VI ESCUELA DE VERANO
IV ESCUELA DE VERANO
PRODUCTIVIDAD DE YACIMIENTOS
Medellín, 2015
ADSORPTION OF IONIC AND
NONIONIC SURFACTANT ONTO
NANOPARTICLES FOR CHEMICAL
ENHANCED OIL RECOVERY
Stefanía Betancur, Ph.D Candidate
Farid B. Cortés, Ph.D.
Francisco Carrasco Marín, Ph.D.
Universidad Nacional de Colombia Sede Medellín
Universidad de Granada
26 de Mayo de 2017
Recobro y Productividad: La Agenda
para Afrontar la Curva de Declinación
de Hidrocarburos en Colombia
Medellín, Mayo 2017
1. INTRODUCTION
Oil recovery
CHEMICAL METHODS: NON-THERMAL EOR methods
that allow better recovery by injection of water.
Surfactant
Flooding
Reduce
interfacial
tension
between water
and oil
Altering the
wettability of
the porous
medium
Taken from: http://colegio.tamaulipas.gob.mx/maestrias-2/maestria-enestudios-de-la-globalizacion/
In world: Between 20 and 40 % [1,2]
Taken from: http://femepa.org/oportunidades-de-negocio-e-inversion-paraempresas-del-sector-metal-en-colombia/
In colombia: About 20 %
Recover the
residual oil from
the reservoir
[3]
[4]
SO3- Na+
Obtaining additional oil through EOR
methods (Enhanced Oil Recovery)
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Lipophilic group
Hydrophilic group
1. INTRODUCTION
Simultaneous application of surfactants
+ nanoparticles as EOR method
Surface or interfacial
adsorption
When the surface or interface
is saturated
Air or
water
Water
Water
TEM micrograph of silica nanoparticles. Taken from:
Micelles formation
Adsorption of surfactant on
porous medium
It may interfere with the transport of
the injecting fluid in the porous medium
[5]
Additional costs: Project not
economically viable [6]
Own elaboration.
[7]
Reduction of
surfactant
adsorption on
rock
Alteration of rock
wettability
Reduction of
interfacial tension
between water
and oil
Increase in
viscosity of
injection fluid
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2. METHODOLOGY
Cationic
Surfactant: CTAB
Nonionic
surfactant:
Tween 20
Anionic
surfactant: SDS
Silica gel
Nanoparticles
Critical Micellar Concentration (CMC)
Surfactant:
CMC
Tween 20
SDS
100 ppm
500 ppm
2000 ppm
Nanoparticles dosification: 100 mg/10 mL
4000 ppm
8000 ppm
Dynamic Light
Scattering (DLS)
Spectrophotometry
UV-Vis
Surface
tension
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2. METHODOLOGY
Adsorption isotherms: Route I
Surfactant
Calculations and
construction of
isotherms
Leave to rest for 24 hrs
Stirring for 2 hrs
Nanoparticles
Q (mg/g)
Brine preparation
Take absorbance
measurements
1000
800
600
400
200
0
0
20
CE (mg/L)
40
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2. METHODOLOGY
Adsorption isotherms: Route II
Surfactant
Brine preparation
Calculations and construction
of isotherms
Leave to rest for 24 hrs:
Micelles formation
Nanoparticles
Stirring for 2 hrs
Q (mg/g)
1000
800
600
400
200
0
Take absorbance
measurements
Leave to rest for 24 hrs:
Micelles formation
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0
50
CE (mg/L)
2. METHODOLOGY
Desorption isotherms
Calculations and construction
of isotherms
Stirring for 2 hrs
Q (mg/g)
Dry samples with surfactant
adsorbed on the nanoparticles:
120 °C
Nanoparticles with
adsorbed surfactant:
100 mg/10 mL
Leave to rest for 24 hrs
Take absorbance
measurements
1000
800
600
400
200
0
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0
20
CE (mg/L)
40
3. RESULTS
Critical Micelle Concentration (CMC)
2.5
b 2.5
2
2
1.5
4000 ppm
1
0.5
Average size (nm)
Average size (nm)
a
TWEEN 20
1.5
0
5000
10000
Surfactant concentration (ppm)
2.5
c
600 ppm
1
0.5
2
2000 ppm
1.5
1
0.5
0
0
SDS
Average size (nm)
CTAB
0
5000
10000
Surfactant concentration (ppm)
0
0
5000
10000
Surfactant concentration (ppm)
Figure 1. The average size of molecule/micelle of a) CTAB, b) Tween 20 and C) SDS for
different surfactant concentrations at 25°C.
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3. RESULTS
Effect of chemical nature of surfactant
200
q (mg/g)
800
q (mg/g)
600
150
100
Zoom for CE < 500 mg/L
50
0
0
400
100
200 300
CE (mg/L)
400
500
CTAB
Tween 20
Adsorbed amount:
CTAB > Tween 20 > SDS
SDS
SLE Model
200
0
0
2000
4000
6000
CE (mg/L)
Figure 2. Adsorption isotherms for CTAB, Tween 20 and SDS onto SiO2 nanoparticles from Route II at 25°C. The
symbols are experimental data, and the continuous lines are from the SLE model.
