Surfactant EOR

12/2/2010
Success in Surfactant EOR: Avoid the Failure Mechanisms
GeorgeJ.Hirasaki PetroleumEngineering,TexasA&M November9,2010
12/2/2010
RequirementsforSurfactantEOR
UltraLowIFT MobilityControl TransportAcrossReservoir
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Phase Behavior of Anionic Surfactant, Brine, and Oil

Reed and Healy, 1977
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Interfacial Tension Correlates with the Volume Ratios in the Microemulsion

Healey, Reed, and Stenmark, 1975
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Capillary Number Required for Displacement Depends on Wettability

Stegemeier, 1975
Waterfloods
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AsuccessfulASPProcess
Dolomite sand pack
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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Layeredsandpack with19:1permeabilitycontrastabouthalfswept withwateronlybutaboutcompletelysweptwithsurfactant alternatedgas(SAG)
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OilRecoverybyGravityDrainage
9monthsinF.B.
50 40
0.05%Blend/0.3MNa2CO3,aged,122md,Soi=0.68, Sor=0.38 0.05%TDA4PO/0.3MNa2CO3,aged,90md, Soi=0.71,Sor=0.51 0.05%Blend/0.3MNa2CO3,40md,Soi=0.82,Sor=0.70
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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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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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
1:1 N67:IOS (w/w)
4:1 9:1 N67
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PhasebehaviorsofdifferentASPsolutionsafter1week
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Concentrationprofilesshowsoap/surfactantratiopassing acrossoptimalwithresultingultralowIFT
0.5PV 1.0PV
Surfactant Soap
Soap/surfactant IFT
Oilsaturation
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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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MinimumIFTnotultralow;>102 mN/m
Lowsolubilization ratio Poorsurfactantactivity Tomuchcosolvent,e.g.alcohol MinimumIFTbasedontransientvalue
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MinimumDynamicIFT
1.E+00
Dynamic IFT of fresh oil and 0.2%NI-1%Na2CO3-1%NaCl
1.E-01 IFT, mN/m
1.E-02
1.E-03
1.E-04 0 50 100 150 Time, minutes 200 250 300
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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)
Reservoirwettability Underestimatereservoirheterogeneity Foamdestabilizedbyoil
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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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Alkali (Na2CO3) reduces adsorption of surfactant on calcite Surfactant: NI Blend

4.0
without alkali
2
3.5
Adsorption Density, 10 mmol/m
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
with ~1% Na2CO3
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
Anionic surfactant on dolomite without alkali, plateau=83 2/molecule

1.0
Adsorption Density(mg/m )
0.8
0.6
0.4
Nonionic surfactant on dolomite plateau=714 2/molecule
Anionic surfactant with Na 2CO3(0.2M,0.3M,0.4M) plateau = 830 2/molecule
0.2
0.0
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
Residual Surfactant Concentration(Wt% )
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Comparisons of Anionic Surfactant (CS330) and Nonionic Surfactant (Nonylphenol-12EO-3PO) Adsorption on SILICA Powder
0.9 0.8
Nonionic surfactant on silica Adsorption Density(mg/m )

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0
2
Plateau 184 2/molecule.
CS330 on silica 5000 2/molecule
0.00
0.02
0.04
0.06
0.08
0.10
0.12
Residual Surfactant Concentration(Wt% )
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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
Without Na2CO3 With 1% Na2CO3
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
SAG fg=2/3, SAG fg=4/5, SAG fg=2/3,
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
Lower phase microemulsion
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Buoyancy Contributes to Mobilization

Pennell, Pope, Abriola, 1996
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
43

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Surfactant EOR

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12/2/2010

Success in Surfactant EOR: Avoid the Failure Mechanisms

GeorgeJ.Hirasaki PetroleumEngineering,TexasA&M November9,2010

Phase Behavior of Anionic Surfactant, Brine, and Oil

Interfacial Tension Correlates with the Volume Ratios in the Microemulsion

Capillary Number Required for Displacement Depends on Wettability

Dolomite sand pack

Layeredsandpack with19:1permeabilitycontrastabouthalfswept withwateronlybutaboutcompletelysweptwithsurfactant alternatedgas(SAG)

0.05%Blend/0.3MNa2CO3,aged,122md,Soi=0.68, Sor=0.38 0.05%TDA4PO/0.3MNa2CO3,aged,90md, Soi=0.71,Sor=0.51 0.05%Blend/0.3MNa2CO3,40md,Soi=0.82,Sor=0.70

1:1 N67:IOS (w/w)

4:1 9:1 N67

Dynamic IFT of fresh oil and 0.2%NI-1%Na2CO3-1%NaCl

1.E-01 IFT, mN/m

1.E-04 0 50 100 150 Time, minutes 200 250 300

Reservoirwettability Underestimatereservoirheterogeneity Foamdestabilizedbyoil

Alkali (Na2CO3) reduces adsorption of surfactant on calcite Surfactant: NI Blend

Adsorption Density, 10 mmol/m

with ~1% Na2CO3

Anionic surfactant on dolomite without alkali, plateau=83 2/molecule

Nonionic surfactant on dolomite plateau=714 2/molecule

Anionic surfactant with Na 2CO3(0.2M,0.3M,0.4M) plateau = 830 2/molecule

Residual Surfactant Concentration(Wt% )

Nonionic surfactant on silica Adsorption Density(mg/m )

Plateau 184 2/molecule.

CS330 on silica 5000 2/molecule

Residual Surfactant Concentration(Wt% )

Without Na2CO3 With 1% Na2CO3

SAG fg=2/3, SAG fg=4/5, SAG fg=2/3,

Lower phase microemulsion

Buoyancy Contributes to Mobilization

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