surfactant eor
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RequirementsforSurfactantEOR
UltraLowIFT
MobilityControl
TransportAcrossReservoir
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Phase Behavior of Anionic Surfactant, Brine, and OilReed and Healy, 1977
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Interfacial Tension Correlates with the Volume Ratiosin the Microemulsion
Healey, Reed, and Stenmark, 1975
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Capillary Number Required forDisplacement Depends on Wettability
Stegemeier, 1975
Waterfloods
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0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.90 1.50
Injected Pore Volumes
AsuccessfulASPProcessDolomite
sand pack
0.2% NI, 0.5 PV, 2% NaCl, 1% Na2CO3, 5000ppm polymer,MY4 crude oil (19cp)
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DisplacementprofileswithASPandfoamdrive
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Layeredsandpack with19:1permeabilitycontrastabouthalfswept
withwateronlybutaboutcompletelysweptwithsurfactant
alternatedgas(SAG)
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OilRecoverybyGravityDrainage
0
10
20
30
40
50
0.01 0.1 1 10 100 1000
Time,days
OilR
ecovery,%OOIP
0.05%TDA4PO/0.3MNa2CO3,aged,90md,
Soi=0.71,Sor=0.51
0.05%Blend/0.3MNa2CO3,aged,122md,Soi=0.68,Sor=0.38
0.05%Blend/0.3MNa2CO3,40md,Soi=0.82,Sor=0.70
9
months
in
F.B.0.05%Blend/
0.3MNa2CO3
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ConditionsFavorableorChallengingforSurfactantEOR
Favorable
Low moderatesalinity
Moderatetemperature
Cleansandstone
Noanhydrite(CaSO4)
Waterwet
Med highpermeability
Homogeneous HighSorw Onshore
DoASPfloodASAP
Challenging
Highsalinity
Loworhightemperatures
Carbonate
Anhydrite
Oilwet
Lowpermeability
Fractured LowSorw Offshore
Doresearch
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ChallengestoUltraLowIFT(1/4)
Systembecomingoveroptimumbecause
Mixingwithhighersalinityformationbrine
Ionexchangewithclays
Dissolutionofanhydrite
LiveoildifferentfromSTO;GORdependent
Oil/waterratioisparameterinASP
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Clays Act Like an Ion-Exchange Bed and Micellesas Mobile Ion-Exchange Media
Hirasaki, 1982; Gupta, 1980
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ChallengestoUltraLowIFT(1/4)
Systembecomingoveroptimumbecause
Mixingwithhighersalinityformationbrine
Ionexchangewithclays
Dissolutionofanhydrite
LiveoildifferentfromSTO;GORdependent
Oil/waterratioisparameterinASP
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Optimalsalinityofalkalinesurfactantsystemisfunctionof
surfactantconcentrationandwater/oilratio
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Optimalsalinitycorrelateswith
soap/surfactantratio
0
2
4
6
8
10
12
14
1.E-02 1.E-01 1.E+00 1.E+01
Soap/Synthetic surfactant Mole Ratio
OptimalNaClConc.,
%
WOR=1 (TC Blend)
WOR=3 (TC Blend)
WOR=10 (TC Blend)
NI blend
NI Blend
TC Blend
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Simulationsshowhighrecoverypossiblewithcombinationsof
injectedsalinityandsystemsoap/surfactantratio
Soap/(Soap+Surfactant)
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ChallengestoUltraLowIFT(2/4)
Injectedunderoptimumbecause
Surfactantprecipitationatoptimalsalinity
Polymerseparatesatoptimalsalinity
Surfactantretentionhighatoptimalsalinity
SoapgeneratedinsituwithASP
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Thereissynergisminblendingsurfactants.
* Cloudy after9 months.
