Ultra-Low IFT Using Surfactants Dr. Jeffrey H. Harwell Ultra-Low IFT Using Surfactants Research Presentation By: Eric Henderson Ch E Junior

What are surfactants? Surfactant: SURFace ACTive AgeNT Adsorbs or accumulates at surfaces and interfaces or form structures to create new molecular surfaces1 Lipophobic – Fat fearing Lyophobic – solvent (water) hating Lipophilic – Fat loving Lyophilic – water loving

Micellization When concentrations are high enough, surfactant molecules will form micelles The concentration at which this occurs is specific to each surfactant and is called the Critical Micelle Concentration (CMC) More monomers until CMC, wherein there’s a constant monomer to micelle concentration. Low concentration of micelles, high for micelles

Surfactant Types Type I – Normal micelles are formed in water or aqueous solution. Brine (Salt Water) dissolved in oil Type II – Inverse micelles are formed in nonpolar solvent. Oil dissolved in brine Type III – Bilayer structure. Oil & Brine dissolved in middle phase Specific chemical process with pics Polar dissolves in polar Different types Nonpolar dissolves in nonpolar Why Type 3 is best Oil is hydrophobic Type II – Oil Soluble Type I – Water Soluble

Formation

For this experiment, only salt concentration was varied Control Increasing the temperature or salt concentration makes the spherical micelles less stable  Gravitating towards a planar bilayer formation (Type III) Decreasing the temperature or salt concentration makes the reverse micelles less stable  For this experiment, only salt concentration was varied

Surfactant Concentration The Fish Diagram Type IV Type I Type II Surfactant Concentration Type III Percent Salt

Other Terminology Emulsion – a mixture of two or more liquids that are normally immiscible (nonmixable or unblendable).2 Macroemulsion - kinetically stabilized mixtures of at least two immiscible liquids where one of the liquids has droplets with a diameter greater than 0.1 μm. Macroemulsions scatter light effectively and therefore appear milky, because their droplets are greater than a wavelength of light.3 Microemulsion - clear, thermodynamically stable, isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a cosurfactant.4

Oil-in-Water Microemulsion Winsor Type I Water-in-Oil Microemulsion Winsor Type II Can lead to larger sample final volume This swelling can lead to a larger final volume of the sample

Real-World Application Generation of fish diagrams for all crude mimics will provide non-site specific surfactant concentration estimates Method Step 2 Step 1 Step 3 Find successful water flooding site Perform chemical floods to maximize recovery Lab Testing

http://seca.doe.gov/newsroom/100yr/images/09-Chemical_Flooding_Micellar_Polymer_lg.jpg

Ultra-low IFT = Ultra-high solubilization = Ultra Money Bottom Line Microemulsion benefits: Ultra-low interfacial tension Maximum oil solubilization capacity Ultra-low IFT = Ultra-high solubilization = Ultra Money 82% of OK’s oil remains in oil wells

Other Applications Medical & Pharmaeutical Soaps & Detergents (Hygiene) Nanoparticle research Cosmetic industry Although the surfactants used were for oil and gas related, this type of work applies to many areas of research.

Although the surfactants used were for oil and gas related, this type of work applies to many areas of research. http://www.nanoparticles.org/pdf/Salager-E300A.pdf

Medical Applications Ultra-low IFT is desirable in many microbial compounds Biosurfactants: Similar emulsifying properties Used as anti-adhesive agents Antibacterial, antifungal, & antiviral Coatings for insertional medical tools Lung surfactants Used in a broad range of medical applications http://www.drugs.com/drug-class/lung-surfactants.html

http://jac.oxfordjournals.org/content/57/4/609/T1.expansion.html

Materials Salt Surfactants NaCl Cosmacol CaCl2 145-4S Mimic Crude Oils Dodecane Decane Octane Hexane Salt NaCl CaCl2 Crude oil – Liquid alkane hydrocarbons Sodium chloride Calcium chloride

Surfactants Cosmacol AES-70-3-24 AL Alfoterra® 145-4S 90

Cosmacol AES-70-3-24 AL5 Alcohol ether sulphate chemical structure6

Alfoterra® 145-4S 907 Weight percent: 82.2% Chemical structure8,9 Alfoterra 145-4S is a C14-15 branched alcohol sulfate, 4 mole propoxylate

