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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. Presentation Outline. Special requirements for CEOR surfactants - PowerPoint PPT Presentation
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Synthesis and Application of High Molecular Weight Surfactants
Oil Chem TECHNOLOGIES
Surfactants Bringing Chemical IOR TO THE NEXT
GENERATION
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
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
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)xCH=CH(CH2)yCOOH
CH3(CH2)aCH(CH2)bCOOM
CH3(CH2)xCH(CH2)ySO3M
R'R
CH3(CH2)aCH(CH2)bCOO(PO)m(EO)nM
CH3(CH2)xCH(CH2)ySO3M
R'R
Surfactants Based on Unsaturated Fatty Acids & Alcohols
CH3-(CH2)xCH=CH(CH2)yCOOH
CH3(CH2)aCH(CH2)bO-(PO)x(EO)nCH2COOM
R R'
CH3(CH2)xCH(CH2)ySO3M
HO
SO3Na
CH3(CH2)aCH(CH2)bCOOM
CH3(CH2)xCH(CH2)ySO3M
R'R
CH3(CH2)x(PO)y(EO)zCH2CH2CH2SO3Na
CH3-(CH2)xCH=CH(CH2)yCH2OH
CH3(CH2)aCH(CH2)bCOO(PO)m(EO)nM
CH3(CH2)xCH(CH2)ySO3M
R'R
CH3(CH2)aCH(CH2)bO-(PO)x(EO)nOH
R R'
CH3(CH2)xCH(CH2)ySO3M
Internal olefin ether sulfonates
Internal Olefin Ether Sulfonate
CH3-(CH2)mCHCH(CH2)nCH2O(CH2CHO)y(CH2CH2O)xH
SO3Na
CH3OH
Alcohol Ether SulfonateIOS
Internal Olefin Ether Sulfonate
CH3-(CH2)mCHCH(CH2)nCH2O(CH2CHO)y(CH2CH2O)xH
SO3Na
CH3OH
Alcohol Ether SulfonateIOS
CH2(PO)x(EO)yOHSO3Na
Guerbet Structure on the oil/water interface to minimize the adsorption
Internal Olefin Ether Sulfonate
CH3-(CH2)mCHCH(CH2)nCH2O(CH2CHO)y(CH2CH2O)xH
SO3Na
CH3OH
Alcohol Ether SulfonateIOS
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
CH2(PO)x(EO)yOHSO3Na
Guerbet Structure on the oil/water interface to minimize the adsorption
Thermal Stability 1100 MW Internal Olefin Ether Sulfonate
Activity @ 90⁰C 0.1% Surfactant in Sea Water
0 20 40 60 80 1000.0001
0.001
0.01
Days at 90°CIF
T, m
N/m
, 0.1
wt%
0 20 40 60 80 1000.065
0.070
0.075
0.080
0.085
Days at 90°C
Act
ive
,wt%
Why Blends of Surfactants are not Recommended?
CH3(CH2)x(PO)y(EO)zCH2SO4Na
+
CH3(CH2)xCHCH(CH2)yCH3
SO3Na
HO
Internal Olefin Sulfonates (IOS)
Alcohol Ether Sulfate
Chromatography separation
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
SULFATES ARE UNSTABLE AT HIGHER TEMPAND IN PRESENCE OF Ca/Mg EXCEPT OVERA NARROW pH RANGE
Comparison of IOS and IOES
INTERNAL OLEFIN SULFONATE INTERNAL OLEFIN ETHER SULFONATE
x + y =14
x + y = 16-20
x + y = 14 derived from oleic
x + y = 18 derived from erucic
Petroleum based Green , Renewable resources
Not electrolyte tolerant Electrolyte tolerant
CH3(CH2)xCH(OH)CH(CH2)yCH3
SO3NaCH3(CH2)xCH(OH)CH(CH2)yCH2(PO)a(EO)bOH
SO3Na
Alkylaryl Ether Sulfonates
Ether Sulfonates from Unsaturated Fatty Alcohols
CH3(CH2)aCH(CH2)bSO3H
CH3(CH2)cCH=CH(CH2)dO(PO)x(EO)yH+
NaOH
CH3(CH2)aCH(CH2)bSO3Na
CH3(CH2)cCH2CH(CH2)dO(PO)x(EO)yH
Ether Sulfonates from Phenols
Sulfonation with SO3
R
O(PO)x(EO)yH
2SO3
R
O(PO)x(EO)y SO3Na
SO3Na+
2NaOH
Sulfate
Sulfonate
Ether Sulfonates from Phenols
Sulfonation with olefin sulfonic acid
O(PO)x(EO)yH
+ CH3(CH2)zCH=CH2SO3HNaOH
O(PO)x(EO)yH
CH3(CH2)aCH(CH2)bSO3Na
Sulfonate only
R
R
Ether Sulfonates from Phenols
+
O(PO)x(EO)yHH(EO)y(PO)xOCH3(CH2)zCH=CH2SO3H
O(PO)x(EO)yHH(EO)y(PO)xO
NaOH
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
R-(PO)x(EO)yNH ClCH2CHOHCH2SO3Na+
NaCl+
NaOH+
R-(PO)x(EO)yNH
CH2CHOHCH2SO3Na
H
+ H2O
R-(PO)x(EO)yNCH3
CH2CHOHCH2SO3Na
+CH3Cl NaOH
+ 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.