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Anhydrite's Role in Reducing Anionic Surfactant Adsorption: Impact of Polyacrylate Sacrificial Agent

This study investigates the use of anhydrite and polyacrylate as sacrificial agents to reduce the adsorption of anionic surfactants on different rocks and minerals. Experimental evidence suggests that anhydrite can react with sodium carbonate to increase adsorption, while polyacrylate can potentially reduce adsorption by altering surface charges. The research explores the effectiveness of sodium polyacrylate, considering factors like molecular weight, salinity, and cost implications. Findings indicate the potential for polyacrylate to serve as a sacrificial agent in mitigating anionic surfactant adsorption, especially by modulating surface charges and influencing adsorption kinetics.

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Anhydrite's Role in Reducing Anionic Surfactant Adsorption: Impact of Polyacrylate Sacrificial Agent

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  1. Sacrificial Agent for Reducing Adsorption of Anionic Surfactants By: Hadi ShamsiJazeyi, George J. Hirasaki, Rafael Verduzco Rice University Chemical and Bio-molecular Engineering Department 17thAnnual Meeting of Rice University Consortium for Process in Porous Media April 29, 2013

  2. Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? Any role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  3. Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used? Adsorption of anionic surfactant on a positively-charged surface of rock/mineral First-layer adsorption is governed by electrostatics Second-Layer adsorption can happen at high concentrations 2

  4. Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used? Adsorption of anionic surfactant can be decreased by turning the surface charge negative when an alkali is used to raise the pH above pHpzc 2

  5. Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used? 2

  6. Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used? 2

  7. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? Any role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  8. List of surfactants Trade or descriptive name Activity (%) Chemical structure Supplier Neodol-67 (N) bC16-17(CH3-CH-CH2-O)7-SO4Na 22.88 STEPAN R-CH(OH)-CH2-CH(SO3)-R (~75%) R-CH=CH-CH(SO3-)-R (~25%) where R+R’ = C12-15 IOS15-18 (I) 21.29 STEPAN A Blend of Neodol-67-7PO-Sulfate and IOS15-18 (N:I)=4:1 NI-Blend -- -- Petro-step S13B i-C13-(PO)7–SO4Na 85.50 TIORCO 3

  9. List of polyacrylates Trade or descriptive name FLOSPERSE 1000 Activity (%) Chemical structure Supplier Sodium Polyacrylate (Mw=2200 Da) 44 SNF FLOSPERSE 3000 Sodium Polyacrylate (Mw=4500 Da) 44 SNF FLOSPERSE 15000 Sodium Polyacrylate (Mw=150 KDa) SNF 30 FLOPAM AN 995 BPM Sodium Polyacrylate (Mw~3 MDa) SNF 100 ACUMER 1100 47-49 DOW Chem. Sodium Polyacrylate (Mw=4500 Da) Poly(acrylic sodium salt) Sigma- Aldrich Sodium Polyacrylate (Mw= 5100 Da) 100 4

  10. Measurement of Adsorption  Plateau region of adsorption isotherms should be measured.  Both initial and equilibrium concentrations are measured.  Equilibrium concentration should be far enough from initial concentration, so that the noise in measurement can be neglected.  Concentration of anionic surfactant is measured using potentiometric titration.  Concentration of sodium polyacrylate is measured using a colorimetric method. 5

  11. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? Any role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  12. Anhydrite Can Affect Sodium Carbonate and Increase Adsorption of Anionic Surfactant SAR = (# of moles of sodium carbonate) / (# of moles of anhydrite) 10 9 8 Pure Calcite + 5 % Anhydrite No Sacrificial Agent (SAR=0) 7 Adsorption (mg/g) 6 SAR=0.6 5 SAR=0.7 0.9 Variable SAR (24 h Eq. time) 0.8 4 1.3 Variable SAR (72 h Eq. time) 1.2 3 2.5 2.6 1% Sodium Carbonate + Pure Calcite (SAR=∞) 2 1 Adsorption of NI-Blend, Initial Concentration of NI-Blend = 0.5 % 3.5 % NaCl Salinity, Room Temperature, 24 h Equilibrium Time 0 0.0 0.1 0.2 0.3 0.4 0.5 Equilibrium Concentration (wt%) 6

