Micellar recovery

Microemulsions became well known from about 1975 to 1980 because of their use ia "micellar-polymer" enhanced oil recovery (EOR) (35). This technology exploits the ultralow iaterfacial tensions that exist among top, microemulsion, and bottom phases to remove large amounts of petroleum from porous rocks, that would be unrecoverable by conventional technologies (36,37). Siace about 1990, iaterest ia the use of this property of microemulsions has shifted to the recovery of chloriaated compounds and other iadustrial solveats from shallow aquifers. The latter appHcatioa (15) is sometimes called surfactant-enhanced aquifer remediation (SEAR). 

Micellar/polymer (MP) chemical enhanced oil recovery systems have demonstrated the greatest potential of all of the recovery systems under study (170) and equivalent oil recovery for mahogany and first-intent petroleum sulfonates has been shown (171). Many somewhat different sulfonate, ie, slug, formulations, slug sizes (pore volumes), and recovery design systems were employed. Most of these field tests were deemed technically successful, but uneconomical based on prevailing oil market prices (172,173). 

Petroleum sulfonates are widely used as solubilizers, dispersants (qv), emulsifiers, and corrosion inhibitors (see Corrosion and corrosion inhibitors). More recentiy, they have emerged as the principal surfactant associated with expanding operations in enhanced oil recovery (66). Alkaline-earth salts of petroleum sulfonates are used in large volumes as additives in lubricating fluids for sludge dispersion, detergency, corrosion inhibition, and micellar solubilization of water. The chemistry and properties of petroleum sulfonates have been described (67,68). Principal U.S. manufacturers include Exxon and Shell, which produce natural petroleum sulfonates, and Pilot, which produces synthetics. 

E. A. Knaggs and J. W. Hodge, Petroleum Sulfonates—Key Process Chemicals in Micellar Polymer Oil Recovery Systems, American Chemical Society,... 

Optimizing the formulation of micellar surfactant solutions used for enhanced oil recovery consists of obtaining interfacial tensions as low as possible in multiphase systems, which can be achieved by mixing the injected solution with formation fluids. The solubilization of hydrocarbons by the micellar phases of such systems is linked directly to the interfacial efficiency of surfactants. Numerous research projects have shown that the amount of hydrocarbons solubilized by the surfactant is generally as great as the interfacial tension between the micellar phase and the hydrocarbons. The solubilization of crude oils depends strongly on their chemical composition [155]. 

Micellar flooding is a promising tertiary oil-recovery method, perhaps the only method that has been shown to be successful in the field for depleted light oil reservoirs. As a tertiary recovery method, the micellar flooding process has desirable features of several chemical methods (e.g., miscible-type displacement) and is less susceptible to some of the drawbacks of chemical methods, such as adsorption. It has been shown that a suitable preflush can considerably curtail the surfactant loss to the rock matrix. In addition, the use of multiple micellar solutions, selected on the basis of phase behavior, can increase oil recovery with respect to the amount of surfactant, in comparison with a single solution. Laboratory tests showed that oil recovery-to-slug volume ratios as high as 15 can be achieved [439]. 

The state of the art in chemical oil recovery has been reviewed [1732]. More than two thirds of the original oil remains unrecovered in an oil reservoir after primary and secondary recovery methods have been exhausted. Many chemically based oil-recovery methods have been proposed and tested in the laboratory and field. Indeed, chemical oil-recovery methods offer a real challenge in view of their success in the laboratory and lack of success in the field. The problem lies in the inadequacy of laboratory experiments and the limited knowledge of reservoir characteristics. Field test performances of polymer, alkaline, and micellar flooding methods have been examined for nearly 50 field tests. The oil-recovery performance of micellar floods is the highest, followed by polymer floods. Alkaline floods have been largely unsuccessful. The reasons underlying success or failure are examined in the literature [1732]. 

R. Daharu, S. Thomas, and Ali. S. M. Farouq. Micellar flooding for tertiary recovery Recent advances and potential. In Proceedings Volume, pages 414-428. 10th SPE Trinidad Tobago Sect Tech Conf (Port of Spain, Trinidad, 6/26-6/28), 1991. 

Product recovery from reversed micellar solutions can often be attained by simple backextraction, by contacting with an aqueous solution having salt concentration and pH that disfavors protein solubilization, but this is not always a reliable method. Addition of cosolvents such as ethyl acetate or alcohols can lead to a disruption of the micelles and expulsion of the protein species, but this may also lead to protein denaturation. These additives must be removed by distillation, e.g., to enable reconstitution of the micellar phase. Temperature increases can similarly lead to product release as a concentrated aqueous solution. Removal of the water from the reversed micelles by molecular sieves or silica gel has also been found to cause a precipitation of the protein from the organic phase. 

Recent research and field tests have focused on the use of relatively low concentrations or volumes of chemicals as additives to other oil recovery processes. Of particular interest is the use of surfactants as CO (184) and steam mobility control agents (foam). Also combinations of older EOR processes such as surfactant enhanced alkaline flooding and alkaline-surfactant-polymer flooding have been the subjects of recent interest. Older technologies polymer flooding (185,186) and micellar flooding (187-189) have been the subject of recent reviews. In 1988 84 commercial products polymers, surfactants, and other additives, were listed as being marketed by 19 companies for various enhanced oil recovery applications (190). 

The works of various investigators such as Gogarty and Tosch (1), Healy and Reed (2), and Davis and Jones (2), have shown that the micellar flooding process can be used effectively to mobilize residual oil in watered-out light oil reservoirs. Many field tests conducted in the U.S. have further proved its effectiveness. However, the economics of the process remain unattractive for implementing the process for tertiary oil recovery. 

Process efficiency, in this study, is defined as the tertiary oil recovery per unit volume of the slug injected. This refers to the efficiency of an oil-rich slug. Economic recovery efficiency varies from slug to slug due to variations in the surfactant content. it should be noted that the micellar slugs were formulated with an effort to keep the cost a minimum. 

Formulate efficient micellar slugs for the tertiary recovery of three light oils viz. Bradford crude, Bonnie Glen crude, and Provost crude ... 

Table III. Tertiary Recovery with Single Micellar Slugs...

Figure 7. Effect of Micellar Slug Size on the Oil Recovery Efficiency of Micellar Slug B4...

Micellar Slug Total Size, Slug % pv Tertiary Recovery. % oil in place... 

Oil recovery increases with an increase in micellar slug size. But the process efficiency drops and the surfactant loss increases. 

Gogarty, W.B. and Tosch, W.C. "Miscible-Type Waterflooding Oil Recovery with Micellar Solutions , J. Pet. Tech. (Dec. 1968) 1407-1415. 

Lee et al. [30] described a micellar electrokinetic capillary chromatographic method for the determination of some antiepileptics including valproic acid. They used a fused silica capillary column (72 cm x 50 pm) and SDS as the micellar phase and multiwavelength UV detection. Reaction conditions, such as pH and concentration of running buffer were optimized. Solutes were identified by characterizing the sample peak in terms of retention time and absorption spectra. Recoveries were 93-105%. 

Micellar flooding, 13 628 Micellar-polymer (MP) chemical enhanced oil recovery systems, 23 531 Micellar-polymer enhanced oil recovery (EOR), 16 429... 

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