12/2/2010

Success in Surfactant EOR: Avoid the Failure Mechanisms

George J. Hirasaki Petroleum Engineering, Texas A&M November 9, 2010

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Requirements for Surfactant EOR
• Ultra‐Low IFT • Mobility Control • Transport Across Reservoir

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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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12/2/2010 Capillary Number Required for Displacement Depends on Wettability Stegemeier. 1975 Waterfloods 5 .

1% Na2CO3.55 0.70 0.65 0.50 0. 0.35 0.2% NI.5 PV.15 0.90 1.25 0.75 0.10 0.30 0.MY4 crude oil (19cp) 0.12/2/2010 A successful ASP Process  Dolomite sand pack 0.45 0.20 0.40 0. 2% NaCl.60 0. 5000ppm polymer.50 Injected Pore Volumes 6 .05 0.

12/2/2010 Displacement profiles with ASP and foam drive 7 .

12/2/2010 Layered sandpack with 19:1 permeability contrast about half‐swept  with water only but about completely swept with surfactant‐ alternated‐gas (SAG) 8 .

 aged.38 0. 40 md. 90 md.70 0.05% Blend/0.3M Na2CO3.  Soi=0.05% Blend/ 0.12/2/2010 Oil Recovery by Gravity Drainage 9 months in F.71.  Sor=0.51 0.68. days 9 . aged.B. Sor=0.3M Na2CO3. Sor=0.3M Na2CO3 Oil Recovery.01 0.3M Na2CO3.05%Blend/0. Soi=0. 50 40 0.1 1 10 100 1000 Time. 122 md. Soi=0. %OOIP 30 20 10 0 0.82.05% TDA‐4PO/0.

12/2/2010 Conditions Favorable or Challenging for Surfactant EOR  Favorable • • • • • • • • • • Low – moderate salinity Moderate temperature Clean sandstone No anhydrite (CaSO4) Water‐wet Med ‐ high permeability Homogeneous High Sorw On shore Do ASP flood ASAP Challenging • • • • • • • • • • High salinity Low or high temperatures Carbonate Anhydrite Oil‐wet Low permeability Fractured Low Sorw Off shore Do research 10 .

 GOR dependent – Oil/water ratio is parameter in ASP 11 .12/2/2010 Challenges to Ultra‐Low IFT (1/4) • System becoming over‐optimum because – Mixing with higher salinity formation brine – Ion exchange with clays – Dissolution of anhydrite – Live oil different from STO.

12/2/2010 Clays Act Like an Ion-Exchange Bed and Micelles as Mobile Ion-Exchange Media Hirasaki. 1980 12 . Gupta. 1982.

 GOR dependent – Oil/water ratio is parameter in ASP 13 .12/2/2010 Challenges to Ultra‐Low IFT (1/4) • System becoming over‐optimum because – Mixing with higher salinity formation brine – Ion exchange with clays – Dissolution of anhydrite – Live oil different from STO.

12/2/2010 Optimal salinity of alkaline surfactant system is function of  surfactant concentration and water/oil ratio 14 .

E-02 1.. % 12 10 8 6 4 2 0 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 15 .E-01 1.12/2/2010 Optimal salinity correlates with  soap/surfactant ratio 14 Optimal NaCl Conc.E+00 1.

12/2/2010 Simulations show high recovery possible with combinations of  injected salinity and system soap/surfactant ratio Soap/(Soap+Surfactant) 16 .

12/2/2010 Challenges to Ultra‐Low IFT (2/4) • Injected under‐optimum because – Surfactant precipitation at optimal salinity – Polymer separates at optimal salinity – Surfactant retention high at optimal salinity – Soap generated in situ with ASP 17 .

12/2/2010 There is synergism in blending surfactants. 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 18 .

12/2/2010 Challenges to Ultra‐Low IFT (2/4) • Injected under‐optimum because – Surfactant precipitation at optimal salinity – Polymer separates at optimal salinity – Surfactant retention high at optimal salinity – Soap generated in situ with ASP 19 .

