OCT PRESENTATION - staging.files.cms.plus.com

Report
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.

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