a single signal at 26 C, meaning that the emulsion has an
only continuous free water phase. Such results corroborated the narrowed particle size distribution and a lower viscosity as discussed
earlier. The second and third cooling cycle showed a slight displacement of the free water signal to minor temperature and attributed to
partial water phase inversion, i.e. free water started to form small
drops enveloped by an oil phase. Such behavior was evident when
the biosurfactant 6d was employed and less with the mixture 3c/
6d. The latter is evidence of an enhanced stability of prepared O/W
emulsion with the biosurfactant mixture. The pipeline transport of
heavy or extra heavy crude oils must be accomplished with this
latter kind of emulsion where a narrow particle size distribution,
thermal stability and lower viscosity are present.
After 4 days of emulsion annealing at ambient temperature, we
observed that thermograms are quite similar to those of freshly
prepared emulsions, and only the O/W emulsion prepared with
the biosurfactant mixture showed a new signal around 28 C.

These thermograms tell us that the O/W emulsions are quite stable
in the explored period of time and temperature, but that the biosurfactant mixture permits a major stability when compared to
biosurfactant 6d, mostly because of the initial complex emulsion.
Hence, the mixture of alkyl-O-glucoside and -cellobioside biosurfactants allowed a more stable O/W emulsion, making evident
the synergistic effect between these compounds in the preparation
and properties of corresponding emulsions.

4. Conclusion
We prepared O/W emulsions using biosurfactants comporting alkyl-O-glucosides and -cellobiosides. The emulsifying effect of studied
biosurfactants depends mainly on parameters like pC20 and CMC/C20
ratio. The more stable O/W emulsions were prepared with a mixture
of long alkyl chain glucosides and tetradecanoyl-O-cellobioside.
In addition, it is important to consider the solubility of the

R. Cern-Camacho et al. / Fuel 110 (2013) 310317

biosurfactants in the water continuous phase as well as the length of

the biosurfactants alkyl chain, since water solubility facilitates the
partition of biosurfactants into the wateroil interphase with an
important diminution of the surface tension for preparation of a
stable O/W emulsion. The more viscous crude oil phase may delay
or avoid the partition of biosurfactants to the wateroil interphase.
The formation of complex emulsions, i.e. W/O/W; is undesirable for
pipelining of crude oil because they present polydispersity, are less
stable and are more viscous. Such effect was observable for the O/W
emulsion prepared with only one biosurfactant (6d). It is evident
that tested biosurfactants have better emulsifying properties when
mixed with others that when they are used individually. The
mixtures of biosurfactants showed a synergistic effect and have a
great potential for the application in the pipeline transport of heavy
crude oil emulsions because they are the least viscous, are more
stable for a larger time and may segregate or cream a larger volume
of water, facilitating the breaking of the O/W emulsion for further
crude oil processing.
Acknowledgments
We thank Instituto Mexicano del Petrleo (IMP project
D.01225) and CONACyT for nancial support and a postdoctoral
grant, respectively.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2012.11.023.
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