Sodium Ions for Optimal Salinity of ASP Lei Ding Maura C. Puerto Clarence A. Miller George J. Hirasaki 2015-04-22 1 Presentation for the Rice University.

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Presentation transcript:

Sodium Ions for Optimal Salinity of ASP Lei Ding Maura C. Puerto Clarence A. Miller George J. Hirasaki Presentation for the Rice University Consortium for Processes in Porous Media 19 th Annual Meeting

Contents 2  Single Sodium Salt/Single Surfactant/Alcohol/ Model Oil System  Sodium Salts Mixture/Surfactant Mixture/ Alcohol/ Model Oil System  Sodium Activity as a function of Soap/Surfactant Ratio (Alkali/Oleic Acid/Surfactant/Alcohol/ Model Oil)

Contents 3  Single Sodium Salt/Single Surfactant/Alcohol/ Model Oil System  Sodium Salts Mixture/Surfactant Mixture/ Alcohol/ Model Oil System  Sodium Activity as a function of Soap/Surfactant Ratio (Alkali/Oleic Acid/Surfactant/Alcohol/ Model Oil)

Optimal Salinity of Single Anionic Surfactants 2% Dodecyl Benzene Sulfonate (OA) /2% 2-Butanol (OA)/Toluene/Na 2 CO 3 4 In Aqueous Phase

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) 2% Dodecyl Benzene Sulfonate/ 2% 2-Butanol/ NaCl NaOH Na 2 CO

Activity Coefficient Models Activity Coefficient (Phreeqc® Software): Extended Debye–Hückel Equation: Pitzer Equation: 6

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 2% Dodecyl Benzene Sulfonate/ 2% 2-Butanol/ NaCl NaOH Na 2 CO

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 2% Dodecyl Benzene Sulfonate/ 2% 2-Butanol/ NaCl NaOH Na 2 CO % IOS /2.7% NaCl NaOH Na 2 CO

Contents 9  Single Sodium Salt/Single Surfactant/Alcohol/ Model Oil System  Sodium Salts Mixture/Surfactant Mixture/ Alcohol/ Model Oil System  Sodium Activity as a function of Soap/Surfactant Ratio (Alkali/Oleic Acid/Surfactant/Alcohol/ Model Oil)

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 2.7% IOS /2.7% 2-Butanol/Octane NaCl NaOH Na 2 CO NaCl+NaOH NaCl+Na 2 CO Na 2 CO 3 +NaOH % SDS/2% 1- Butanol/Heptane NaClNo Classical Phase Behavior Obtained NaOH Na 2 CO NaCl+NaOH NaCl+Na 2 CO Influence of Brine Mixtures on Optimal Salinity 10

Mixtures of Anionic Surfactants, Mixtures of Sodium Salts Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) 3% S 13 D+3% IOS NaCl NaOH Na 2 CO Na 2 SO NaCl+NaOH NaCl+Na 2 CO Influence of Brine Mixtures on Optimal Salinity 11

Contents 12  Single Sodium Salt/Single Surfactant/Alcohol/ Model Oil System  Sodium Salts Mixture/Surfactant Mixture/ Alcohol/ Model Oil System  Sodium Activity as a function of Soap/Surfactant Ratio (Alkali/Oleic Acid/Surfactant/Alcohol/ Model Oil)

13 Background Mixing Rule for mixtures of anionic surfactants Liu, S. (2010). Alkaline/Surfactant/Polymer Processes: Wide Range of Conditions for Good Recovery. SPEJ, SPE PA,

Optimal salinity of Oleic Acid Concentration (%) TAN (mg/ g oil) 2- Butanol, % Alkali Type Alkali Molarity (M) Ionic Strength (M) Weight Percent % Sodium Equivalence (M) Sodium Activity (M) Solubilization Parameter NaOH Na 2 CO NaOH Na 2 CO NaOH Na 2 CO Comparison Between Different Alkalis 14 Sodium Activity at optimal depends on alcohol concentration! Chun Huh Model:

