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Optimum Formulation Relationship topredict a solution in micro/macroemulsions
applications in SOW systems
J.L. Salager, A.M. Forgiarini & J.Bullón
Lab FIRPUniversity of the Andes,
Mérida - Venezuela
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Emulsion persistance (stability)has been studied for more than 100 years
vs surfactants, polymers and particles
It was only ~ 40 years ago that ageneral rule was found
from the surfactant effects in relationto EOR Optimum formulation
What is the physicochemical formulation ?A concept based on interactions at O/W interface
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Winsor’s Ratio (1954)between molecular interaction energies
R =Aco
Acw
very pedagogicalbut qualitative!
R < 1, R = 1 or R > 1related to phase behavior
oil(O)
water(W)
Aco
Acw
surfactant(C)
Winsor P., Solvent Properties of Amphiphilic Compounds, Butterworth London (1954)
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Winsor researchshowed a relation between R
and the phase behavior
R < 1 R > 1
S1 micelle micelle S2 micelleS
OW
S
O W
2 2__
W IW I W IIW IIPhase behavior (in two-phase zone at )
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S
W Ocomplex phase behavior
liquid crystal microemulsion
W III S 2
S 1
R = 1
Winsor researchshowed a relation between R
and the phase behavior
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Formulation Scanchanges the phase behavior
Example: Formulation variable = Salinity of aqueous phase
R = Aco
Acw
If salinity increasesAcw decreases R increasestransition R < 1 R = 1 R > 1
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Formulation Scanphase behavior
1.0 1.4 2.0 2.8 4.0 5,6 % NaCl
R > 1R < 1 R = 1
Salinity
W I W IIW III
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Formulation Scan
W IIIW III
Optimum Formulation
W IW I2
W IIW II2
Shah D., Schechter R., Eds,. Improved Oil Recovery by Surfactant andPolymer Flooding, Academic Press New (1977)
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Same transition (R < 1 R >1)with all formulation variables able
to alter Axx interactions
Salinity (type and conc.) ACN and structure Surfactant (Hydroφ part) Surfactant (Lipoφ part) Temperature Alcohol (type and conc.)
R = Aco - 1 / 2 Aoo - 1 / 2 ALL
Acw - 1 / 2 Aww - 1 / 2 AHHoil(O)
water(W)
Aco
Acw
surfactant(C)
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two-dimensional scan =series of one-dimensional scans
formulationvariable #1(Salinity)
formulation variable # 2 (ACN)
2 φ (W I)
2 φ (W II)
3 φW III
OptimumFormulationS - ACN
Optimum Formulationsystematic studies
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Ln S
ACN
Relation:LnS = K ACN + ...or dLnS = K dACN
For all systemscontaining ionicsurfactants3φ
2
2
Optimum Formulationsystematic studies
Salager J. L. et al., Soc. Petroleum Eng. J., 19: 107 (1979) ANIONIC SYSTEMSBourrel M. et al., J. Colloid Interface Science, 75: 451 (1980) NONIONIC SYSTEMSAntón R. E. et al., J. Dispersion Science Technology, 18: 539 (1997) CATIONIC SYSTEMS
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OPTIMUM FORMULATION
lnS - K ACN - f(A) + σ - aT ∆T = 0
α - EON + b S - k ACN - φ(A) + cT ∆T = 0
Salinity Oil Alcohol Temperature
ionic
nonionic
empirical correlations(thousands of experiments)
Σ c X = 0i iWhich may be written as :
Surfactant
Surfactant
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Surfactant Affinity Difference(Affinity = - µ*)
µ = µ* + RT ln C = µ* + RT ln Cw w o o
SAD = µ* - µ* = RT ln C /Coow w
At optimum formulationCw = Cothus SAD = 0
(anionic systems)
Salager et al., Langmuir, 16: 5534 (2000)
Surfactant Partition Coefficient
CO
CW
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Conceptual SupportSurfactant Affinity Difference SAD
complex but quantitative
><HLD = SAD/RT = lnS - K ACN - f(A) + σ - aT ∆T = 0
HLD = SAD/RT = β + b S - k ACN - φ(A) + cT ∆T = 0
ionic
nonionic Salinity Oil Alcohol Temperature
Surfactant
HLD = Hydrophilic-Lipophilic Deviation
Surfactant
Salager J.L., in Pharmaceutical Emulsions and Suspensions,Nielloud F., Marti-Mestres G., Eds., Chap. 2, Dekker (2000)
<>
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Minimuminterfacial
tension
γ*minAt a very preciseformulation value in ascan (here salinity)
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16 / 30 It is a general phenomenonlow interfacial tension in WIII system (HLD ~ 0)
in a narrow zone of any formulation scan
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∆P Poiseuille∆P Laplace
Capillary Number NCav η γ