Phase boundary
Precipitation
Clear solution
2 clear phases
Cloudy solution%
NaCl
0
12
3
4
5
6
7
8
910
IOSN67
1:1 4:1
N67:IOS (w/w)
9:1
1-Phase
Region
*
*
*
*
Multi-PhaseRegion
Phase boundary
Precipitation
Clear solution
2 clear phases
Cloudy solution%
NaCl
0
12
3
4
5
6
7
8
910
IOSN67
1:1 4:1
N67:IOS (w/w)
9:1
1-Phase
Region
*
*
*
*
Multi-PhaseRegion
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ChallengestoUltraLowIFT(2/4)
Injectedunderoptimumbecause
Surfactantprecipitationatoptimalsalinity
Polymerseparatesatoptimalsalinity
Surfactantretentionhighatoptimalsalinity
SoapgeneratedinsituwithASP
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PhasebehaviorsofdifferentASPsolutionsafter1week
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ChallengestoUltraLowIFT(2/4)
Injectedunderoptimumbecause
Surfactantprecipitationatoptimalsalinity
Polymerseparatesatoptimalsalinity
Surfactantretentionhighatoptimalsalinity
SoapgeneratedinsituwithASP
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Concentrationprofilesshowsoap/surfactantratiopassing
acrossoptimalwithresultingultralowIFT
Surfactant
Soap
Soap/surfactant
IFT
Oilsaturation
0.5PV 1.0PV
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ChallengestoUltraLowIFT(3/4)
Salinitygradientversusconstantsalinity
Constantsalinitycanhavedivalents change
Mineraldissolution
Ionexchange
Salinitygradientdependentonmixing
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Mixing with Formation Water and Polymer DriveGovern Transport Across Formation
Nelson, 1981
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Surfactant is Retarded by High Salinity Ahead of Slugand Mobilized by Low Salinity Behind Slug
Hirasaki, 1983, Nelson, 1982
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ChallengestoUltraLowIFT(3/3)
MinimumIFTnotultralow;>102 mN/m
Lowsolubilization ratio
Poorsurfactantactivity
Tomuchcosolvent,e.g.alcohol
MinimumIFTbasedontransientvalue
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Minimum DynamicIFT
Dynamic IFT of fresh oil and 0.2%NI-1%Na2CO3-1%NaCl
1.E-04
1.E-03
1.E-02
1.E-01
1.E+00
0 50 100 150 200 250 300Time, minutes
IFT,mN/m
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ChallengestoMobilityControl
Polymergels
Polymer
degradationBio orthermaldegradationofxanthan
Sheardegradationofpolyacrylamide,PAM
ChemicaldegradationofPAM Oxygen
Iron
Freeradicals
PolymersurfactantinteractionsColloidalinteraction
Additionof highMWoil
Surfactantinmiddlephase,polymerinexcessbrine
Microemulsion withviscosity
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ChallengestoMobilityControl(2/2)
ViscousemulsionsandgelsUsuallyassociatedwithoveroptimumconditions
Liquidcrystal lowtemperature,possibleneedforalcohol
Linearversusbranchedsurfactant(e.g.,IOS,iTD,N67)
Reservoirwettability Underestimatereservoirheterogeneity
Foamdestabilizedbyoil
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TransportAcrossReservoir(1/2)
Chemicalstability
HydrolysisofsulfatesurfactantPolymerstability
AlkaliconsumptionAnhydrite(calciumsulfate)canconsumealkaliClaysexchangedivalentandhydrogenions
SurfactantretentionPartitionintooilphase(overoptimum)Adsorptiononrock(oppositecharge)
Sandstoneversuscarbonate Redox potential;siderite,pyrite
Alkalicanreduceadsorptionandsequesterdivalentions
Nonionicforcarbonateformation
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Alkali (Na2CO3) reduces adsorption of surfactant on calcite
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
0.0 0.5 1.0 1.5 2.0Residual Surfactant Concentration (mmol/L)
Adsor
ptionDensity,10-3mmol/m2
3% NaCl
5% NaCl
Surfactant: NI Blend
5% NaCl
without alkali
3% NaCl
with ~1% Na2CO3
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0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14
Residual Surfactant Concentration(Wt%)
AdsorptionDensity(mg/m2)
Anionic surfactant on dolomite without alkali, plateau=83 2/molecule
Anionic surfactantwith Na2CO3(0.2M,0.3M,0.4M)
plateau = 830 2/molecule
Nonionic surfactanton dolomite
plateau=714 2/molecule
Comparisons of Anionic Surfactant (CS330+TDA-4PO 1:1) and NonionicSurfactant (Nonylphenol-12EO-3PO) Adsorption on DOLOMITE Powder
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0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.00 0.02 0.04 0.06 0.08 0.10 0.12
Residual Surfactant Concentration(Wt%)
AdsorptionDensity(mg/m2)
Nonionic surfactant on silica
CS330 on silica
5000 2/molecule
Plateau
184 2/molecule.