12/2/2010 Phase behaviors of different ASP solutions after 1 week  20 .

12/2/2010 Challenges to Ultra‐Low IFT (2/4) • Injected under‐optimum because – Surfactant precipitation at optimal salinity – Polymer separates at optimal salinity – Surfactant retention high at optimal salinity – Soap generated in situ with ASP 21 .

5 PV 1.12/2/2010 Concentration profiles show soap/surfactant ratio passing  across optimal with resulting ultra‐low IFT 0.0 PV Surfactant Soap Soap/surfactant IFT Oil saturation 22 .

12/2/2010 Challenges to Ultra‐Low IFT (3/4) • Salinity gradient versus constant salinity – Constant salinity can have divalents change • Mineral dissolution • Ion exchange – Salinity gradient dependent on mixing 23 .

12/2/2010 Mixing with Formation Water and Polymer Drive Govern Transport Across Formation Nelson. 1981 24 .

1983. Nelson.12/2/2010 Surfactant is Retarded by High Salinity Ahead of Slug and Mobilized by Low Salinity Behind Slug Hirasaki. 1982 25 .

 e.g.12/2/2010 Challenges to Ultra‐Low IFT (3/3) • Minimum IFT not ultra‐low. alcohol – Minimum IFT based on transient value 26 . >10‐2 mN/m – Low solubilization ratio – Poor surfactant activity – To much co‐solvent.

E+00 Dynamic IFT of fresh oil and 0. mN/m 1.2%NI-1%Na2CO3-1%NaCl 1.E-01 IFT.E-04 0 50 100 150 Time. minutes 200 250 300 27 .E-02 1.12/2/2010 Minimum  Dynamic IFT 1.E-03 1.

 PAM – Chemical degradation of PAM • Oxygen • Iron • Free radicals • Polymer‐surfactant interactions – – – – Colloidal interaction Addition of  high MW oil Surfactant in middle phase. polymer in excess brine Microemulsion with viscosity 28 .12/2/2010 Challenges to Mobility Control • Polymer gels • Polymer degradation – Bio‐ or thermal degradation of xanthan – Shear degradation of polyacrylamide.

12/2/2010 Challenges to Mobility Control (2/2) • Viscous emulsions and gels – Usually associated with over‐optimum conditions – Liquid crystal – low temperature. i‐TD.g.. IOS. possible need  for alcohol  – Linear versus branched surfactant (e.  N67) • Reservoir wettability • Underestimate reservoir heterogeneity • Foam destabilized by oil 29 .

 siderite. pyrite – Alkali can reduce adsorption and sequester divalent ions – Nonionic for carbonate formation  30 .12/2/2010 Transport Across Reservoir (1/2) • Chemical stability – Hydrolysis of sulfate surfactant – Polymer stability • Alkali consumption – Anhydrite (calcium sulfate) can consume alkali – Clays exchange divalent and hydrogen ions • Surfactant retention – Partition into oil phase (over‐optimum) – Adsorption on rock (opposite charge) • Sandstone versus carbonate • Redox potential.

0 -3 3% NaCl with ~1% Na2CO3 5% NaCl 3% NaCl 31 .0 0.0 1.0 2.0 0. 10 mmol/m 5% NaCl 3.5 2.5 1.0 1.5 Residual Surfactant Concentration (mmol/L) 2.5 0.5 1.0 without alkali 2 3.12/2/2010 Alkali (Na2CO3) reduces adsorption of surfactant on calcite Surfactant: NI Blend 4.0 0.5 Adsorption Density.