Optimal Salinity (Na 2 CO 3 ) of Oleic Acid 15 Oleic Acid Concentration (%) TAN (mg/g oil) Optimal Molarity (M/L) Sodium Activity (M/L) % 2-Butanol

Y% Oleic Acid+ X% SDS+7.5% 2- Butanol/Octane 16

1) When a mixture of sodium salts is used, the sodium activity at optimal conditions is invariant; 2) Solubilization parameter at optimal was independent of anions for sulfate and sulfonate surfactants; 3) Solubilization parameter at optimal for oleic acid depends on alkali types; a higher solubilization parameter is obtained when Na 2 CO 3 is used than that of NaOH; 4) A good correlation is obtained when the total sodium activity is used in the log mean mixing rule for optimal salinity. Conclusions 17

Acknowledgement This work was financially supported by Rice University Consortium for Processes in Porous Media Thank you! Questions? 18

Backup 19

Optimal Salinity of Single Anionic Surfactants 2% Dodecyl Benzene Sulfonate/2% 2-Butanol/Toluene/NaCl systems 20

Optimal Salinity of Single Anionic Surfactants 2% Dodecyl Benzene Sulfonate/2% 2-Butanol/Toluene/NaOH systems 21

pH Dependent Phase Behavior Qutubuddin S., Miller C.A., Journal of Colloid and Interface Science,

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 2.7% IOS /2.7% 2-Butanol/Octane NaCl NaOH Na 2 CO % IOS /2.7% 2-pentanol/Octane NaCl NaOH Na 2 CO % IOS /2.7% 1-Hexanol/Octane NaCl >18.2 NaOH >18.2 Na 2 CO >18.2 Influence of Alcohol on Optimal Salinity 23

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 2% Dodecyl Benzene Sulfonate/2% 2- Room Temperature NaCl NaOH Na 2 CO % IOS /2.7% 2- Room Temperature NaCl NaOH Na 2 CO % IOS /2.7% 2- Room Temperature NaCl NaOH Na 2 CO Influence of Temperature on Optimal Salinity 24

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 2% Dodecyl Benzene Sulfonate/2% 2- NaCl NaOH Na 2 CO % IOS /2.7% NaCl NaOH Na 2 CO % IOS /2.7% NaCl NaOH Na 2 CO Influence of Temperature on Optimal Salinity 25

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 2% Dodecyl Benzene Sulfonate/2% 2- Butanol/Toluene NaCl NaOH Na 2 CO % Dodecyl Benzene Sulfonate/3% 2- Butanol/Toluene NaCl NaOH Na 2 CO Influence of Surfactant/Alcohol Concentration on Optimal Salinity 26

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 2.7% IOS /2.7% 2-Butanol/Octane NaCl NaOH Na 2 CO % SDS/2% 1- Butanol/Heptane NaClNo Classical Phase Behavior Obtained NaOH Na 2 CO % IOS /2.7% 2-Butanol/Octane NaCl+NaOH NaCl+Na 2 C O Na 2 CO 3 +Na OH % SDS/2% 1- Butanol/Heptane NaCl+NaOH NaCl+Na 2 C O Influence of Brine Mixtures on Optimal Salinity 27

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 3% Dodecyl Benzene Sulfonate/3% 2- Butanol/Octane NaCl NaOH Na 2 CO % Dodecyl Benzene Sulfonate/3% 2- Butanol/Toluene NaCl NaOH Na 2 CO % AOT/Dodecane No Classical Phase Behavior Obtained 1.35% IOS /1.35% 2- Butanol/Octane No Classical Phase Behavior Obtained Influence of Oil Type on Optimal Salinity 28

Optimal Salinity of Single Anionic Surfactants Surfactant/Alcohol (Overall Concentration) Electrolytes Type Molarity (M) Ionic Strength (M) Weight Percent (%) Sodium Equivalence (M) Sodium Activity (M) V o /V s V w /V s 2% Dodecyl Benzene Sulfonate/2% 2- Butanol/Toluene NaCl NaOH Na 2 CO % IOS /2.7% 2-Butanol/Octane NaCl NaOH Na 2 CO

