Oil Chem TECHNOLOGIES Surfactants Bringing Chemical IOR TO THE NEXT GENERATION Synthesis and Application of High Molecular Weight Surfactants 104th AOCS Annual Meeting & Expo April 28 – May 1, 2013, Montreal Canada 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 Chemical EOR • ASP, SP, Low Surfactant Added Water Flood, Foam, etc. •Single surfactant component – no co-surfactant, no-co-solvent, no salinity optimization, etc. Injection fluid Injection Pump Producing well Oil Injection well Low IFT, Low adsorption Compatibility with the reservoir conditions and the other additives in the injection fluid Minimal phase trapping, Chromatographic separation 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 Limitations of Some CEOR Surfactants Temp Adsorption Electrolytes Ether Sulfates X √ √ Ether Sulfonates √√ √ √ Ether Carboxylates √ X √√ Amidopropyl betaines * X X √√ Betaines &sultaines * √ X √√ Internal & alpha olefin sulfonates √√ √ X * on sandstone 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 Difficult Brine Situations >1000 TDS >100,000 TDS Hydrophobe Long Chain Short Chain Ethylene Oxide Low or none High Classification Hydrophobic Hydrophilic Fatty acid derived CEOR surfactants 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 Surfactants Based on Unsaturated Fatty Acids & Alcohols CH3(CH2)aCH(CH2)bCOOM R R' CH3(CH2)xCH(CH2)ySO3M CH3(CH2)aCH(CH2)bCOO(P O)m(EO)nM R R' CH3(CH2)xCH(CH2)ySO3M CH3-(CH2)xCH=CH(CH 2)yCOOH Surfactants Based on Unsaturated Fatty Acids & Alcohols CH3(CH2)aCH(CH2)bCOO(P O)m(EO)nM CH3(CH2)aCH(CH2)bCOOM R R R' R' CH3(CH2)xCH(CH2)ySO3M CH3(CH2)xCH(CH2)ySO3M CH3-(CH2)xCH=CH(CH 2)yCOOH CH3-(CH2)xCH=CH(CH2)yCH2OH HO CH3(CH2)x(P O)y(EO)zCH 2CH2CH2SO 3Na SO 3Na CH3(CH2)aCH(CH2)bO-(P O)x(EO)nOH R R' CH3(CH2)xCH(CH2)ySO3M CH3(CH2)aCH(CH2)bO-(P O)x(EO)nCH 2COOM R R' CH3(CH2)xCH(CH2)ySO3M Internal olefin ether sulfonates Internal Olefin Ether Sulfonate OH CH3 CH3-(CH2)mCHCH(CH2)nCH2O(CH2CHO)y(CH2CH2O)xH SO 3Na IOS Alcohol Ether Sulfonate Internal Olefin Ether Sulfonate OH CH3 CH3-(CH2)mCHCH(CH2)nCH2O(CH2CHO)y(CH2CH2O)xH SO 3Na Alcohol Ether Sulfonate IOS CH2(P O)x(EO)yOH SO 3Na Guerbet Structure on the oil/water interface to minimize the adsorption Internal Olefin Ether Sulfonate OH CH3 CH3-(CH2)mCHCH(CH2)nCH2O(CH2CHO)y(CH2CH2O)xH SO 3Na Alcohol Ether Sulfonate IOS Advantages • Combine IOS and Alcohol ether sulfonate into one CH2(P O)x(EO)yOH SO 3Na Guerbet Structure on the oil/water interface to minimize the adsorption 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 Thermal Stability 1100 MW Internal Olefin Ether Sulfonate Activity @ 90⁰C 0.1% Surfactant in Sea Water 0.01 IFT, mN/m, 0.1 wt% 0.085 Active ,wt% 0.080 0.075 0.070 0.065 0.001 0.0001 0 20 40 60 80 Days at 90°C 100 0 20 40 60 80 Days at 90°C 100 Why Blends of Surfactants are not Recommended? SO 3Na CH3(CH2)xCHCH(CH2)yCH3 Internal Olefin Sulfonates (IOS) HO + SULFATES ARE UNSTABLE AT HIGHER TEMP AND IN PRESENCE OF Ca/Mg EXCEPT OVER A NARROW pH RANGE CH3(CH2)x(P O)y(EO)zCH 2SO 4Na Advantages Potential 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 Alcohol Ether Sulfate Chromatography separation Comparison of IOS and IOES INTERNAL OLEFIN SULFONATE INTERNAL OLEFIN ETHER SULFONATE CH3(CH 2)xCH(OH)CH(CH 2)yCH 3 CH3(CH 2)xCH(OH)CH(CH 2)yCH 2(PO) a(EO) bOH SO3Na SO3Na x + y =14 x + y = 14 derived from oleic x + y = 16-20 x + y = 18 derived from erucic Petroleum based Green , Renewable resources Not electrolyte tolerant Electrolyte tolerant Alkylaryl Ether Sulfonates Ether Sulfonates from Unsaturated Fatty Alcohols + CH3(CH2)cCH=CH(CH2)dO(P O)x(EO)yH CH3(CH2)aCH(CH2)bSO 3H NaOH CH3(CH2)cCH2CH(CH2)dO(P O)x(EO)yH CH3(CH2)aCH(CH2)bSO 3Na Ether Sulfonates from Phenols O(PO)x(EO)y SO 3Na O(PO)x(EO)yH + 2SO 3 SO 3Na 2NaOH R R Sulfonation with SO3 Sulfate Sulfonate Ether Sulfonates from Phenols O(PO)x(EO)yH O(PO)x(EO)yH + CH3(CH2)zCH=CH2SO 3H Sulfonate only NaOH R CH3(CH2)aCH(CH2)bSO 3Na R Sulfonation with olefin sulfonic acid Ether Sulfonates from Phenols O(P O)x(EO)yH H(EO)y(P O)xO + CH3(CH2)zCH=CH2SO 3H NaOH H(EO)y(P O)xO O(P O)x(EO)yH • CH3(CH2)mCH(CH2)nSO3Na • • • Twin-Tailed Sulfonates Partially derived from renewable resources Thermally stable Electrolyte tolerant Low adsorption Ether Amine Sulfonates Ether Amine Sulfonates H R-(PO)x(EO)yNH + NaOH + ClCH2CHOHCH2SO 3Na R-(PO)x(EO)yNH + H2O CH2CHOHCH2SO 3Na +CH3Cl NaOH R-(P O)x(EO)yNCH 3 CH2CHOHCH2SO 3Na + NaCl + NaCl Potential Commercial Applications Potential Commercial Applications CEOR Mining Lubricant Oil Field Detergents Others 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. 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.