Surfactants in situ

Monomers and prepolymers that are useful to form shellwalls were reacted with interface modifying molecules to create novel surfactants in-situ leading to stable emulsions [23], The reactions are designed to create polymers with surfactant properties rather than encapsulating shellwalls at the OAV interface. The emulsions were formed without conventional emulsifiers, and were shown to have long term stability without creaming. Absence of classical emulsifiers reduces the tendency toward foaming. 

Recently we have carried out laboratory tests (17, 18, 19) in which the sodium silicate was added directly to a dilute surfactant solution to recover oil. Such a process would be akin to alkaline flooding processes where a dilute surfactant is formed in-situ. In this case however the crude is lighter and does not contain the natural acids necessary to form surfactants in-situ. Therefore surfactant is injected and protected or enhanced by the sodium silicate such that a low tension waterflood is assured. Such a system is less complex and therefore more widely applicable than micellar/polymer techniques thus filling the void between the alkaline and micellar/polymer EOR processes. 

Amott method, to be preferentially oil-wet, RDI= —0.82. Laboratory work was undertaken to determine the feasibility of injecting alkaline solutions to improve oil recovery. These experiments were designed to produce surfactants in-situ. The surfactants would both lower the interfacial tension and react with the reservoir rock surface to modify the wettability of the porous media. The experimental work considered the injection of seawater and sodium hydroxide mixtures into cores. The experimental results show that the oil recovery was higher than 50% when the alkaline solution was injected. The conclusion was that surfactant produced by alkaline injection altered the rock wettability from oil-wet to intermediate-wet, increasing oU recovery. One precaution with alkaline flooding is that the range of reactions and the change in pH can cause unexpected variation in oil recovery if the reservoir and fluids are not well characterized. 

The third generation are latices made with independentiy prepared surfactant to mimic the in situ prepared functional monomer surfactant. These emulsifiers are often A—B block polymers where A is compatible with the polymer and B with the aqueous phase. In this way surface adsorption of the surfactant is more likely. These emulsions are known to exhibit excellent properties. 

Microbial-enhanced oil recovery involves injection of carefully chosen microbes. Subsequent injection of a nutrient is sometimes employed to promote bacterial growth. Molasses is the nutrient of choice owing to its low (ca 100/t) cost. The main nutrient source for the microbes is often the cmde oil in the reservoir. A rapidly growing microbe population can reduce the permeabiHty of thief zones improving volumetric sweep efficiency. Microbes, particularly species of Clostridium and Bacillus, have also been used to produce surfactants, alcohols, solvents, and gases in situ (270). These chemicals improve waterflood oil displacement efficiency (see also Bioremediation (Supplement)). 

Additions of halogen fluorides to the more electrophilic perfluonnated olefins generally require different conditions Reactions of iodine fluoride, generated in situ from iodine and iodine pentafluoride [62 102 103, /05] or iodine, hydrogen fluoride, and parapeiiodic aud [104], with fluormated olefins (equations 8-10) are especially well studied because the perfluoroalkyl iodide products are useful precursors of surfactants and other fluorochemicals Somewhat higher temperatures are required compared with reactions with hydrocarbon olefins Additions of bromine fluoride, from bromine and bromine trifluonde, to perfluonnated olefins are also known [lOti]... 

Various initiation strategies and surfactant/cosurfactant systems have been used. Early work involved in situ alkoxyamine formation with either oil soluble (BPO) or water soluble initiators (persulfate) and traditional surfactant and hydrophobic cosurfactants. Later work established that preformed polymer could perform the role of the cosurfactant and surfactant-free systems with persulfate initiation were also developed, l90 222,2i3 Oil soluble (PS capped with TEMPO,221 111,224 PBA capped with 89) and water soluble alkoxyamines (110, sodium salt""4) have also been used as initiators. Addition of ascorbic acid, which reduces the nitroxide which exits the particles to the corresponding hydroxylamine, gave enhanced rates and improved conversions in miniemulsion polymerization with TEMPO.225 Ascorbic acid is localized in the aqueous phase by solubility. 