X% Oleic Acid+ 6% 2-Butanol/Decane Procedure: 1) Salinity Scan (X% Na 2 CO 3 ) Stock concentrated brine, DIW, stock surfactant solution, Decane 2) 2.0% oleic acid + 6% 2-Butanol (overall) 2.67% oleic acid + 6% 2-Butanol (overall) 4.0% oleic acid + 6% 2-Butanol (overall) 5.3% oleic acid + 6% 2-Butanol (overall) 3) Sodium Activity at Optimal calculated by Phreeqc software 30

2.25% Oleic Acid+ X% IOS+6.75% 2- Butanol/Octane Procedure: 1) Prepare 20% IOS in DI Water 2) Salinity Scan (4% Na 2 CO 3 + NaCl) Stock concentrated brine, DIW, stock surfactant solution, Octane 3) 2.25% oleic acid % 2-Butanol (overall) 2.25% oleic acid % 2-Butanol (overall) +0.5% IOS (overall) 2.25% oleic acid % 2-Butanol (overall) +1.0% IOS (overall) 2.25% oleic acid % 2-Butanol (overall) +2.0% IOS (overall) 2.25% oleic acid % 2-Butanol (overall) +3.0% IOS (overall) 2.25% oleic acid % 2-Butanol (overall) +4.0% IOS (overall) 1.68 % IOS % 2-Butanol (overall) 5) Sodium Activity at Optimal calculated by Phreeqc software 6) Optimal salinity as a function of IOS molar fraction IOS molarity: 333 (IOS 16.5 ) 31

X% DBS+ Y% 2-Butanol/Toluene SystemOptimal Activity, Na +,M 2%DBS+3%2-Butanol %DBS+3%2-Butanol %DBS+2%2-Butanol %DBS+2%2-Butanol

Y% Oleic Acid+ X% SDS+2-Butanol/Octane Supplement Data Points: 1) 2.5% oleic acid + 7.5% 2-Butanol (overall) +2.0% SDS (overall) 2.5% oleic acid + 7.5% 2-Butanol (overall) +2.5% SDS (overall) 2) Prepare 33% Oleic Acid+67% 2-Butanol 3.8% oleic acid + 7.5% 2-Butanol (overall) +1.5% SDS (overall) 3.8% oleic acid + 7.5% 2-Butanol (overall) +1.0% SDS (overall) 3) SDS/2-Butanol added separately (solubility) 2.5% SDS+7.5% 2-Butanol (overall) 1.5% SDS+7.5% 2-Butanol (overall) 3) 1.0% Oleic acid in Octane (0.5% overall) 0.725% SDS+7.5% 2-Butanol (overall); 1.16% SDS+7.5% 2- Butanol (overall); 2.4% SDS+7.5% 2-Butanol (overall) *In order to demonstrate Na activity at opt. conditions depends on Xsoap but not on total surfactant concentration, a point that overlap point from the experiments with fixed oleic acid and variable SDS was conducted. i.e., a couple of examples of points with the same surfactant fraction of soap (Xsoap on your plots) but with different overall surfactant concentrations % Oleic Acid+1.5% SDS; 2.5% Oleic Acid+ 1% SDS

Optimal Salinity of Oleic Acid 34

Optimal Salinity of Oleic Acid 35

36 Background 1% Na 2 CO 3 Liu, S. (2008). Favorable Attributes of Alkaline-Surfactant-Polymer Flooding. SPEJ, SPE PA,, 5-16.

37 Brine: 4% Na 2 CO 3 + NaCl 2.25% Oleic Acid+ X% IOS % 2- Butanol/Octane

38 Brine: 4% Na 2 CO 3 + NaCl 2.25% Oleic Acid+ X% IOS % 2- Butanol/Octane

Y% Oleic Acid+ X% SDS+7.5% 2- Butanol/Octane 39 Brine: 2% Na 2 CO 3 + NaCl

Y% Oleic Acid+ X% SDS+2- Butanol/Octane 40 Brine: 6% Na 2 CO 3 + NaCl 3.8% Oleic Acid+1.5% SDS; 2.5% Oleic Acid+ 1% SDS