  13. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? Any role for Mw of polyacrylate? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. What is the adsorption of polyacrylate in comparison with anionic surfactant? How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  14. Characterization of the Rocks/Minerals Multi-point BET Surface Area* (m2/g) T-Method External Surface Area (m2/g) T-Method Micro-Porous Pore Volume (cc/g) Average Pore Diameter (nm) Adsorbent (Powdered Rock/Mineral) Anhydrite Percentage (%) Other Notes (99.5 wt% CaCO3) Alfa Aesar [Lot # C270009] purified calcite 1.318 1.222 5.008E-5 1.820 0.07 97.00 wt% CaCO3 (38.80 wt% Ca) Franklin Industrial Minerals industrial calcite 1.608 1.297 1.617E-5 1.780 0.11 (20.00 wt% Ca) (10.00 wt% Mg) Earthsafe Organics Carlpool Products Carlpool dolomite 0.7846 0.7426 1.726E-5 4.181 1.76 Indiana limestone 0.9851 0.9850 1.421E-7 4.363 0.82 Kocurek Industries Sigma-Aldrich [Lot # 048K0046] purified kaolinite 20.8655 19.5626 5.832E-4 4.969 0.03 powdered Berea sandstone 2.6750 2.6730 3.341E-4 1.149 NA Kocurek Industries 7

  15. Polyacrylate vs. Sodium Carbonate for Reducing Adsorption of NI-Blend on Different Rocks/Minerals Room Temperature, 24 h Equilibrium time Initial Concentration of NI-Blend = 0.5 wt% Rotary Mixer (4-5 rpm) W/O Sacrificial Agent 8 up to 18 After Addition of 1 wt % Na2CO3 7 6 After Addition of 2500 ppm of Sodium Polyacrylate (4500 Da) Adsorption (mg/g) 5 4 Almost Zero Adsorption after addition of 2500 ppm Na-Polyacrylate 3 2 1 0 Carlpool Dolomite Franklin Industrial Calcite Kaolinite Indiana LimeStone Powderized Berea Sandstone 8

  16. Reducing Adsorption of Two Different Surfactants using Polyacrylate on Carlpool Dolomite 2.5 2.5 Without Sacrificial Agent 2 NI-Blend Adsorption (mg/g) 2 1.5 S13B After adding 2500 ppm Sodium Polyacrylate (Mw=4500 Da) 1 Adsorption (mg/g) 1.5 0.5 0 1 NI-Blend S13B 0.5 0 0 500 1000 1500 2000 2500 3000 Initial Concentration of Sodium Polyacrylate (Mw=4500 Da) (ppm) 9

  17. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? Any role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  18. Reducing Adsorption of NI-Blend on Carlpool Dolomite: Polyacrylate vs. Different Chemicals 2.0 Adsorption of NI-Blend (mg/g) Polymeric Sacrificial Agents Monomer Sacrificial Agents 1.6 Sodium polyacrylates with different Mw from different vendors 1.2 0.8 0.4 0.0 10

  19. Sodium Polyacrylate vs. Other Sacrificial Agents in the Literature 2.0 Poly(EthyleneGlycol) Methyl Ether (Mw=5000 Da) Adsorption of NI-Blend on Carlpool dolomite 1.8 Sodium Metaborate 1.6 sodium carbonate 1.4 Sodium Polyacrylate (Mw=4500 Da) 1.2 (mg/g) 1.0 0.8 0.6 0.4 0.2 0.0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Concentration of added Sacrificial Agent (wt %) 11

  20. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? What is role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  21. Effect of Molecular Weight of Polyacrylate on adsorption of anionic surfactant 1.8 Sodium Propionate (Repeating Unit of Sodium Polyacrylate) 1.6 1.4 Adsorption of NI-Blend (mg/g) SNF FLOSPERSE 1000 (Sodium Polyacrylate Mw=2200 Da) 1.2 1.0 SNF FLOSPERSE 3000 (Sodium Polyacrylate Mw=4500 Da) 0.8 SNF FLOSPERSE 15000 (Sodium Polyacrylate Mw=150,000 Da) 0.6 0.4 SNF FLOPAM AN 995 BPM (Sodium Polyacrylate Mw=2.5-3.5 M Da) 0.2 0.0 0 Initial Concentration of Sacrificial Agents Added (ppm) 500 1000 1500 2000 2500 12

