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12/2/2010
RequirementsforSurfactantEOR
UltraLowIFT MobilityControl TransportAcrossReservoir
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Waterfloods
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AsuccessfulASPProcess
0.2% NI, 0.5 PV, 2% NaCl, 1% Na2CO3, 5000ppm polymer,MY4 crude oil (19cp)
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
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DisplacementprofileswithASPandfoamdrive
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OilRecoverybyGravityDrainage
9monthsinF.B.
50 40
0.05%Blend/ 0.3MNa2CO3
OilRecovery,%OOIP
30 20 10 0 0.01
0.1
10
100
1000
Time,days
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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 Micelles as 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
14 Optimal NaCl Conc., % 12 10 8 6 4 2 0 1.E-02 1.E-01 1.E+00 1.E+01 Soap/Synthetic surfactant Mole Ratio NI Blend TC Blend WOR=1 (TC Blend) WOR=3 (TC Blend) WOR=10 (TC Blend) NI 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.
10 9 8 7 6 5 4 3 2 1 0
IOS
Multi-Phase Region
Phase boundary Clear solution 2 clear phases Precipitation Cloudy solution * * Cloudy after * 9 months. * *
% NaCl
1-Phase Region
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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
0.5PV 1.0PV
Surfactant Soap
Soap/surfactant IFT
Oilsaturation
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ChallengestoUltraLowIFT(3/4)
Salinitygradientversusconstantsalinity
Constantsalinitycanhavedivalents change
Mineraldissolution Ionexchange
Salinitygradientdependentonmixing
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Mixing with Formation Water and Polymer Drive Govern Transport Across Formation
Nelson, 1981
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Surfactant is Retarded by High Salinity Ahead of Slug and 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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MinimumDynamicIFT
1.E+00
1.E-02
1.E-03
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ChallengestoMobilityControl
Polymergels Polymerdegradation
Bio orthermaldegradationofxanthan Sheardegradationofpolyacrylamide,PAM ChemicaldegradationofPAM
Oxygen Iron Freeradicals
Polymersurfactantinteractions
Colloidalinteraction AdditionofhighMWoil Surfactantinmiddlephase,polymerinexcessbrine Microemulsion withviscosity
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ChallengestoMobilityControl(2/2)
Viscousemulsionsandgels
Usuallyassociatedwithoveroptimumconditions Liquidcrystal lowtemperature,possibleneed foralcohol Linearversusbranchedsurfactant(e.g.,IOS,iTD, N67)
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TransportAcrossReservoir(1/2)
Chemicalstability
Hydrolysisofsulfatesurfactant Polymerstability
Alkaliconsumption
Anhydrite(calciumsulfate)canconsumealkali Claysexchangedivalentandhydrogenions
Surfactantretention
Partitionintooilphase(overoptimum) Adsorptiononrock(oppositecharge)
Sandstoneversuscarbonate Redox potential;siderite,pyrite
Alkalicanreduceadsorptionandsequesterdivalentions Nonionicforcarbonateformation
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without alkali
2
3.5
5% NaCl
3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.0 0.5 1.0 1.5 Residual Surfactant Concentration (mmol/L) 2.0
-3
3% NaCl
5% NaCl 3% NaCl
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Comparisons of Anionic Surfactant (CS330+TDA-4PO 1:1) and Nonionic Surfactant (Nonylphenol-12EO-3PO) Adsorption on DOLOMITE Powder
1.2
Adsorption Density(mg/m )
0.8
0.6
0.4
0.2
0.0
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
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Comparisons of Anionic Surfactant (CS330) and Nonionic Surfactant (Nonylphenol-12EO-3PO) Adsorption on SILICA Powder
0.9 0.8
0.00
0.02
0.04
0.06
0.08
0.10
0.12
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TransportAcrossReservoir(2/2)
Filtrationandplugging
Injectedsurfactantsolutionmustbeclear Nonionicsurfactantmaybeadded Scalingwithdivalent,bicarbonate,andsulfate Softening,chelating,orinhibitingscale Polymer ironinteractions Filtrationpluggingscaleswithvolume/area
Producedemulsions
Modifyemulsionbreaking
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Bottle Tests: Cationic and Amphoteric Surfactants (50 ppm) & Demulsifier A (50 ppm) 21 hours equilibration
1 No added chemicals 4 Demulsifier A + Cocobetaine 2 Demulsifier A + C8TAB 5 Demulsifier A + Octylbetaine 3 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,andtransport acrossreservoirarerequiredforsuccess. SurfactantEORmustbetailoredforspecific reservoirconditions. SomereservoirsareidealforASP. Somereservoirsarechallenging. Oversightofafailuremechanismmayresult infailureoftheprocess.
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PolymerSurfactantinteractionpaper withTham
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Showoveroptimumsystemfollowed bylowsalinity
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Ultralow,equilibriumIFToverwidesalinity rangepossiblewithNa2CO3
1.E+01
1.E+00
IFT(mN/m)
1.E-01
1.E-02
1.E-03
1.E-04
3 4 Salinity(% NaCl)
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SweepefficiencywithSAG,WAG,andwaterfloodas functionofPVliquidinjected
SAG fg=2/3,
SAG
1.0 Sweep Efficiency 0.8 0.6 0.4 0.2 0.0 0 0.5 1 1.5 2 2.5 3 PV's of Liquid Injected
WAG Waterflood
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, 4
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NISurfactantBlendsImproveCalcium Tolerance
2.5% 0.5%N677PO&IOS,2%NaCl
PhaseSeparation Precipitation
2.0%
Clear
Concentration
1.5%
MultiPhaseRegion
1.0%
CaCl
0.5%
1PhaseRegion
0.0% IOS 1:4 1:2 1:1 2:1 4:1 9:1 N677PO
N677POS:IOS15/18(w/w)
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Lowerphasemicroemulsionat2%NaClhasanoilrich layerofcolloidaldispersion
Excess oil
Colloidal dispersion
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2 2 NT N Ca 2 N Ca N B sin N B
N Ca
uw w ow cos
g k krw NB ow cos
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