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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