Mimic Crude Oils - Liquid Alkane Hydrocarbons Salt Dodecane 12 carbon chain Decane 10 carbon chain Octane 8 carbon chain Hexane 6 carbon chain Calcium Chloride (CaCl2) Sodium Chloride (NaCl) CaCl2 99.8% to 10% in stock to varied in samples NaCl 76.2% to 20% in stock to varied in samples 𝐀𝐦𝐨𝐮𝐧𝐭 𝐭𝐨 𝐚𝐝𝐝=𝑻𝒐𝒕𝒂𝒍 𝑴𝒂𝒔𝒔 ∗ 𝒘𝒕 𝑷𝒆𝒓𝒄𝒆𝒏𝒕𝒂𝒈𝒆 𝒚𝒐𝒖 𝒘𝒂𝒏𝒕 𝒘𝒕 𝑷𝒆𝒓𝒄𝒆𝒏𝒕𝒂𝒈𝒆 𝒚𝒐𝒖 𝒂𝒓𝒆 𝒖𝒔𝒊𝒏𝒈

Procedure Perform calculations Make samples Do phase behavior Observe results Take pictures Use machine to get IFT’s

Results

Decane – 5% Surfactant Salt %: 6 8 10 12 14 16 18 20 Type 3’s are boxed in red Salt %: 6 8 10 12 14 16 18 20

Decane Salt %: 12 13 14 Surf %: 5 8

Decane with Sec-butanol Gelation broken Salt %: 14 20 Surf %: 5 Alcohol (Sec-butanol) %: 3

Decane – 0.5% Surfactant Salt %: 6 8 10 12 14 16 18 20

Decane – 0.5% Surfactant With Hexyl Glycoside With Naxan Salt %: 10 12 14 16

Dodecane – 0.5% Surfactant Salt %: 6 8 10 12 14 16 18 20

Dodecane – 0.5% Surfactant With Hexyl Glycoside With Naxan Salt %: 10 12 14 16

Octane – 0.5% Surfactant DIRTY CAPS! Salt %: 6 8 10 12 14 16 18 20

Octane – 0.5% Surfactant With Hexyl Glycoside With Naxan Salt %: 10 12 14 16

Hexane – 0.5% Surfactant Salt %: 6 8 10 12 14 16 18 20

Hexane – 0.5% Surfactant With Hexyl Glycoside With Naxan Salt %: 10 12 14 16

Summary 0.5% Surfactant 12.5 14 16 13 12 10 8 5% Surfactant Salt %   5% Surfactant 0.5% Surfactant Decane Decane w/ Sec-butanol Dodecane Dodecane w/ Hexyl Glycoside Dodecane w/ Naxan Decane w/ Hexyl Glycoside Decane w/ Naxan Octane Octane w/ Hexyl Glycoside Octane w/ Naxan Hexane Hexane w/ Hexyl Glycoside Hexane w/ Naxan Salt % 12.5 Unclear 14 16 13 12 10 8

IFT Didn’t get 14 to 20% salt drop diameters because bubble kept breaking into micro bubbles --- No reading Would expect similar trend to 0.5% surf graph Spinning_Drop_Tensiometer

Color control using sec-butanol and salt Light Scattering Miniemulsions Are generally blue-white Have a particle size intermediate between Macro and Micro emulsions Color control using sec-butanol and salt Blue Green Clear Yellow Sources of error Human Equipment A Red Object An object will appear red when it absorbs all wavelengths of visible light except for red.... red light is scattered to our eye, so the object looks red Error Did go back and re-do ill-trialed samples Inaccuracy of tools (pipettes and scales)

What I’ve learned What I hope to achieve Conclusion What I’ve learned What I hope to achieve

What I’ve learned What I hope to achieve Conclusion What I’ve learned What I hope to achieve

What I’ve learned What I hope to achieve Conclusion What I’ve learned What I hope to achieve

What I’ve learned What I hope to achieve Conclusion What I’ve learned What I hope to achieve

With a very special thank you to Ajay Raj and Kahnery Mai

References 1. Applied Surfactant Science and Technology. Norman: Surfactant Associates, 2014. Print. Short Course Lab Sessions 2. http://en.wikipedia.org/wiki/Emulsion 3. http://en.wikipedia.org/wiki/Macroemulsion 4. http://en.wikipedia.org/wiki/Microemulsion 5. http://www.sasoltechdata.com/MarketingBrochures/Surfactants.pdf 6. http://en.wikipedia.org/wiki/Sodium_laureth_sulfate 7. http://www.sasoltechdata.com/MSDS/ALFOTERRA145-4S90.pdf 8. https://drive.google.com/viewerng/viewer?url=patentimages.storage.googleapis.com/pdfs/US20080167445.pdf 9. http://sasolnorthamerica.com/Images/Interior/productsearchdocuments/eor%20bulletin%20sept%2025%202013.pdf 10. http://seca.doe.gov/newsroom/100yr/images/09-Chemical_Flooding_Micellar_Polymer_lg.jpg 11. http://vecto.rs/1024/vector-of-a-cartoon-black-and-white-outline-design-of-father-time-carrying-an-hourglass-outlined-coloring-page-by-ron-leishman-20120.jpg 12. http://www.graceinstrument.com/images/products/M6500_Spinning_Drop_Tensiometer_255w.jpg