Comparisons of Anionic Surfactant (CS330) and Nonionic Surfactant(Nonylphenol-12EO-3PO) Adsorption on SILICA Powder
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TransportAcrossReservoir(2/2)
FiltrationandpluggingInjectedsurfactantsolutionmustbeclear
Nonionicsurfactantmaybeadded
Scalingwithdivalent,bicarbonate,andsulfate
Softening,chelating,orinhibitingscale
Polymer ironinteractions
Filtrationpluggingscaleswithvolume/area
ProducedemulsionsModifyemulsionbreaking
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Bottle Tests: Cationic and Amphoteric Surfactants (50 ppm) &Demulsifier A (50 ppm)
21 hours equilibration
1 2 3 4 51 No added chemicals 4 Demulsifier A + Cocobetaine
2 Demulsifier A + C8TAB 5 Demulsifier A + Octylbetaine3 Demulsifier A + capryl/capraamidopropyl betaine
C8TAB diluted to 2.5wt% in water, Amphoterics diluted to 5wt.% in
water, and Demulsifier A diluted to 5 wt.% in Heavy Aromatic Naphtha.
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Conclusions
Lowtension,mobilitycontrol,andtransportacrossreservoirarerequiredforsuccess.
SurfactantEORmustbetailoredforspecificreservoirconditions.
SomereservoirsareidealforASP.
Somereservoirsarechallenging.
Oversightofafailuremechanismmayresultinfailureoftheprocess.
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PolymerSurfactantinteractionpaper
withTham
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Showoveroptimumsystemfollowed
bylowsalinity
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Ultralow,equilibriumIFToverwidesalinity
rangepossiblewithNa2CO3
1.E-04
1.E-03
1.E-02
1.E-01
1.E+00
1.E+01
0 1 2 3 4 5 6Salinity(% NaCl)
IFT(mN/m
Without Na2CO3
With 1% Na2CO3
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SweepefficiencywithSAG,WAG,andwaterfloodas
functionofPVliquidinjected
0.0
0.2
0.4
0.6
0.8
1.0
0 0.5 1 1.5 2 2.5 3
PV's of Liquid Injected
SweepEfficiency
SAG fg=2/3,
SAG fg=2/3,
SAG fg=4/5,
SAG fg=2/3,
SAG fg=3/4,
SAG fg=2/3,
SAG fg=1/3,
SAG fg=1/2,WAG fg=4/5,
WAG fg=3/4,
WAG fg=2/3,
WAG fg=1/2,
Water fg=0,
SAG
WAG
Waterflood
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NISurfactantBlendsImproveCalcium Tolerance
1PhaseRegion
MultiPhaseRegion
N677POS:IOS15/18(w/w)
0.5%N677PO&IOS,2%NaCl
0.0%
0.5%
1.0%
1.5%
2.0%
2.5%
N677PO
CaCl
2
Concentration
PhaseSeparation
Precipitation
Clear
IOS 1:4 1:2 1:1 2:1 4:1 9:1
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Lowerphasemicroemulsionat2%NaClhasanoilrich
layerofcolloidaldispersion
Colloidal
dispersion
Lower phasemicroemulsion
Excessoil
Colloidal
dispersion
Lower phasemicroemulsion
Excessoil
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Buoyancy Contributes to MobilizationPennell, Pope, Abriola, 1996
2 22 sin
cos
cos
T Ca Ca B B
w wCa
ow
rwB
ow
N N N N N
uN
g k kN
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