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.