  22. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? What is role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  23. Adsorption of Polyacrylate (Mw=4500Da) on Carlpool Dolomite 2.0 Initial Concentration of Polymer = 0.5 %wt Initial Concentration of Surfactant Varies All solution @ 3.5 % NaCl, Room Temperature Dolomite (from Carlpool) 20% Ca, 10% Mg NI-Blend Adsorption 1.8 1.6 Adsorption (mg/g) 1.4 Compare Adsorption of NI-Blend and that of Sodium Polyacrylate (Mw=4500Da) on the same Adsorbent (Carlpool Dolomite) 1.2 1.0 0.8 Polyacrylate Adsorption 0.6 0.4 0.2 0.0 No Surfactant 0.3 wt% NI-Blend Added 0.5 wt% NI-Blend Added Adsorption of NI- Blend 13

  24. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? What is role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  25. Effect of salinity NI-Blend Adsorption Powdered Berea Sandstone NI-Blend Adsorption Carlpool Dolomite 2.5 2.0 Adsorption of NI-Blend on Powdered Adsorption of NI-Blend on Carlpool No sacrificial agent added 1.8 Berea Sandstone (mg/g) 2 1.6 After addition of 2500 ppm sodium polyacrylate (Mw=4500 Da) Dolomite (mg/g) 1.4 1.5 1.2 No sacrificial agent added 1.0 1 0.8 After addition of 2500 ppm sodium polyacrylate (Mw=4500 Da) 0.6 0.5 0.4 0.2 0 0.0 0 1 2 3 4 0 1 2 3 4 NaCl Salinity (wt %) NaCl Salinity (wt %) 14

  26. Effect of divalent ions NI-Blend Adsorption Kaolinite NI-Blend Adsorption Pure Calcite 5.0 30 On Pure Kaolinite W/O Sacrificial Agent 4.5 NI-Blend Adsorption (mg/g) 25 NI-Blend Adsorption (mg/g) On Pure Kaolonite W/ 2500 ppm Sodium Polyacrylate (4500 Da) Initial Solution Becomes Hazy 4.0 Initial Solution becomes Hazy On Pure Calcite W/O Sacrificial Agent 3.5 20 3.0 On Pure Calcite W/ 2500 ppm Sodium Polyacrylate (4500 Da) 2.5 15 2.0 10 1.5 1.0 5 0.5 0.0 0 0 1000 2000 3000 0 1000 2000 3000 Concentration of added CaCl2(ppm) Concentration of Added CaCl2(ppm) 15

  27. Effect of divalent ions NI-Blend Adsorption on Powdered Berea Sandstone NI-Blend Adsorption on Carlpool Dolomite 3.0 5 On Powdered Berea Sandstone W/O Sacrificial Agent On Carlpool Dolomite W/O Sacrificial Agent 2.5 Initial Solution Becomes Hazy 4 NI-Blend Adsorption (mg/g) NI-Blend Adsorption (mg/g) Initial Solution Becomes Hazy On Powdered Berea Sandstone W/ 2500 ppm Sodium Polyacrylate (4500 Da) On Carlpool Dolomite W/ 2500 ppm Sodium Polyacrylate (4500 Da) 2.0 3 1.5 2 1.0 1 0.5 0 0.0 0 1000 2000 3000 0 1000 2000 3000 Concentration of Added CaCl2(ppm) Concentration of Added CaCl2(ppm) 16

  28. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? What is role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  29. Economical Study: Effect of Reservoir/Injection (Alfa Dimensionless Number) * * * * * * * * * * 17

  30. Economical Study: Effect of Cost of Polyacrylate to Cost of Surfactant Cost Dimensionless Number ******* * * * 18

  31. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? What is role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  32. Dynamic Adsorption of 0.5 wt% NI-blend on Carlpool Dolomite with no sacrificial agent 19