12 0.4 Nonionic surfactant on dolomite plateau=714 Å2/molecule Anionic surfactant with Na 2CO3(0.0.6 0.02 0.8 0.0.2 0.14 Residual Surfactant Concentration(Wt% ) 32 .4M) plateau = 830 Å2/molecule 0. plateau=83 Å2/molecule 1.12/2/2010 Comparisons of Anionic Surfactant (CS330+TDA-4PO 1:1) and Nonionic Surfactant (Nonylphenol-12EO-3PO) Adsorption on DOLOMITE Powder 1.04 0.08 0.10 0.3M.06 0.0 Adsorption Density(mg/m ) 2 0.2M.0 0.2 Anionic surfactant on dolomite without alkali.00 0.

10 0.6 0.04 0.9 0.0 2 Plateau 184 Å2/molecule.02 0.2 0.06 0.3 0.1 0.5 0.00 0.8 Nonionic surfactant on silica Adsorption Density(mg/m ) 0.12 Residual Surfactant Concentration(Wt% ) 33 .08 0. CS330 on silica 5000 Å2/molecule 0.12/2/2010 Comparisons of Anionic Surfactant (CS330) and Nonionic Surfactant (Nonylphenol-12EO-3PO) Adsorption on SILICA Powder 0.4 0.7 0.

 chelating.12/2/2010 Transport Across Reservoir (2/2) • Filtration and plugging – Injected surfactant solution must be clear – Nonionic surfactant may be added  – Scaling with divalent. or inhibiting scale – Polymer – iron interactions – Filtration plugging scales with volume/area • Produced emulsions – Modify emulsion breaking 34 . bicarbonate. and sulfate – Softening.

5wt% in water.% in Heavy Aromatic Naphtha. 35 .% in water. Amphoterics diluted to 5wt. and Demulsifier A diluted to 5 wt.12/2/2010 Bottle Tests: Cationic and Amphoteric Surfactants (50 ppm) & Demulsifier A (50 ppm) 21 hours equilibration 1 2 3 4 5 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.

• Some reservoirs are challenging.  36 . and transport  across reservoir are required for success. • Surfactant EOR must be tailored for specific  reservoir conditions.12/2/2010 Conclusions • Low tension. mobility control. • Some reservoirs are ideal for ASP. • Over sight of a failure mechanism may result  in failure of the process.

12/2/2010 Polymer Surfactant interaction paper  with Tham 37 .

12/2/2010 Show over‐optimum system followed  by low salinity 38 .

E-01 1.E+00 IFT(mN/m) 1.E-04 0 1 2 3 4 Salinity(% NaCl) 5 6 39 .E-02 1. equilibrium IFT over wide salinity  range possible with Na2CO3 1.E-03 1.12/2/2010 Ultra‐low.E+01 Without Na2CO3 With 1% Na2CO3 1.

0 0 0. WAG fg=2/3. SAG fg=2/3.6 0.2 0. WAG.5 2 2. SAG fg=4/5.8 0. Water fg=0. SAG fg=2/3.4 0. 4 40 .5 1 1. WAG fg=3/4.12/2/2010 Sweep efficiency with SAG.0 Sweep Efficiency 0.5 3 PV's of Liquid Injected SAG fg=2/3. WAG fg=1/2. and waterflood as  function of PV liquid injected SAG fg=2/3. SAG fg=1/2. WAG Waterflood SAG fg=3/4. SAG fg=1/3. WAG fg=4/5. SAG 1.

0% CaCl  0.0% Clear Concentration 1.5% 2 1‐Phase Region 0. 2% NaCl Phase Separation Precipitation 2.5% Multi‐Phase Region 1.12/2/2010 NI Surfactant Blends Improve Calcium Tolerance 2.5% N67‐7PO&IOS.5% 0.0% IOS 1:4 1:2 1:1 2:1 4:1 9:1 N67‐7PO N67‐7PO S:IOS‐15/18 (w/w) 41 .

12/2/2010 Lower‐phase microemulsion at 2% NaCl has an oil‐rich  layer of colloidal dispersion Excess oil Colloidal dispersion Lower phase microemulsion 42 .

Pope. Abriola.12/2/2010 Buoyancy Contributes to Mobilization Pennell. 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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