By performing in situ the polymerization of acrylamide in water/AOT/toluene microemulsions, clear and stable inverse latexes of water-swollen polyacrylamide particles stabilized by AOT and dispersed in toluene have been found [192-194], It was shown that the final dispersions consist of two species of particles in equilibrium, surfactant-coated polymer particles (size about 400 A) with narrow size distribution and small AOT micelles (size about 30 A). 

Finally, Jessop and coworkers describe an organometalhc approach to prepare in situ rhodium nanoparticles [78]. The stabilizing agent is the surfactant tetrabutylammonium hydrogen sulfate. The hydrogenation of anisole, phenol, p-xylene and ethylbenzoate is performed under biphasic aqueous/supercritical ethane medium at 36 °C and 10 bar H2. The catalytic system is poorly characterized. The authors report the influence of the solubility of the substrates on the catalytic activity, p-xylene was selectively converted to czs-l,4-dimethylcyclohexane (53% versus 26% trans) and 100 TTO are obtained in 62 h for the complete hydrogenation of phenol, which is very soluble in water. 

OS 31] ]R 4] ]P 23] Under electroosmotic flow conditions, the reactant benzene was mobilized as a microemulsion using sodium dodecyl sulfate (SDS) as surfactant [103] (see also [14]). The nitronium ions, generated in situ from sulfuric and nitric acid, were moved by electrophoretic forces. By this means, a 65% yield of a nitrobenzene was obtained consecutive nitration products such as 1,3-dinitrobenzene (8% yield) and 1,3,5-trinitrobenzene (5% yield) were also produced. 

An extraordinary way of stabilizing RUO2-coated CdS colloids for H2 generation was chosen by Fendler and co-workers The colloidal particles were generated in situ in surfactant vesicles of dioctadecyldimethylammonium chloride and dihexa-decyl phosphate. Thiophenol as a membrane permeable electron donor acted as a sacrificial additive. Later, a surface active re-usable electron donor (n-C,gH3,)2N — (CHj)—CH2—CHj—SH, Br was incorporated into the vesicles. Its R—SS—R oxidation product could be chemically reduced by NaBH to regenerate the active electron donor. The H2 yields in these systems were only 0.5 %. However, yields up to 10% were later reported for a system in which CdS was incorporated into a polymerizable styrene moiety, (n-C,jH3jC02(CH2)2) N (CH3) (CH2CgH4CH=CH2>, CP, and benzyl alcohol was used as the electron donor. 

Waste gas from produced hydrocarbons can be safely disposed by reinjecting into a formation. The waste gas is mixed with a surfactant to form a foam that, in turn, is placed within a disposal zone of a subterranean formation. The waste gas is trapped within the foam, thereby reducing the mobility of the gas in the formation, which, in turn, restricts the ability of the waste gas to readily flow out of the disposal zone and into the producing zone of the formation. The waste gas foam can be placed into the formation by coinjecting the surfactant and the waste gas, or it can be formed in situ by first injecting the surfactant and then injecting the waste gas [1356]. 

Various bacterial species have proven useful in MEOR. The principle is based on the species biochemical byproducts produced, such as gases, surfactants, solvents, acids, swelling agents, and cosurfactants, which facilitate the displacement of oil. In field experiments, in situ fermentation is often desirable for producing a great quantity of gases. Clostridium hydrosulfuricum 39E was found to have surface-active properties during simulated enhanced oil recovery experiments [1874]. 

B. Bubela. In situ biological production of surfactants for enhanced oil recovery. Australia Dep Resources Energy End of Grant Rep 151, March 1983. 

D. T. Wason. Enhanced oil recovery through in-situ generated surfactants augmented by chemical injection. US DOE Rep DOE/BC/10847-20, Inst Gas Technol, Chicago, IL, August 1990. 

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