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Fuel
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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
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
312
313
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
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
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
314
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
Concentration (ppm)
20
18
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).
70
65
60
55
(mN/m)
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.
315
CMC (ppm)
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).
316
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
317