Surfactants

Gary A. Pope Workshop on Heavy Oil Recovery May 23, 2005 The University of Texas at Austin

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Background on Surfactant EOR

Extensive research and development was done on surfactant EOR in the 60s, 70s and 80s including many field pilots By the mid 80s surfactants had been developed with high salinity tolerance and other characteristics far superior to the earlier products By the mid 90s surfactant structure could be tailored to the specific conditions needed The surfactant cost is on the order of $10 per incremental Bbl of oil The use of alkaline agents such as sodium carbonate with surfactants can reduce chemical costs to less than $5 per Bbl of incremental oil in some cases and this has been applied commercially on a limited scale, but is limited to certain reservoir conditions

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Background on Surfactant EOR

Many pilot tests done in the 1970s did not adequately recognize the importance of reservoir characterization and mobility control Oil recovery is usually very low without mobility control Under favorable conditions, either hydrolyzed polyacrylamide or xanthan gum polymers can be used for mobility control, but both have limitations Our capability to simulate surfactant flooding with UTCHEM has continued to improve and is vastly better than it was during the 1970s and 1980s The limitations of most surfactants is usually related to high viscosity emulsions or microemulsions and high retention The key to reducing both viscosity and surfactant retention is the same: surfactant structure with special emphasis on branched hydrophobes

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Examples of Alcohol Ether Sulfate Surfactants

C14 EO3-sulfate C14 EO3-sulfate (C4 branch at the #2 carbon)

(linear alcohol)

C14 PO3-sulfate
(C4 branch at the #2 carbon; propylene oxide instead of ethylene oxide)

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Custom Designed Surfactant

Hydrophobic Tail Hydrophilic Head

CH3(CH2)m O CHCH2 O CH2 CH O S O x Where m+n = Desirable hydrophobe tail O Na+

-

CH3(CH2)n

CH3

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Microemulsion phase behavior

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Microemulsion Viscosity
3.50 UTCHEM Model Measurement

Microemulsion Viscosity, cp

3.00 2.50 2.00 1.50 1.00 0.50 0.00 0.0

0.2

0.4

0.6

0.8

1.0

Oil Concentration in Microemulsion

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Examples of Commercial Surfactants for EOR

Stepan Alpha Olefin Sulfonates Alcohol Ether Sulfates Harcros Alcohol Ether Sulfates Sasol Alcohol Ether Sulfates Shell Chemical Internal Olefin Sulfonates Cytec Ester Sulfonate Oil Chem Alcohol Ether Sulfonates C14 C1618 C2024 C13 C1618 C12 C13 C12 C16 C15-C17 C12 C14

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Example of Current Surfactant/Solvent/Polymer Mixture for EOR of Light Oil in Dolomite Reservoir
Surfactant mixture C16-17Alcohol Propoxy Sulfate (APS) with 7 POs C20-24 Alpha Olefin Sulfonate (AOS) Secondary Butyl Alcohol (SBA) Hydrolyzed Polyacrylamide Polymer (HPAM)

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Phase Behavior Screening

An optimum formulation of APS/AOS/SBA with polymer Increasing Na+ Conc.

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Solubilization Ratios

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Summary
Phase behavior screening method allows rapid design of surfactant flood systems Oil recovery in both sandstone and dolomite cores about 90% Surfactant adsorption in dolomite core similar to sandstones

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Example of Successful Recovery of Viscous Fuel Oil at Pearl Harbor Site

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Background
High viscosity oil 1000-3000 cp Commercially-available surfactants gave very poor solubilization of the NSFO No published data on how to use surfactants for 1000 cp oils Complex hydrogeology

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Hydrogeology

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Viscosity of Fuel Oil

1000

Viscosity (cp)
100 10 100

Temperature (degrees Celsius)

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Approximate Structure of Sodium Alkyl Propoxylated Sulfate

C5H11 CHCH2 C5H11 O CH2 CH CH3 8 O

O S O O-Na+

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Sodium Alkyl Propoxylated Sulfates

Robust high-performance surfactants Low viscosity microemulsions High contaminant solubilizations High tolerance to calcium Favorable biodegradation properties

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Solubilization of Pearl Harbor Fuel Oil at 50C

450,000 400,000

Solubilization, mg/L

350,000 300,000 250,000 200,000 150,000 100,000 50,000 0 0 500 1000 1500 2000

Concentration of Calcium, mg/L

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Microemulsion Viscosity
5

Microemulsion Viscosity (cp)

4 Camp Lejeune DNAPL 4% C 14-C15(PO)4, 3 16% IPA, 0.2% CaCl 2

2 Pearl Harbor Fuel Oil 4% C 12-C13(PO)8, 8% SBA, 1% NaCl, 0.1% CaCl 2 0 0.0 0.2 0.4 0.6 0.8 1.0

NAPL Weight Fraction

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Effluent Samples Collected During Surfactant Flooding at Pearl Harbor

t ta n c fa ur S rt on Stajecti In nt a t fac ur S p on Stojecti In

Silty Clay

to

Day 1 first 12 hrs

Day 2

Days 3 - 12

Days 13-18

Fracd Fractured Tuff Tuff

Packer

Upper zone
NAPL

Silty Clay

Lower zone
Silty Sand

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Summary of Pearl Harbor Results

Phase behavior and viscosity measurements effective in identifying high-performance surfactants for recovery of highly viscous fuel oil Alkyl propoxylated surfactants found to be a robust and cost-effective class of surfactants Thermally enhanced SEAR tested in laboratory and field to remove1000 cp fuel oil Approximately 88% of viscous fuel oil removed from fractured tuff at Pearl Harbor

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Proposal
Enhancement of Mass Transfer in Heavy Oil Recovery Processes using Surfactants, Solvents, Alkali and Heat Custom design surfactant structures for heavy oil Explore novel recovery methods with surfactants Develop models of both microscopic and macroscopic phenomena as needed to understand and scale up mechanisms

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