= = 10 - 6
should be x 100 or 1000 to produce displacement
Capillary Number =
EOR Displacement criterion
Value in Sor
vusual = 1 ft/dayηwater = 1 cP, ηpolymers 100 cPγwater/crude = 10 mN/m
General phenomenon
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Correlation NCa Recovery
Stegemeir G. L., Mechanism of entrapment and mobilization of oil in porous materials.In Improved Oil Recovery by Surfactant and Polymer Flooding,Shah D. O., Schechter R. S., Eds. Academic Press (1977)
NCa = v η γ
Res
idua
l Sat
urat
ion
S or
10 - 4 10 - 210 - 6 10 - 4 10 - 210 - 6
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STA
BIL
ITY
(sec
)
Emulsion stability vs formulation Experimental Results
Salager et al., JDST (1982)
Another general phenomenon
O / W W / O
Hydrophilic LipophilicSurfactant Behavior
at optimum: 3 phases, emulsion inversion and instability
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Emulsion stability vs formulation Experimental Results
Another general phenomenon
Bourrel et al. JCIS (1979) Salager et al. JCIS (1980)
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Milos & Wasan COLS (1982) Anton & Salager JCIS (1986)
Stability - Formulation Experimental Results
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22 / 30 Same instability whatever thesurfactant concentration : At HLD = 0surfactant does not seem to be at O-W interfaceto stabilize emulsion
Anton & Salager JCIS (1986)
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23 / 30 Why are emulsions very unstable at HLD=0?Various explanations
Surfactant is trapped in a microemulsion Surfactant forms liquid crystal bridges Holes in interdrop films are unstable Tension ~ 0 and thus tension gradient ~ 0 (no Gibbs-Marangoni effect) Fast transfer to interface and quick apparent equilibration Zero curvature is inconsistent with spherical drops etc...
Bourrel M. et al., J. Colloid Interface Sci., 72: 161 (1979)Salager J.L. et al., J. Colloid Interface Sci., 77: 288 (1980)Anton R., Salager J.L., J. Colloid Interface Sci., 111: 54 (1986)Hazlett R. D., Schechter R. S. Colloids Surfaces, 29: 53 (1988)Kabalnov A. et al., Langmuir, 12: 8 & 12: 276 (1996)Ivanov I. et al., Colloids Surfaces A, 128: 155 (1997)Fillous L. et al. J, Surfactants & Detergents 2: 303 (1999)Salager JL et al. Langmuir, 18: 607 (2002)
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Principle of Desestabilization is basedon a mixture to attain HLD = 0
natural surfactant (asphaltene) is lipophilic demulsifier surfactant should be hydrophilic so
that the mixture of both is balanced (HLD = 0).
natural surfactant(asphaltenes …)
propermixturedemulsifier
surfactant
unstableemulsion
- HLD = 0 +Salager J. L., Int. Chem. Eng., 30: 103 (1990)
Emul
sion
Stab
ility
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25 / 30Precise Asphaltene (A) – Demulsifier (D)
Mixture
for a given reservoir ... S, EACN and T are fixed,thus the Surfactant Characteristic Parameter Cp(σ or β) for the mixture must satisfy:
lnS - K ACN + σ - aT ∆T = 0
CpSYS = K ACN – lnS + aT ∆T = Constant
Optimum at HLD = 0
CpMix = xD CpD + xA CpA = CpSYS
Simple A-D surfactants mixture condition (Linear rule)
CpMix = xD CpD + (1-xD) CpA = CpSYS
Salager J. L., SPE J., 19: 271 (1979)
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"Bottle test"in practice
originalW/ O
emulsion
Add CD (hence xD)ppm of demulsifier
Homogenize
Pour inbottle
Wait some time
Measure water separation
crude
water
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Aspect of test bottles(changing formulation, i.e. type or concentration of demulsifier)
naturalsurfactant(asphaltenes)
Propermixturedemulsifier
surfactant
unstableemulsion
- HLD = 0 +
Emul
sion
Stab
ility
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28 / 30Other applications at HLD = 0
Formation dammage > microemulsions to breakdrilling fluid emulsion plugging the posousmedium close to well bottom
High solubilization in microemulsion with non-alkane oils and extended surfactants forcosmetics and pharmaceutical
Phase inversion by transitional/catastrophicmechanisms to make or destroy emulsions
Special detergency mechanisms and differenttypes of cleaning of soils, lathers …
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Applications away from HLD = 0 High stability of simple emulsions W/O and O/W
with HLD ≠ 0 … at ± 2 to 4 units (any kind)
Minimum drop size at HLD ≠ 0 but close to it (± 0.5 units) in many applications (paints,cosmetics, pharmaceuticals)
Multiple emulsions by changing WOR with twosurfactants at HLD ± 2-3 units in food, medicine ...