9/14
3. RESULTS
For all surfactants, evaluated, the adsorption
amount is higher for Route II than Route I
Effect of surfactant micellization
800
Route I
Route II
SLE Model
Route I
Route II
SLE Model
600
400
300
c
800
q (mg/g)
600
q (mg/g)
b
200
q (mg/g)
a
400
Route I
100
Route II
200
200
SLE Model
0
0
0
0
10
20
CE (mg/L)
30
0
100
CE (mg/L)
200
0
5000
CE (mg/L)
Figure 3. Adsorption isotherms for a) CTAB, b) Tween 20 and c) SDS onto SiO2 nanoparticles from Route I and II at
25°C. The symbols are experimental data, and the continuous lines are from the SLE model.
10000
10/14
3. RESULTS
Desorption experiments
1.8
b 6
1.6
1.6
1.1
1
0.8
0.6
0.2
0.2
0.3
0.1
0.3
0.1
4.7
Route I
Route II
3
1.8
1.3
2
0.5
0.2
4
%des
%des
1.2
c 94
4.1
Route II
1.4
0.4
5
Route I
1.5
5.3
5.2 5.05.2
%des
a 2
Percentages of desorption:
SDS > Tween 20 > CTAB
1
1.1
0.8
0
0
100
500
1000 4000
Co (mg/L)
8000
100
500
1000 4000
Co (mg/L)
8000
92
90
88
86
84
82
80
78
76
74
72
Route I
90.8
88.6
81.7
80.3
100
Route II
87.0
85.9 86.186.1
83.5 84.0
500
Figure 4. Percentages of desorption (%) for a) CTAB, b) Tween 20 and c) SDS from fumed silica
nanoparticles for Route I and II at 25°C.
1000
4000
Co (mg/L)
8000
11/14
4. CONCLUSIONS
 Adsorption isotherms were successfully constructed for evaluated the interactions between ionic and nonionic surfactants
onto silica nanoparticles. Cationic and nonionic surfactants (CTAB and Tween 20, respectively) showed isotherms Type III,
while anionic surfactant (SDS) presented isotherm Type I (a) according to the IUPAC scheme.
 CTAB showed the highest adsorptive capacity among the surfactants. Meanwhile, SDS presented the lowest adsorbed
amount. This behavior can be related mainly due to the silanol functional groups of SiO2 nanoparticles presents attractive
electrostatic interactions with the cetyltrimethylammonium cation of CTAB, which can be stronger than the interactions of
dipole- dipole showed by Tween 20 and the repulsive charges that are generated between SDS and silica nanoparticles.
 Route II showed the higher adsorbed amount of surfactant onto nanoparticles than Route I, which suggests that the
formulation of injection fluid for surfactant flooding application should be performed following the Route II.
 CTAB showed percentages of desorption from nanoparticles surface below 1.6 % at 25°C and values below of 0.71 % at 50
and 70°C. The percentages of desorption of Tween 20 were lower than 5.3 %. In contrast, SDS desorbed about 90 %, which
indicates that CTAB and Tween 20 adsorption is an irreversible process while SDS showed a reversible adsorption process.
 From the adsorption process of ionic and nonionic surfactants onto silica nanoparticles evaluated in this research, was
obtained a new and alternative chemical material based on adsorption of surfactant onto nanoparticles surface for
chemical enhanced oil recovery applications. In this way, a synthesis of a complex material that requires more costs and
equipment is avoided.
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Ph.D. Thesis
Nanomaterials based on the
Surfactant/Nanoparticles
interactions
•
•
•
•
•
•
Fluid-Fluid compatibility tests
Detergency tests
Interfacial tension measurements
Rheology
Experiments of adsorption of
Surfactant/Nanomaterial onto rock
surface
Wettability tests
Range of concentration of the nanomaterial:
100-5000 ppm
Select the best
nanomaterial
Modify and evaluate
the nanomaterial
Optimize the
nanofluid
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5. REFERENCES
[1] Muggeridge, A., Cockin, A., Webb, K., Frampton, H., Collins, I., Moulds, T., & Salino, P. (2014). Recovery rates, enhanced oil recovery
and technological limits. Phil. Trans. R. Soc. A, 372(2006), 20120320.
[2] Birol, F. (2008). World energy outlook. Paris: International Energy Agency.
[3] CASTRO, R., & GORDILLO, G. (2008). Historia y Criterios Empíricos en la Aplicación de Inyección de Agua en la Cuenca del Valle
Medio del Magdalena.Revista de investigación Universidad América, Colombia, 1(1), 32-51.
[4] Schramm, L. L. (2000). Surfactants: fundamentals and applications in the petroleum industry. Cambridge University Press.
[5] Li, K., Jing, X., He, S., & Wei, B. (2016). Static Adsorption and Retention of Viscoelastic Surfactant in Porous Media: EOR
Implication. Energy & Fuels, 30(11), 9089-9096.
[6] Austad, T., & Milter, J. (2000). Surfactant flooding in enhanced oil recovery. Surfactants: Fundamentals and Applications in the
Petroleum Industry, 203-249.
[7] El-Diasty, A. I., & Aly, A. M. (2015, September). Understanding the Mechanism of Nanoparticles Applications in Enhanced Oil
Recovery. In SPE North Africa Technical Conference and Exhibition. Society of Petroleum Engineers.
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Gracias
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