  33. Dynamic Adsorption of 0.5 wt% NI-blend On Carlpool Dolomite with 1000 (ppm) sodium polyacrylate 20

  34. Comparison of Static and Dynamic Adsorptions PAR = (# of repeating units in polyacrylate) / (# of moles of anhydrite) 1.8 NI-Blend Adsorption dynamic test static test 1.6 1.4 1.2 (mg/g) 1 0.8 0.6 0.4 0.2 0 0 ppm sodium polyacrylate 1000 ppm sodium polyacrylate 2500 ppm sodium polyacrylate 8.9 Pure Calcite + 5% Anhydrite without Sacrificial Agent Various PAR NI-blend Adsorption 7.9 6.9 5.9 4.9 (mg/g) 3.9 2.9 1.9 0.9 Polyacrylate on Calcite no anhydrite -0.1 0 0.1 0.2 0.3 0.4 0.5 Equilibrium Concentration of NI-blend (wt%) 22

  35. Introduction and Problem Definition Materials and Methods Results and Discussions Experimental Evidence for the effect of anhydrite on adsorption of anionic surfactants? Does polyacrylate reduce adsorption of different anionic surfactants on different rocks and minerals? Why Sodium Polyacrylate? What is role for Mw of polyacrylate? What is the adsorption of polyacrylate in comparison with anionic surfactant? Effect of salinity and divalent ions on application of polyacrylate as sacrificial agent. How does application of polyacrylate affect the total material cost? How dynamic and static adsorption tests compares? Conclusions

  36. Conclusion 1. Sodium polyacrylate strongly reduces adsorption of different anionic surfactants on different rocks/minerals more than other traditional sacrificial agents even in presence of anhydrite. 2. No high molecular weight polyacrylate to be used (4500 Da is enough). 3. Adsorption of sodium polyacrylate does NOT change with presence of anionic surfactant, and is almost 1/4thof the adsorption of NI-Blend on same rock. 4. Effect of salinity and divalent ions in the brine was tested. In the absence of anhydrite, sodium polyacrylate acts as a better sacrificial agent in purified water. In the presence of anhydrite, purification of water does NOT add advantage. 5. By choosing the optimal concentration of polyacrylate the total material cost of a dynamic injection can be significantly reduced. 23

  37. THANK YOU 25

  38. Back-Up Slides 26

  39. Is Polyacrylate Affecting the titration of Surfactant? Sodium Polyacrylate has negative charge in neutral pH Does this mean that Sodium Polyacrylate can interfere with measuring concentration of anionic (sulfate-based) surfactant? Surfactant has negative charge in neutral pH 27

  40. 40 Is Polyacrylate Affecting the titration of Surfactant? (…Continued) Our strategy is to do the potentiometric titration at pH=3 so that the polyacrylate does not have any charge, but sulfate-based anionic surfactant does. 7 The surfactant used is S13B. Concentration of Surfactant = 0.75 % Concentration of Polymer Added = 0.56 % pH 3 was provided in the titration experiment using HCl solution. The source of Polyacrylate is Acumer 1100. two solutions were made. The first one has ~0.75% of surfactant at 3.5 % NaCl. The second one has ~0.75% of surfactant, ~0.56% of polymer at 3.5 % NaCl. Different sample sizes were taken from these two solutions, diluted to about 30 (g) using DI-Water, and then HCl was added and pH was measured to be about 3. Then, titration was done by potentiometric titration. W/O Polymer 6 Volume of titrant used for EP (cc) W/ Polyacrylate 5 4 y = 10.985x R² = 0.9982 3 2 1 0 1E-15 -0.2 0.2 0.4 0.6 Sample Size (cc) 28

  41. Measurement of Concentration of Sodium Polyacrylate (Colorimetric Method) Effect of S13B On Colorimetric Measurement 29

  42. Dynamic Adsorption of 0.5 wt% NI-blend on Carlpool Dolomite with 2500 (ppm) sodium polyacrylate 21

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