1. Synthesis and Application of High Molecular Weight Surfactants Surfactants Bringing Chemical IOR TO THE NEXT GENERATION 104 th AOCS Annual Meeting & Expo April 28 – May 1, 2013, Montreal Canada

2. Presentation Outline Special requirements for CEOR surfactants Limitations of some CEOR surfactants Fatty acid derived CEOR surfactants Internal olefin ether sulfonates Alkylaryl ether carboxylates Ether amine sulfonates Other commercial applications

3. Injection fluid Injection Pump Injection well Producing well Oil Chemical EOR ASP, SP, Low Surfactant Added Water Flood, Foam, etc. Single surfactant component – no co-surfactant, no-co-solvent, no salinity optimization, etc. Low IFT, Low adsorption Compatibility with the reservoir conditions and the other additives in the injection fluid Thermo Stability Minimal phase trapping, Chromatographic separation

4. Examples of High Molecular Weight Anionic Surfactants for CEOR Tri-styrylphenol ether sulfates Guerbet alcohol ether sulfates Guerbet alcohol ether carboxylates Extended chain ether sulfates Polypropoxylated alcohol ether sulfates Internal and alpha olefin sulfonates

5. Limitations of Some CEOR Surfactants TempAdsorptionElectrolytes Ether SulfatesX √√ Ether Sulfonates √√√√ Ether Carboxylates √ X √√ Amidopropyl betaines *XX √√ Betaines &sultaines * √ X √√ Internal & alpha olefin sulfonates √√√ X * on sandstone

6. Difficult Brine Situations Low Salinity (0-1000 ppm TDS) Highly hydrophobic but still remains in the water phase before partitioning between oil and water. Long chain hydrophobe Low or no EO High Salinity (100,000 + ppm TDS) Highly hydrophilic and remains in the water phase before partitioning between the oil and water. Short chain hydrophobe Higher levels of EO

7. Difficult Brine Situations >1000 TDS>100,000 TDS HydrophobeLong ChainShort Chain Ethylene OxideLow or noneHigh ClassificationHydrophobicHydrophilic

8. Fatty acid derived CEOR surfactants

9. Design Concepts Extended chain surfactants employing polypropylene oxide (Witthayapanyanon, Acosta, Salager, and many others Guerbet type branched structures (Weerasoorlya, Aoudia, Wade, O’Lenick, et. al.) HLD Concept (Salager, Acosta, Hammond, et al.) Sulfonates for thermal stability Renewable resources wherever possible

10. Surfactants Based on Unsaturated Fatty Acids & Alcohols

12. Internal olefin ether sulfonates

13. Internal Olefin Ether Sulfonate Alcohol Ether Sulfonate IOS

14. Internal Olefin Ether Sulfonate Alcohol Ether Sulfonate IOS Guerbet Structure on the oil/water interface to minimize the adsorption

15. Internal Olefin Ether Sulfonate Alcohol Ether Sulfonate IOS Advantages Combine IOS and Alcohol ether sulfonate into one structure. Eliminate chromatographic separation High temperature stable High salinity tolerant Hydophobe can be easily altered based on the reservoir properties Save off-shore storage space Can be used for ASP or SP Green renewable resources raw material Low adsorption onto sandstone reservoir Can be manufactured as high active low viscosity 65-85 wt% liquids Guerbet Structure on the oil/water interface to minimize the adsorption

16. Thermal Stability 1100 MW Internal Olefin Ether Sulfonate Activity @ 90⁰C0.1% Surfactant in Sea Water

17. Why Blends of Surfactants are not Recommended? Internal Olefin Sulfonates (IOS) Alcohol Ether Sulfate Chromatography separation AdvantagesPotential Issues Provide good IFT, solubility, phase behavior in the lab testing Reservoir is like a huge GC column. Chromatographic separation due to differential product adsorption in the reservoir –The effectiveness of original composition designed in the lab is lost when propagating into reservoir SULFATES ARE UNSTABLE AT HIGHER TEMP AND IN PRESENCE OF Ca/Mg EXCEPT OVER A NARROW pH RANGE

18. Comparison of IOS and IOES INTERNAL OLEFIN SULFONATEINTERNAL OLEFIN ETHER SULFONATE x + y =14 x + y = 16-20 x + y = 14 derived from oleic x + y = 18 derived from erucic Petroleum basedGreen, Renewable resources Not electrolyte tolerantElectrolyte tolerant

19. Alkylaryl Ether Sulfonates

20. Ether Sulfonates from Unsaturated Fatty Alcohols

21. Ether Sulfonates from Phenols Sulfonation with SO3

22. Ether Sulfonates from Phenols Sulfonation with olefin sulfonic acid

23. Ether Sulfonates from Phenols Twin-Tailed Sulfonates Partially derived from renewable resources Thermally stable Electrolyte tolerant Low adsorption

24. Ether Amine Sulfonates

26. Potential Commercial Applications

27. CEORMiningLubricantOil FieldDetergentsOthers

28. Summary There exists an increasing demand for high volumes of surfactants to meet the unique requirements for CEOR. Several new surfactant types have been developed to provide large volumes of first intent surfactants that can tolerate high temperatures and high salinities. Surfactants for very low salinities are difficult to design because they require high molecular weights that still remain water soluble. Natural feedstocks can be used to wholly or partially replace petroleum feedstocks. Single surfactant systems are preferred over blends.

29. Thank You! The information contained in this presentation is to the best of our knowledge the most current and accurate. No warranties expressed or implied are made by Oil Chem Technologies, Inc. with respect to the information set forth herein.